CN107683295A - Porous propylene polymer - Google Patents

Porous propylene polymer Download PDF

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Publication number
CN107683295A
CN107683295A CN201680032425.8A CN201680032425A CN107683295A CN 107683295 A CN107683295 A CN 107683295A CN 201680032425 A CN201680032425 A CN 201680032425A CN 107683295 A CN107683295 A CN 107683295A
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less
propylene
bigger
catalyst
acrylic polymers
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Inventor
M·W·赫尔特卡姆
G·S·戴
J·杨
罗鲁斌
S·D·布朗
R·A·胡勒
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

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  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to high porosity (>=15%) and/or low bore dia (PD<165 μm) acrylic polymers and the propene polymerizing method using the single site catalysts system with carrier, the carrier has high surface area (SA >=400m2/ g), low pore volume (PV≤2mL/g), specific average pore diameter scope (PD=1 20nm) and high particle mean size (PS >=30 μm).

Description

Porous propylene polymer
Inventor：Matthew W.Holtcamp,Gregory S.Day,Jian Yang,Lubin Luo,Steven D.Brown and Rohan A.Hule
Priority
The EP applications that 16, USSN62/171581 and 2015 on the July that application claims are submitted on June 5th, 2015 submits 15177118.5 priority and rights and interests.
Invention field
The present invention relates to porous propylene polymer and its preparation and application.
Background of invention
Recently, have been carried out making great efforts to use metallocene newly developed (MCN) catalysis technique to prepare heterophasic copolymer The benefit that (such as impact copolymer (ICP)) is provided with catalyst as utilization.With such " single active center " catalyst The homopolymer of preparation often has a narrow molecular weight distribution (MWD), low extractable, and various other associated favourable Performance, and copolymer often also there is narrow composition to be distributed.
Unfortunately, the conventional MCN being fixed on the conventional carrier coated with activator (such as MAO (MAO)) is not Copolymer component with sufficiently high molecular weight and/or rubber load capacity can be provided under the conditions of business correlation technique.With it The homologue of Z-N (ZN) system catalysis compare, there is low hole using the MCN ICP iPP matrix prepared Rate, and the sufficiently high rubber content in toughness and iPP matrix needed for impact resistance can not be kept.In addition, MCN-ICP has There is such MWD, its is narrow and can not obtain the enough crystallizations, low-molecular weight polymer needed for rigidity.Outside the matrix Separation phase in the formation of rubber be undesirable, such as it can cause serious reaction fouling.
Pore structure in conventional iPP (no matter coming from ZN or MCN systems) is understood to be by low point of polymer Caused by the rapid crystallization of son amount part comes, it causes volume contraction in crystallization process.Nello Pasquini (editor), Polypropylene Handbook, second edition, 78-89 pages of Hanser Publishers, Munich, the (2005) are reported pair In limited rubber load capacity, volume contraction process only generates low porosity, such as comes from conventional ZN caltalysts 7% porosity of system, and by handling MgCl2The ZN systems of load obtain more than 16% porosity by controlled dealcoholysis, This allows for iPP matrix to be filled with the rubber content close to 25wt%.Cecchin, G. et al., Macromol.Chem.Phys., volume 202, page 1987 (2001) report the titanium tetrachloride based on magnesium chloride-load (MgCl2/TiCl4) the titanium miniplate of catalyst system the form of polymer pellets is had an impact.However, reactor is obtained from, it is single Such ICP of catalyst system rubber content is still significantly lower than what can be realized in blend polymer ICP 40wt% rubber contents, it provides the flexibility of sometimes desired rubber content.
Accordingly, it is difficult to what is grasped is to balance a kind of catalyst, sequential polymerization ICP toughness and rigidity, because on the one hand, it is tough Property needed for the formation of high porosity and high filled rubber load capacity need to exist the hydrogen of high concentration and shunk to form rapid crystallization Required low-molecular weight polymer, and on the other hand, be used to make it that maximumlly polymerization detracts porosity under these conditions The ICP formed rigidity.
By using the second component of ethylene/butylene (or high alpha-olefin) copolymer, (it uses hafnocene to US5990242 It is prepared by type MCN), rather than propylene copolymer, to solve this problem.Such hafnium MCN is generally used for producing of a relatively high The polymer of molecular weight；However, the zirconocene of their activity typically well below more often.Anyway, second component Molecular weight and inherent viscosity are desired less than good impact strength.
WO2004/092225 discloses MCN polymerization catalysts, and it is carried on 10-50 μm of granularity (PS), 200- 800m2On the silica of/g surface areas and 0.9-2.1mL/g pore volumes, and show with 97 μm of PS, 643m2/ g surfaces The embodiment (page 12, Table I, carrier E (MS3060)) of the silica of product and 3.2mL/g pore volumes is used to obtaining iPP (the 18-19 pages, Table V and VI, operation is 21).
EP1380598 discloses some MCN catalyst, and it is carried on 2-12 μm of PS, 600-850m2/ g surface areas On the silica of 0.1-0.8mL/g pore volumes, and show with 6.9 μm of PS, 779m2/ g surface areas and 0.23mL/ The embodiment (page 25, table 3, embodiment 16) of the silica of g pore volumes obtains polyethylene.
EP1541598 discloses some MCN catalyst, and it is carried on 2-20 μm of granularity, 350-850m2/ g surface areas With (the 15-35 rows of page 4) on the silica of 0.1-0.8mL/g pore volumes, and show with 10.5 μm of granularities, 648m2The embodiment (referring to page 17, embodiment 12) of the silica of/g surface areas and 0.51mL/g pore volumes, to be used for second Alkene polymerize.
EP1205493 describes 1126m2/ g specific surface areas (SA) and 0.8cc/g structural porous volume (only aperture) two Silica support, it is used for ethylene copolymer (embodiment 1,6 and 7) together with MCN catalyst.
JP2003073414 describes 1-200 μm of granularity (PS), 500m2/ g or bigger SA and 0.2-4.0mL/g hole bodies Product (PV) silica, but the embodiment of the propylene polymerization using some MCN is showing, the granularity of wherein silica is 12 μm-20μm。
JP2012214709 describes 1.0-4.0 μm of PS, 260-1000m2/ g SA and 0.5-1.4mL/g PV titanium dioxides Silicon, it is used for polypropylene.
Other bibliography interested include US2011/0034649；US2011/0081817；Madri Smit et al., Journal of Polymer Science：Part A：Polymer Chemistry, volume 43, page 2734-2748 (2005)；" Microspherical Silica Supports with High Pore Volume for Metallocene Catalysts ", Ron Shinamoto and Thomas J.Pullukat, in " Metallocenes Europe ' 97Dusseldorf, Germany, are proposed 8-9 days in April, 1997.
Therefore, it is necessary to which new catalyst and/or method, it produces the polypropylene material met for application-specific demand, For example following one or more of the demand：Porosity, rigidity and the good balance of toughness, and/or needed for high impact Other performances；Such homopolymer and copolymer, it has narrow MWD, and low extractable, bimodal MWD, bimodal PSD are narrow Composition distribution, and/or other benefits of the homopolymer of MCN catalysis and copolymer；High porosity acrylic polymers；It is poly- with second The heterophasic copolymer of polymer component high filling load capacity in first polymer component；In single catalyst, sequential polymerization processes Prepare bimodal MWD or PSD heterophasic copolymers；Use commercial size method and condition economical production；And combinations thereof.
Summary of the invention
In some embodiments of the present invention, it is proposed that porous polypropylene and propene polymerizing method, this method can give birth to New acrylic polymers is produced, it has the benefit for the polymer that metallocene (MCN) is catalyzed, and high impact or using institute Other desired performances.Importantly, these polymer can use commercial-scale method and condition economically to produce.
On the one hand, embodiment of the present invention is related to acrylic polymers, and it is included：At least 50mol% propylene；1% just It is at least 1000MPa to cut flexural modulus (1%SFM), and it is determined according to ASTM D790 (A, 1.0mm/min)；More than 5 to Less than 200 area defects/10000 propylene units, it is to pass through13C NMR measure；If there is comonomer, then group Into Distribution Breadth Index (CDBI) it is 50% or bigger；And matrix, its include porosity be about 15% or it is bigger and in For value PD between more than 6 μm and less than 160 μm, it is determined by mercury injection method.In some embodiments of the present invention, should Acrylic polymers includes multimodal PSD, multimodal MWD, the heterophasic copolymer comprising filling phase or its combination.
On the other hand, embodiment of the present invention is related to the method for polypropylene, and it includes：(a) propylene monomer is existed Contacted under polymerizing condition with catalyst system, the catalyst system includes single site catalysts precursor compound, activator And carrier, the particle mean size (PS) of the carrier are more than 30 μm, are greater than 50 μm and/or at most 200 μm, specific surface area (SA) is 400m2/ g is bigger, such as 400-1000m2/ g (such as 400-650m2/ g or 650-1000m2/ g), pore volume (PV) is 0.5-2mL/g, such as 0.5-1.5mL/g, and average PD is 1-20nm, such as 1-7nm or 7-20nm；Form propylene (b) Polymer substrate, it includes at least 50mol% propylene, and porosity is 15% or bigger, such as 30-85%, and it is logical Cross mercury injection method measure.In some embodiments of the present invention, the carrier in (a) includes the agglomerate of multiple primary granules, And/or the intermediate value PD of the propylene polymer matrix formed in (b) is less than 165 μm, is, for example, less than 160 μm, it is to pass through mercury injection method Measure.
Accompanying drawing briefly describes
Fig. 1 is showing the electron micrograph of the D 150-60A silica of the primary granule comprising agglomeration.
Fig. 2 is showing the electron micrograph of the silica of PD 13054 of the primary granule comprising agglomeration.
Fig. 3 is showing the electron micrograph of the contrast silica of MS 3050.
Fig. 4 is showing the increment intrusion (mL/g) for the PiPP4 that the MCN produced according to embodiment 3 is catalyzed to aperture diameter The diagram of (μm).
Fig. 5 is showing the increment intrusion (mL/g) for the CiPP2 that the contrast MCN produced according to embodiment 3 is catalyzed to aperture The diagram of diameter (μm).
The increment that Fig. 6 is showing the CiPP3 of the contrast ziegler-natta catalyzed produced according to embodiment 3 invades (mL/ G) to the diagram of aperture diameter (μm).
Fig. 7 is showing the common granularity of CiPP6 particles using the Catalyst Production being carried on contrast silica It is distributed the diagram of (PSD), it is shown that come from the PSD of the heat treatment catalyst carrying method according to embodiment 6.
Fig. 8 is showing according to embodiment 6, and using the catalyst of load, (it is prepared by low temperature controlled method suppresses to carry Body fragmentation) production PiPP12 particles PSD diagram.
Fig. 9 is showing according to embodiment 6, and using the catalyst of load, (it is by heat-treated under medium temperature preparation come control section Fragmentation) production PiPP13 particles PSD diagram.
Figure 10 is showing according to embodiment 6, and using the catalyst of load, (it promotes carrier by high-temperature process preparation Fragmentation) production PiPP14 particles PSD diagram.
Figure 11 is according to the figure of the heterophasic copolymer ICP1 of embodiment 7 4D gel permeation chromatographies (GPC-4D), the ICP1 With about 40% ethylene-propylene rubber being loaded into porous iPP matrix.
Definition
For the present invention and its purpose of appended claims, Chemical and Engineering have been used News, 63 (5), the new numbering scheme for periodic table race described in page 27 (1985).
For this paper purpose, " average " refers to statistical average or average value, i.e. a series of observations or statistics Observation number in sum divided by the series, and term is average and average value is used interchangeably；" intermediate value " refer to The median of a series of observed values or statistics cumulative or that gradually drop sequential arrangement, i.e. if observed number is odd number, be Median, or be then the arithmetic average of two medians if observed number is even number.
For this paper purpose, most probable value (mode), also referred to as peak value or maximum, refer in a series of sights Examine the value or project of most frequent appearance in either statistics, i.e. flex point.Flex point is the quadratic derivative symbols change of curve Point.For this paper purpose, multi-modal is the distribution with two or more peak value, i.e. has multiple parts most The distribution being worth greatly；Bimodal distribution has two flex points；There is a peak or flex point with Unimodal Distribution.
For this paper purpose, granularity (PS) or diameter and its distribution are to use to be obtained from England by laser diffraction The Malvern Instruments, Ltd. of Wu Site prefectures MASTERSIZER3000 (1-3500 μm of scope) measure.It is average PS refers to distribution of the particle volume on granularity.Unless otherwise expressly provided or context state otherwise, otherwise " Grain " refers to whole granule either assembly such as aggregation (aggregate), agglomerate (agglomerate) or bag In " primary granule " or aggregation in the agglomerate of envelope, rather than the subelement of the body or part, such as agglomerate " basic granules ".
For this paper purpose, surface area (SA, also referred to as specific surface area or BET surfaces of catalyst carrier material Product), pore volume (PV) and average or average value bore dia (PD) they are by Brunauer-Emmett-Teller (BET) sides Method, use nitrogen adsorption-desorption (liquid nitrogen temperature：77K), with the instruments of MICROMERITICS TRISTAR II 3020, by powder What end determined after being deaerated 4 hours at 350 DEG C.Can be for example in " Characterization of on the more information of this method Porous Solids and Powders：Surface Area, Pore Size and Density ", S.Lowell et al., Springer, find in 2004.PV refers to total PV, including both inside and outside PV.Average PD refer to total PV relative to PD distribution.
For this paper purpose, the porosity of polymer beads refers to including the skeleton or matrix of acrylic polymers The particle either PV volume fractions or percentage in body, based on the particle or the overall volume of body relative to cumulative volume.It is poly- The porosity and intermediate value PD of polymer beads are determined using mercury injection method.Mercury injection method includes sample being placed in penetrameter neutralization mercury Surround the sample.Mercury is the non-additive fluid of most of material, and keeps out into space, only can just enter when the pressure is exerted Enter in space.Pressure during mercury access aperture is inversely proportional with the size of the opening to space.When mercury is driven into sample material During hole in material, it run out of capillary column (stem) memory being connected on specimen cup.After each pressure change, exhaust Incremental volumes be that change by measuring column capacity determines.The intrusion volume records together with corresponding pressure. Unless otherwise defined, whole mercury injection method data be using MICROMERITICS ANALYTICAL SERVICES and/or AUTOPORE IV9500 mercury porosimeters obtain.
The skeleton of the discrete phase of honeycombed grain material (wherein forming hole) is included in the intraskeletal non-polymer and/or nothing Machine includes material, such as caltalyst based material, and it includes carrier material, active catalyst system particle, and catalyst system is residual Stay composition granule or its combination.As used herein, " cumulative volume " of matrix is referred to occupied by the particle comprising the discrete phase Volume, i.e. not including the clearance space between particle, but including the inside pore volume or internal porosity in particle. " interior " either " inside " hole surface or volume refer to hole surface and/or the volume limited by particle inner surface, and it is not Particle that can be similar with other contacts, and this is with outer surface on the contrary, it is the surface that can contact another like particle.
In the case where the acrylic polymers is completely or partially filling, such as containing filled rubber or non-third In the case of the hole of the packing material of alkene polymer, porosity is also referred to as the particle or internal void space or hole Fraction, whether fill or be not filled by but regardless of the void space or hole, i.e. the porosity of the particle or body is to pass through bag The volume of packing material is included as void space to calculate, as the packing material is not present.
For this paper purpose, " being determined by mercury injection method " should also include and comprising " as surveyed by mercury injection method It is fixed ", such as example in the case where that can not use mercury injection method technology, such as hole is filled out by non-gaseous material (such as filling phase) wherein Situation about filling.In this case, mercury injection method can be used on such material sample, and it is before hole is filled with material Obtain will either carrying out obtaining before another procedure of processing (which prevent use mercury injection method) or for such material Expect on sample, its be with preparing preparing under the same conditions used in the method for the material, until such time point, That is, before will filling before the hole or will carrying out another procedure of processing (which prevent using mercury injection method).
As used herein, term " agglomerate " refers to such material, first comprising being kept together by adhesion The assembly of grade particles, i.e. weak Physical interaction is characterised by, to allow the particle by mechanical force come easily Separation, such as particle are mainly combined together at turning or edge.Term " primary granule " refer to it is minimum in agglomerate, The single particulate units (not rupturing) disintegrated, and can be the agglomerate of encapsulating, aggregation or monolith particles successively.It is attached Aggressiveness is generally characterised in that, with such SA, it is not significantly different from the SA for forming its primary granule.Silica Agglomerate is for example to be commercialized manufacture by spray drying process.
Fig. 1-2 shows the example of the agglomerate 10 of encapsulating, and it is as visible in partly open particle, comprising multiple first Grade particles 12.Fig. 1 shows the electron micrograph of D 150-60A silica, and it shows as integral spherical particle or thin Grain 10, its as visible in partly open particle, actually outer spherical shell or aggregate surface 14 (its partly or Person encloses the agglomerate completely) in the agglomerate comprising multiple minor structures or primary granule 12.Equally, Fig. 2 is PD 13054 electron micrograph, which show internal agglomerate 10, and it includes about 5-50 μm primary granule and encapsulating aggregation 14.Shown example is merely illustrative purpose, and the size of shown particle can not represent statistically larger sample；It is this Or most of primary granule in other commercially available silica can be more than or less than shown image, be, for example, 2 μm or smaller, this depends on the specific silica production method used in manufacturer.
" aggregation " is the assembly of the basic granules of the crystalline texture of share common, such as passes through sintering or other things Reason-chemical method (such as when particle syntrophism).Aggregation is typically that machinery is non-breakable, and the ratio table of aggregation Area is significantly less than the specific surface area of corresponding basic granules." basic granules " refers to individual particle or particulate, wherein Or aggregation is assembled by it.For example, the primary granule in agglomerate can be basic granules or basic granules Aggregation.On agglomerate and the more information of aggregation, referring to Walter, D., Primary Particles- Agglomerates-Aggregates, Nanomaterials (editor Deutsche Forschungsgemeinschaft), Wiley-VCH Verlag GmbH＆Co.KGaA, Weinheim, Germany, doi：10.1002/9783527673919 1-24 Page (2013).
Term " material all in one piece " or " material all in one piece " refer to the material formed by monolithic (single mass) material, and wrap Aggregation and large volume material are included, without the geometry or acinose texture of any restriction.Fig. 3 shows comparison vehicle MS 3050, it includes integral spherical particle 20, and assemble completely or material all in one piece core 22, lack the agglomeration of Fig. 1-2 carriers Primary granule and interior pore morphology.
Either " encapsulating " or " micro- encapsulating " is used interchangeably herein term " capsule ", to represent 1-1000 μm The agglomerate of size, comprising outer surface, it is coating or otherwise has Physical barriers, and it suppresses primary granule From disintegrating for the inside of the agglomerate of micro- encapsulating.The barrier layer or coating can be aggregations, such as primary and/or basic The aggregation of grain, it with agglomerate identical material by forming.Fig. 1-2 shows the example of the agglomerate 10 of micro- encapsulating, its Outer aggregate surface either includes multiple primary granules 12 in shell 14 (it partly or entirely encapsulates the agglomerate), at it Middle primary granule can allow, by rupture, to destroy, and dissolving, chemical degradation or otherwise remove all or part Shell 14 disintegrate.
Unbodied in spray drying, in the case that hydration surface silica dioxide is as an example, agglomerate 10 is logical The overall dimensions scope that can often have is 1-300 μm (such as 30-200 μm), and the size range of primary granule 12 is 0.001- 50 μm (such as 50-400nm or 1-50 μm), and the size range of basic granules is 1-400nm (such as 5-40nm).As herein Used, " spray drying " refers to metal oxide (such as silica), and it is by with the evaporation liquid from colloidal sol What mode obtained colloidal sol expansion, such as by the way that silicon dioxide gel is passed through into spout or nozzle with hot gas.
" disintegrating " or " disintegrating " refers to agglomerate degraded to discharge free primary granule and/or smaller fragment, It can also include reaction product and/or the material being carried on its surface, such as load activator thereon and/or catalysis Agent precursor compound.For example, it is usual way to disperse in a liquid, can be disintegrated by the non-encapsulated agglomerate of this method. Optionally, smaller agglomerate can also be formed by disintegrating (has released one or more primary therefrom as residue Grain) and/or agglomeration again as dissociate primary granule and/or smaller fragment result.
As used herein, " rupture " refers to the degraded of material all in one piece, aggregation, primary granule, shell etc.." fragmentation " or " fragmentation " uniformly refers to discharging relatively small particle, either by disintegrating, rupture, and/or some other methods, As the case may be.Term " fragment " is used to refer to less particle herein, including residual agglomerate and by fragmentation Any new particle that the first larger particles formed are formed, include the agglomerate residue of primary granule, dissociate primary granule, Residue (no matter less than or greater than primary granule) is ruptured, and including any such particle, is had thereon or wherein Or without loaded product.Fragmentation, particularly in the case where disintegrating and being dominant mechanism, can not formed substantially it is thin Occur in the case of powder, i.e. form the fine powder less than 2vol%, the cumulative volume based on agglomerate.As used herein, " fine powder " It is commonly referred to as the particle less than 0.5 μm.
Fragmentation can occur as got off：Such as during calcinated support particle by outside to apply heating power (such as high Heat), and/or the mechanical force for coming from crushing under compression be present or come from mobile particle with other particles and/or to admittedly Determine the impact (sometimes referred to as " stirring fragmentation ") contacted on surface.Fragmentation can also be in some embodiments in this paper In by inserting, expansion and/or other interactions of the material related to particle hole produce, as example when MAO inserts in the hole Or polymer is in hole when forming, and the subelement of carrier granular destroys or carrier granular is otherwise expanded to force The subelement of particle leaves other subelements, such as causes capsule to split, and forces primary granule away from each other and/or makes primary During grain rupture, such as either it can occur in the course of the polymerization process in the heat treatment process for catalyst preparation or activation. The fragmentation of the latter type is herein referred to as " expansion fragmentation " and/or (is including the agglomeration of micro- encapsulating from agglomerate Body) in disintegrate and be referred to as " expansion is disintegrated " in the case of particle.
For this specification and its purpose of appended claims, when referring at least X mmol hydrogen or other chains When polymerizeing in the presence of transfer agent or terminator (" CTA ")/mol propylene, the ratio be based on feed reactor hydrogen or The amount of other chain-transferring agents and propylene determines." chain-transferring agent " is hydrogen or can urged in the course of the polymerization process in coordination polymerization The reagent that hydrocarbon and/or polymeric groups exchange is carried out between agent and CTA metal center.
Unless otherwise directed, otherwise " catalyst productivity " is to use the polymerization catalyst for including Wg catalyst (cat), The measurement of how many grams of polymer (Pol or P) is produced in the period of T hours；And it can be represented by following formula：P/ (TxW) and with unit polymer grams divided by catalyst grams and the product of hour time (gPol gcat-1h-1) represent.
Unless otherwise directed, otherwise " conversion ratio " is the amount for the monomer for changing into polymer product, and is as mol% Come what is reported, and calculated based on polymer yield and the amount for the monomer for feeding reactor.
Unless otherwise directed, otherwise " catalyst activity " is that catalyst has much active measurements, and is as being produced Catalyst (cat) transition metal (kg P/mol cat) used in quality/mol of raw resulting polymer (P) is come what is reported.
" alkene (olefin) ", alternatively it is referred to as " alkene (alkene) ", is linear, the branch with least one double bond Change or the carbon of ring-type and the compound of hydrogen.For purposes of the invention, ethene should be considered as alpha-olefin." alkene " base Group is linear, the group of branched or ring-type carbon and hydrogen with least one double bond.
For this specification and its purpose of appended claims, when polymer or copolymer are referred to as including alkene During hydrocarbon, the alkene in the presence of such polymer or copolymer is the polymerized form of alkene.Such as when copolymer it is said that " second When alkene " content is 35wt%-55wt%, it should be understood that " monomer " unit in copolymer derived from ethylene in the polymerization, And described derived units are the weight based on the copolymer with existing for 35wt%-55wt%." polymer " has two Or more identical or different monomeric units." homopolymer " is the polymer for having same monomer unit." copolymer " is With two kinds or more kinds of monomeric units different from each other polymer." terpolymer " is different from each other with three kinds The polymer of monomeric unit.For represent monomeric unit it is " different " expression monomeric units differ each other at least one atom or Person be isomerism it is different.Therefore, as used herein, the definition of copolymer is including terpolymer etc..
" ethene polymers " either " polyethylene " or " ethylene copolymer " is the ethylene derivative list for including at least 50mol% The polymer or copolymer of member, " acrylic polymers " either " polypropylene " or " propylene copolymer " is to include at least 50mol% Propylene derived unit polymer or copolymer etc..Term " polypropylene " is intended to include isotactic polypropylene (iPP), and (it is fixed Justice is with least 10% or bigger unit group of isotaxy five), (it is defined as having height isotactic polypropylene The 50% or bigger unit group of isotaxy five), (it is defined as having 10% or bigger to syndiotactic polypropylene (sPP) Syndiotaxy five-tuple), homopolymer polypropylene (hPP, also referred to as Noblen or homo-polypropylene), and so-called random Co-polymer polypropylene (RCP, also referred to as random copolymer of propylene).Herein, RCP is expressly defined as being propylene and 1-10wt% Be selected from ethene and C4-C8The copolymer of the alkene of 1- alkene.It is preferred that isotachyte (such as IPP) has at least 20% (preferably at least 30%, the unit group of isotaxy five preferably at least 40%).If polyolefin has complete with vertical less than 10% The unit group of structure five and syndiotaxy five-tuple, then it is " atactic ", also referred to as " unbodied ".
Term " ethylene-propylene rubber " or " EP rubber " (EPR) represent ethene and propylene, and optional one kind or more The copolymer of kind diene monomers, wherein ethylene contents are 35-85mol%, and total diene content is 0-5mol%, and surplus is third Alkene, minimum propylene content are 15mol%.
Either " multiphase " refers to existing in the composition comprising two kinds or more kinds of polymer to term " multiphase " Two kinds or the phase of more kinds of forms, wherein each mutually include different polymer or different polymer ratios, it is portion Divide ground or the fully result of immiscible property (i.e. thermodynamics incompatibility).Common example is by continuous discrete phase and at least A kind of form of scattered or discontinuous phase composition.Dispersed phase, which is taken and is distributed in matrix, (or to be more than two-phase as existed, then exists In other phase regions) discrete domain (particle) form.Another example is co-continuous form, wherein two-phase is observed, but which It is individual be continuous phase and which be that discontinuous phase is unclear, such as discrete phase generally have continuous endoporus and fill mutually sink In the case that product is in the hole, or mutually expansion is (right by porous matrix spheroid in the hole of original sphere discrete phase in filling The polymer that Ying Yu is initially formed on or in support agglomerate body) being expanded into sub- spheroid, (it can be either partially or fully Separation and/or it is co-continuous or be dispersed in filling phase in, corresponding to the polymer formed on or in carrier primary granule) In the case of.For example, polymer spheres can initially have such discrete phase, its porosity corresponds to support agglomerate body, But with higher filling phase (being attributed to the expansion in gap of the filling mutually between the sub- spheroid of discrete phase).
The presence of multiphase is identified below：Use micrology technology, such as light microscopy, scanning electronic microscopy , or atomic force microscopy (AFM) (SEM)；Or two glass transitions in being tested by dynamic mechanical analysis (DMA) (Tg) presence at peak；Or carry out the preferential one kind that separates by physical method such as solvent extraction, such as the extraction of dimethylbenzene high temperature and gather Compound is mutually carried out；In the case of inconsistent in these methods, should use according to US2008/0045638 pages 36 (including Wherein cited any bibliography) described program carry out DMA.
" polypropylene impact copolymer " or referred to as " impact copolymer " (ICP) are crystallization and amorphous polymer (such as example Such as iPP and rubber) combination (being usually multiphase), it is provided with rigidity and toughness (that is, more than one or more without fixed The rigidity of the rigidity of shape polymer and more than one or more crystalline polymers toughness toughness) ICP of the two.ICP is usual There can be such form, to cause discrete phase to include the crystalline polymer of higher proportion, and rubber exists with higher proportion In scattered or co-cable transmission, for example, the iPP matrix comprising 60-95wt% and 5-40wt% ethene, propylene or other Polymer (Tg- 30 DEG C or lower) blend.
Term " sequential polymerization " refers to such polymerization, wherein different polymer is identical or different anti- Answer in device, produced in the different periods, such as to produce multimodal and/or multiphase polymer.Term " gas-phase polymerization ", " become silted up Slurry phase-polymerization ", " homogeneous polymerization method " and " bulk polymerization " are defined below.
Term " continuous " expression system is uninterrupted or not out of service.For example, the continuous side of production polymer Method will be such method, and wherein reactant is continually introduced into one or more reactors, and polymer product is continuously extracted out.
As used herein, Mn is number-average molecular weight, and Mw is weight average molecular weight, and Mz is z average molecular weights, and wt% is weight hundred Divide ratio, and mol% is molar percentage.Molecular weight distribution (MWD), also referred to as polydispersity (PDI), are defined as Mw divided by Mn. Unless otherwise directed, otherwise all molecular weight (such as Mw, Mn and Mz) are g/mol, and are surveyed as described below by GPC-DRI It is fixed.Following abbreviation can be used for herein：Me is methyl, and Et is ethyl, and Pr is propyl group, and cPr is cyclopropyl, and nPr is positive third Base, iPr are isopropyls, and Bu is butyl, and nBu is normal-butyl, and iBu is isobutyl group, and sBu is sec-butyl, and tBu is the tert-butyl group, and Oct is Octyl group, Ph are phenyl, and Bn is benzyl, and THF or thf are tetrahydrofurans, and MAO is MAO, and OTf is trifluoromethayl sulfonic acid Ester (salt).
Environment temperature, also referred to as room temperature (RT), is 23 DEG C ± 3 DEG C, unless otherwise directed herein.
" catalyst system " is at least one catalyst precursor compounds, at least one activator, optional activator promotor With the combination of carrier material.Polymerisation catalyst system is the catalyst system that monomer can be aggregated into polymer.With regard to the present invention And its for the purpose of appended claims, when catalyst system is described as the neutral stable form comprising component, this Art personnel are well known that the ionic species of component is to produce the form of polymer with monomer reaction.
In description herein, single site catalysts precursor compound can be described as catalyst precarsor, catalyst Precursor compound, pre-catalyst compound, metallocene or MCN, metallocene compound, metallocene catalyst, metallocene catalysis Immunomodulator compounds, metallocene catalyst precursors compound either transistion metal compound or similar variant, and these terms are It is used interchangeably.Catalyst precursor compounds are neutral compound (such as the Cp of no polymerization activity2ZrCl2), it needs to live Agent (such as MAO) forms active catalyst species (such as [Cp2ZrMe]+), or dormancy active catalyst species (such as [Cp2Zr(μ-Me)2AlMe2]+) come become being capable of polymerization of olefin monomers.Metallocene catalyst is defined as organo-metallic compound (and sometimes can so refer within a context), there are at least one π-bonding cyclopentadienyl moieties (or to take for it The cyclopentadienyl moieties in generation) and the more often cyclopentadienyl moieties of two π-bondings or substituted cyclopentadiene base portion Point.The fluorenes of indenes, substituted indenes, fluorenes and substitution is entirely the cyclopentadienyl moieties substituted.
Word " composition is different " represents that discussed composition differs at least one atom.Such as cyclopentadiene and methyl ring The difference of pentadiene is methyl be present.Such as " double tetrahydroindenyl zirconium dichlorides " is different from " (indenyl) (2- methylindenyls) dichloride Zirconium ", it is different from " (indenyl) (2- methylindenyls) hafnium dichloride ".The mesh that only the different catalyst compounds of isomers are just invented For be considered as identical, such as double (2- methyl 4- phenyl) the dimethyl hafniums of racemic dimetylsilyl be considered as with Double (2- methyl 4- phenyl) the dimethyl hafniums of meso dimetylsilyl are identicals.
Organo-metallic compound is defined as the change for containing at least one key between the carbon atom and metal of organic compound Compound, and generally, although not always, it can be to for example coming from the hydroxyl deprotonation of carrier material.Deprotonation agent defines For such compound or system, its can to coming from the hydroxyl deprotonation of carrier, and can be organic metal or Other compounds such as ammonobase, such as amino aluminium or lithium amide.
" anion ligand " is electronegative part, and it gives one or more pairs of electronics to metal ion." neutral donor is matched somebody with somebody Body " is electroneutral part, and it gives one or more pairs of electronics to metal ion.
Term " co-catalyst " and " activator " are used interchangeably herein, and are defined as any such chemical combination Thing, it can be by the way that neutral catalyst precursor compound to be changed into the catalyst compounds cation of catalytic activity, to activate The catalyst precursor compounds.Term " non-coordinating anion " (NCA), " compatible " NCA, " large volume activator ", " molecule body Product ", " smaller size smaller ", " larger volume " is defined below.
In embodiments, the heterophasic propylene polymer composition produced herein, such as comprising filled rubber, or to divide Stage hydrogen supply is come the heterophasic propylene polymer composition that produces, and/or in regulation, the heterophasic propylene that is produced after period B Polymer composition, impact copolymer can be herein referred to as, either propylene impact copolymer or the punching of reactor inner propene Copolymer, or reactor inner propene impact copolymer composition are hit, and such term is used interchangeably herein.
Term " hydrocarbyl group (radical) ", " alkyl " and " hydrocarbyl group (group) " make entirely interchangeable herein With.Equally, term " group (group) ", " group (radical) " and " substituent " are also used interchangeably herein.With regard to this For disclosed purpose, " hydrocarbyl group " is defined as such group, and it includes hydrogen atom and at most 100 carbon atoms, and It can be it is linear, it is branched or ring-type, and when being ring-type, be aromatics or non-aromatic.
Substituted hydrocarbyl group is such hydrocarbyl group, and wherein at least one hydrogen is by hetero atom or containing hetero atom Group substitution.
Halocarbyl group is such group, and wherein one or more alkyl hydrogen atoms are by least one halogen (such as F, Cl, Br, I) or halogen-containing group (such as CF3) substitution.
The carbon-based group of silicyl (also referred to as silicyl is carbon-based) is such group, and wherein silyl functional degree is straight Connect and be bonded on shown one or more atoms.Example includes SiH3, SiH2R*, SiHR*2, SiR*3, SiH2(OR*), SiH (OR*)2, Si (OR*)3, SiH2(NR*2), SiH (NR*2)2, Si (NR*2)3Deng wherein R* is independently alkyl or halocarbyl Group, and can be joined together to substituted or unsubstituted saturation, part undersaturated by two or more R* Either aromatic cyclic or polycyclic ring structure.
The carbon-based group of germyl (also referred to as germyl is carbon-based) is such group, and wherein germyl degree of functionality is straight Connect and be bonded on shown one or more atoms.Example includes GeH3, GeH2R*, GeHR*2, GeR*3, GeH2(OR*), GeH (OR*)2, Ge (OR*)3, GeH2(NR*2), GeH (NR*2)2, Ge (NR*2)3Deng wherein R* is independently alkyl or halocarbyl Group, and two or more R* can be joined together to substituted or unsubstituted saturation, part unsaturation Either aromatic cyclic or polycyclic ring structure.
Polar group (radical) or polar group (group) are such groups, and wherein heteroatom functional degree is direct On one or more atoms shown in being bonded to.They include the hetero atom of periodic table 1-17 races, and it is single or logical Cross covalent bond or other interactions (such as ionic bond, Van der Waals force or hydrogen bond) are connected in other elements.Functional group Example include carboxylic acid, acid halide group, carboxylate, carboxylate, carboxylic acid anhydrides, aldehyde and their chalcogen (the 14th race) analog, Alcohol and phenol, ether, peroxide and hydroperoxides, carboxylic acid amide, hydrazides and acid imide, amidine and other nitrogen analogs：Acid amides, Nitrile, amine and imines, azo, nitro, other nitrogen compounds, sulfuric acid, selenic acid, mercaptan, sulfide, sulfoxide, sulfone, sulphonic acid ester, phosphine, phosphorus Acid esters, other phosphorus compounds, silane, borine, borate, aluminium alkane, Aluminate.Functional group can also be broadly used for including organic Polymer support or inorganic carrier material, such as aluminum oxide and silica.The example of preferable polar group includes NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SnR*3, PbR*3Deng wherein R* is independently alkyl, substituted Alkyl, halocarbyl or substituted halocarbyl group, as defined above, and two R* can be bonded together and carry out shape Into substituted or unsubstituted saturation, the undersaturated either aromatic cyclic in part or polycyclic ring structure.Further preferably Sulfonate ester group S (=O)2OR*, wherein R* are as defined above.Example includes SO3Me (mesyl), SO3(4- tosyls) (tosylate), SO3CF3(triflate), SO3(n-C4F9) (nine fluorine fourth sulphonic acid esters) etc..
Aromatic yl group is defined as monocyclic groups or multi-fused rings group, and wherein at least one ring is aromatics.Aryl and take The example of the aryl in generation includes phenyl, naphthyl, anthryl, aminomethyl phenyl, isopropyl phenyl, tert-butyl-phenyl, cyclopropyl, ring fourth Base, cyclopenta, cyclohexyl, carbazyl, indyl, pyrrole radicals, and cyclopenta [b] thienyl.Preferable aromatic yl group bag Include phenyl, benzyl, carbazyl, naphthyl etc..
Term " substituted cyclopentadienyl group " is being used, it is foregoing either when " substituted indenyl " or " substituted aryl " Substitution be on bonding ring position, and every time occur be selected from alkyl, substituted alkyl, halocarbyl, substituted halo carbon Base, silicyl is carbon-based, and germyl is carbon-based, halogen group or polar group." bonding ring position " is such ring position Put, it can carry substituent or bridging substituent.For example, cyclopenta [b] thienyl has five bonding ring positions Put (at carbon atom) and a non-bonding ring position (sulphur atom)；Cyclopenta [b] pyrrole radicals is bonding with six Ring position (at carbon atom and at nitrogen-atoms).Therefore, when being related to aromatic yl group, term it is " substituted " represent hydrogen group by Alkyl, substituted alkyl, halocarbyl, substituted halocarbyl, silicyl is carbon-based, and germyl is carbon-based, halogen group or Person's polar group substitutes.For example, " aminomethyl phenyl " is such phenyl, it has by methyl substituted hydrogen.
As used herein, "and/or" represent mentioned term either statement any or the two (or it is any or Person is whole), and " and/or " represent first one (or multiple) or the mentioned term of mentioned term either statement Or the two (whole) of statement, i.e. the term of the latter or statement are optional.
Detailed description of the invention
The present invention provides highly porous acrylic polymers in some embodiments.In some embodiments of the present invention In, the acrylic polymers includes at least 50mol% propylene；1% Secant flexural modulus (1%SFM) is at least 1000MPa, and it is Determined according to ASTM D 790 (A, 1.0mm/min)；More than 5 to less than 200 area defects/10000 propylene units, its It is to pass through13C NMR measure；If there is comonomer, then it is 50% or bigger to form Distribution Breadth Index (CDBI)；With Matrix, it is 15% or bigger that it, which includes porosity, preferably 30% or bigger, and intermediate value PD more than 6 and less than 160 μm it Between, it is determined by mercury injection method.In some embodiments of the present invention, the acrylic polymers includes multimodal PSD, multimodal MWD, include the heterophasic copolymer of filling phase, or its combination.
In some embodiments of the present invention, the polymer is particle form, and wherein at least 95 volume %, which have, to be more than About 120 μm of granularity.
In some embodiments of the present invention, the polymer is further comprising the active catalytic mass being dispersed in matrix System, the catalyst system includes single site catalysts precursor compound, for the activator of precursor compound, and carrier, The specific surface area of the carrier is 400m2/ g is bigger, and pore volume is 0.5-2mL/g and average pore diameter is 1-20nm
In some embodiments of the present invention, the polymer further includes heterophasic copolymer, the heterophasic copolymer bag Filling phase containing the hole in filling substrate at least in part.
In some embodiments of the present invention, the polymer includes：Total propylene content is at least 75wt%；If there is Comonomer, then total comonomer content is that about 3wt% height arrives about 25wt%；If there is comonomer, then CDBI is At least 60%；Matrix pores rate is at least 35%；Matrix median pore size diameter is more than 8 μm and less than 150 μm, and it is to pass through mercury injection method Measure；At least 50% unit group of isotaxy five；More than 10 area defects/10000 propylene units, it is to pass through13C NMR measure；1% Secant flexural modulus is at least 1800MPa；Fusing point (Tm, DSC peak second melting) is at least 145 DEG C；Pass through It is high to 5 that the Mw/Mn of GPC-DRI measurements is greater than 1；Multimodal molecular weight is distributed, and overall Mw/Mn is greater than 1-20 and at least one Individual most probable value has the Mw/Mn more than 1-5；At least 95 volume % have the granularity for being more than 150 μm of height to 10mm；Melt flows Speed (MFR, ASTM1238,230 DEG C, 2.16kg), which is that about 0.1dg/min is high, arrives about 300dg/min；Mw (passes through GPC- DRI is measured) it is 50000-1000000g/mol；Or its combination.
In some embodiments of the present invention, catalyst system and carrier as described herein can be used for polypropylene (example Such as prepare highly porous acrylic polymers) method.In some embodiments of the present invention, the method bag of the polypropylene Include：(a) propylene monomer is contacted with catalyst system under polymerization conditions, the catalyst system includes single site catalysts The average PS of precursor compound, activator and carrier, the wherein carrier is greater than 30 μm, is greater than 50 μm and/or at most 200 μ M, surface area are 400m2/ g is bigger, such as 400-1000m2/ g (such as 400-650m2/ g or 650-1000m2/ g), PV It is 0.5-2mL/g (such as 0.5-1.5mL/g), and average PD is 1-20nm, such as 1-7nm or 7-20nm；Form third (b) Alkene polymer matrix, it includes at least 50mol% propylene, and porosity is 15% or bigger, such as 30-85%, and it is Determined by mercury injection method.In some embodiments of the present invention, the carrier in (a) includes the agglomeration of multiple primary granules The propylene polymer matrix formed in body, and/or (b) includes intermediate value PD and is less than 165 μm or less than 160 μm, and it is to pass through pressure Mercury method measure.In some embodiments of this method, the catalyst system (one or more) can include a kind of or more Kind any catalyst system as described herein.
According to some embodiments of the present invention, contact of the propylene monomer with catalyst system is carried out in slurry 's.According to some embodiments of the present invention, polymerizing condition includes about 0.96MPa (140psi)-about 5.2MPa The pressure of (750psi) and about 50 DEG C -100 DEG C of temperature.
According to some embodiments of the present invention, the propylene monomer in (a) there is no ethene and C4-C20Alhpa olefin, and And the acrylic polymers formed is Noblen.According to some embodiments of the present invention, this method further comprises (a) hydrogen or other CTA concentration are changed in, wherein the acrylic polymers formed in (b) has multimodal MWD.
According to some embodiments of the present invention, this method further comprised the acrylic polymers at 1000 seconds-1Or Melt-processed under bigger shear rate.
According to some embodiments of this method, the acrylic polymers formed in (b) include matrix, its comprising 15% or Bigger porosity, the cumulative volume based on the matrix, and the intermediate value PD less than 160 μm, it is determined by mercury injection method.
Be described in more detail below catalyst system, carrier, activator, catalyst precursor compounds and activator promotor it is excellent The embodiment of choosing.
Carrier material：According in the embodiment invented herein, the catalyst system can include porosu solid Grain is used as inert support material, to thereon can be with the catalyst precursor compounds such as grappling, bonding, absorption and/or activator.It is preferred that Ground, the carrier material are fractionized inorganic oxides.For the suitable inorganic oxide in this paper MCN catalyst systems Thing material includes the 2nd, 4,13 and 14 family metal oxide, such as silica, aluminum oxide, magnesia, titanium dioxide, zirconium oxide Deng and its mixture.However, it is possible to use other suitable carrier materials, such as the functionalised polyolefin of subdivision, such as segment Polyethylene or polypropylene.Particularly useful carrier includes silica, magnesia, titanium dioxide, zirconium oxide, montmorillonite, Phyllosilicate, zeolite, talcum, clay etc..In addition it is possible to use the combination of these carrier materials, such as silica-chromium, Silica-alumina, silica-titania etc..
In some preferred embodiments, the carrier material preferably comprises silica, such as amorphous silica, It can include presenting hydroxyl or other groups (it can form reactive position with deprotonation, come grappling activator and/or Catalyst precarsor) hydration surface.Other porous carrier materials optionally can have conduct with together with preferable silica Carrier, such as talcum are helped, other inorganic oxides, zeolite, clay, organic clay either any other organic or inorganic carrier Material etc., or its mixture.
Unexpectedly resistance to stirring is broken generally during calcining heat for the carrier material of some embodiments of the present invention Piece or expansion fragmentation.In some embodiments, the carrier can there is no fragmentation to calcine, i.e. PS points Cloth does not substantially change and/or generated primary granule (if present) and/or the fine powder less than 5vol%, based on carrier The cumulative volume of material.
According to some embodiments of the present invention, then the carrier material (is described in greater detail below) with activator, At least one single site catalysts precursor compound (being described in greater detail below), and/or co-catalyst is (below more Describe in detail) and optional scavenger or activator promotor (being described in greater detail below) contact.
It is in catalyst system and/or for preparing the carrier of catalyst system according to some embodiments of the present invention It is preferred that having or comprising following：
A) particle mean size (PS) and/or PS most probable values are greater than 30 μm, either more than 40 μm or more than 50 μm, or Person is more than 60 μm, either more than 65 μm or more than 70 μm, either more than 75 μm or more than 80 μm, or more than 85 μm, Either more than 90 μm or more than 100 μm, or more than 120 μm；And/or at most 200 μm, or less than 180 μm, Huo Zhe little In 160 μm, either less than 150 μm or less than 130 μm；Such as 30-200 μm, either 50-200 μm or 60-200 μm；
B) pore volume (PV) is at least 0.1mL/g, either at least 0.15mL/g or at least 0.2mL/g, or at least 0.25mL/g, either at least 0.3mL/g or at least 0.5mL/g；And/or at most 2mL/g, either less than 1.6mL/g or Less than 1.5mL/g, either less than 1.4mL/g or less than 1.3mL/g；Such as 0.5-2mL/g either 0.5-1.5mL/g or 1.1-1.6mL/g；
C) specific surface area (SA) is less than 1400m2/ g, or less than 1200m2/ g, or less than 1100m2/ g, Huo Zhe little In 1000m2/ g, or less than 900m2/ g, or less than 850m2/ g, or less than 800m2/ g, or less than 750m2/ g, or Less than 700m2/ g, or less than 650m2/g；And/or more than 400m2/ g, or more than 600m2/ g, or more than 650m2/ g, or Person is more than 700m2/g；Such as 400-1000m2/ g, or 600-1000m2/ g, or 650-1000m2/ g, or 700- 1000m2/ g, or 400-650m2/ g, or 400-700m2/g；
D) average pore diameter (PD) is greater than 0.1nm, more than 1nm, either more than 2nm or more than 3nm, or is more than 4nm, either more than 5nm or more than 6nm, either more than 7nm or more than 8nm；And/or less than 20nm, or be less than 15nm, either less than 13nm or less than 12nm, either less than 10nm or less than 8nm, either less than 7nm or it is less than 6nm；Such as 1-7nm, either 1-8nm or 1-13nm, either 7-13nm or 8-13nm, either 7-20nm or 8- 20nm；
E) agglomerate is made up of multiple primary granules, and the average PS of the primary granule is that 1nm- is less than 50 μm, or 1 μm- Less than 30 μm；
F) agglomerate of micro- encapsulating；
G) it is spray-dried；
H) silica, such as amorphous silica and/or the silica with hydration surface；And/or
I) its any combination or sub-portfolio.
In some embodiments, the carrier includes the agglomerate of multiple primary granules, and in a further embodiment The carrier is at least partially enveloping.In addition or alternatively, the carrier includes the material of spray drying, such as spraying is done Dry silica.According in embodiment of the present invention, the carrier material outside meeting PS, SA, PV and PD characteristic, It is preferred that it is made up of such method, i.e. by less primary granule (such as averagely PS is 0.001-50 μm of particle), agglomerate into Average PS is 30-200 μm of larger agglomerate, for example, come from spray drying process those.The larger particle is (i.e., Agglomerate) therefore can include little particle, i.e. primary granule.The agglomerate and/or primary granule any or the two can be with With high or low sphericity and circularity, such as Wadell sphericitys are 0.8 or bigger, 0.85 or bigger, 0.9 or more Greatly, either 0.95 or bigger, or less than 0.95, less than 0.90, less than 0.85, or less than 0.8；It is with Wadell circularity 0.1 or lower, it is high to 0.9 or bigger.
SA, PV and average PD are typically inter-related, i.e., in some embodiments, in some scopes of these parameters Interior, average PD and SA product can be proportional to PV.PV, PD and SA are preferably selected to balance in some embodiments Desired mechanical strength and desired activator load capacity, i.e. high SA is suitable to overactivity agent and catalyst loadings, but can not It is too high, to keep enough intensity, to avoid the fragmentation in calcining or stirring and processing procedure, and avoid simultaneously excessive Intensity, it may undesirably suppress fragmentation in the course of the polymerization process in some embodiments.Preferably, in order to meet these It is required that the PS of the carrier material in some embodiments of the present invention is 30-200 μm, SA is 400-1000m2/ g, PV are 0.5-2mL/g and average PD is 1-20nm.Can be with trade name D according to the suitable silica of some embodiments of the present invention 150-60A, D 100-100A, D 70-120, PD 13054, PD 14024 etc. is commercially available.The combination of the performance range be with Other most of silica supports for iPP MCN catalyst are opposite.For example, if SA is too low, activity is probably Low；If PV is too high, the particle is probably mechanically frangible；If PS and/or PV are too small, result is probably low work Property, low porosity, low rubber filling, the rubber and/or reaction fouling of excess surface deposition；If excessive with PS, heat is removed It is poorly efficient to go, and the migration inside monomer to polymer beads is limited, and monomer concentration is insufficient, and chain termination is too early , and/or produce low molecule amount.
In some embodiments, there is SA >=400m2/ g and average PD=1-20nm, relatively low SA, is, for example, less than 700m2/ G or less than 650m2/ g, and/or higher average PD, the agglomerate tool being greater than in 7nm or preferred scope more than 8nm There are higher-strength and the fragmentation being dominant during carrying method more tolerant to chip, the carrying method therefore can be higher Temperature is carried out, and can realize greater catalytic agent load capacity to be used for greater catalytic agent activity.
On the other hand, in some other embodiments, SA is more than 650m2/ g or more than 700m2/ g, and average PD are small Can be with minimum fragmentation in 8nm or agglomerate less than 7nm, with the method condition carefully controlled, (such as low-load is reacted Temperature) prepare, and still can more easily fragmentation in the course of the polymerization process, it can lead in the case of heterophasic copolymer Cause of a relatively high acrylic polymers porosity and/or higher filling phase content.On the other hand, when SA be about 650 or 700m2/ g or it is higher when, in order to keep mechanical strength, PD must be low, be, for example, less than 7nm, and if desired, can make Promote silica chips with loading condition, the loading condition promotes substantially completely or partly fragmentation, example Such as in the temperature higher than about 40 or 60 DEG C.
According to some embodiments of the present invention, except any one or more of above-mentioned carrier material or the catalysis of load Agent system is either outside mixture or in combination, and the carrier material further comprising optional second or can help carrier Material, it can be designed to promote another acrylic polymers or copolymer (such as bimodal volcanic rocks) and/or another olefinic polymerization Thing or copolymer, such as the polymerization of rubber filling material or EP rubber (such as impact copolymer).According to some of the present invention Embodiment, second catalyst carrier material when it is present, most preferably inorganic oxide, its SA be about 10- about 700m2/ g, PV are about 0.1- about 4.0mL/g, and average PS is about 500 μm of about 5-.It is highly preferred that second catalysis The SA of agent carrier material is about 50- about 500m2/ g, PV are that about 0.5- about 3.5mL/g and average PS are that about 10- is big About 200 μm.Most preferably, the SA of second catalyst carrier material is about 100- about 400m2/ g, PV are that about 0.8- is big About 3.0mL/g and average PS is about 100 μm of about 5-.Carried available for the second catalyst in some embodiments of the present invention The average PD of body material is 1-100nmIt is preferred that (50- is about by 5-50nm) and most preferably 7.5- (75- is about by 35nm).In some embodiments of the present invention, second catalyst carrier material is high SA, without fixed Shape silica (surface area=300m2/gm；Pore volume is 1.65mL/gm).Preferable Second support silica, which is worked as, to be present When, it is to be sold with the trade name listed by Table A, particularly Davison Chemical Division of W.R.Grace and Company GRACE 952 (also referred to as DAVISON 952) or GRACE 955 (also referred to as DAVISON 955), and at it GRACE 948 (also referred to as DAVISON 948) Second support is used in his embodiment.
The carrier material can be that hygrometric state uses, i.e. the water containing absorption, or dry state use, i.e. do not inhale Attached water.The amount of the water of absorption can be determined by standard method of analysis, such as come from instrument such as LECO TGA701, In such as 300 DEG C LOD (loss on drying) for carrying out 3 hours of condition.In some embodiments of the present invention, wet carrier material (not calcining) and can add another with activator or other organo-metallic compound (as described in further below) contacts Outer organic metal or other scavenger compounds, it can react or otherwise remove water, such as alkyl with water Metal.For example, by wet silica and alkyl aluminum such as AlMe3(it generally dilutes in organic solvent such as toluene) contact is former Position forms MAO, and if desired, can be added in a manner of similar to below for described in dried silica other MAO controls load desired amounts of MAO on this carrier.
, can be by higher than about 100 DEG C according to some embodiments of the present invention, such as about 100 DEG C-about 1000 DEG C, preferably at least about 200 DEG C are heated or calcined to realize the drying of the carrier material.When the carrier material is dioxy During SiClx, according to some embodiments of the present invention, heat it up at least 130 DEG C, preferably approximately 130 DEG C-about 850 DEG C and Most preferably from about 200-600 DEG C；With progress 1 minute-about 100 hours, such as about 12 hours-about 72 hours, Huo Zhe great The time of about 24 hours-about 60 hours.In some embodiments according to the present invention, the carrier material of calcining includes at least Some have the group (such as reactive hydroxyl (OH)) of reactivity with organo-metallic compound, to produce the load of the present invention Catalyst system.
Load：According to some embodiments of the present invention, the carrier is handled with organo-metallic compound, with the carrier table Deprotonation reactivity position reaction on face.Generally, the carrier is handled with organic metal activator (such as MAO) first, and so The activator MCN of the load afterwards, the processing of optional metal alkyl activator promotor, such as following discussion for explanatory purposes In, although MCN and/or activator promotor can be loaded first, then contact with other catalyst system components, particularly activating In the case that agent is not organo-metallic compound or has reactivity with carrier surface.
In some embodiments, it has reactive surfaces group, typically hydroxyl to the carrier material, such as is calcining (or metal alkyl processing, such as in wet method) after, in non-polar solven slurrying and with organo-metallic compound (in the reality It is activator in example) contact, it is preferably dissolved in solvent, preferably carries out about 0.5 hour-about 24 hours, about 2 hours- About 16 hours, or the period of about 4 hours-about 8 hours.Suitable non-polar solven is such material, wherein In addition to carrier material and its adduct, all reactants (that is, activator and MCN compounds) used herein are at least It is partly solvable, and it is liquid in reaction temperature.Preferable non-polar solven is alkane, such as isopentane, hexane, just Heptane, octane, nonane and decane, although various other materials can also be used, including cycloalkane, such as hexamethylene, aromatic hydrocarbons, example Such as benzene, toluene and ethylo benzene.
In the various embodiments of the present invention, the carrier material and activator (or other organo-metallic compounds) Mixture, which can generally heat, is either maintained at about -60 DEG C height to about 130 or 140 DEG C of temperature, as example：About 40 DEG C or it is lower, about 23 DEG C or lower, about -20 DEG C or lower；About 10 DEG C or 20 DEG C of height to about 60 DEG C or About 40 DEG C of person；About 23 DEG C either about 25 DEG C or higher；Or about 40 DEG C, about 60 DEG C, or about 80 DEG C of height To about 100 DEG C, or about 120 DEG C of temperature.Can be in activator/catalyst precarsor loading process easily by fragment in carrier Change influence (such as SA >=650m2/ g, PD≤7nm) in the case of, fragmentation can be controlled to press down by regulating and controlling reaction condition Fragmentation processed, for example, in relatively low reaction temperature, such as -60 to 40 DEG C, preferably -20 DEG C to 30 DEG C, to realize<10vol%'s Fragmentation particle, preferably<5vol% fragmentation particle；Such as in higher reaction temperatures to promote fragmentation, such as >= 40 DEG C, preferably >=60 DEG C, to realize>10vol% fragmentation particles, such as 10-80vol% fragmentation particles, such as 10- 20vol% fragmentation particles, 20-70vol% fragmentation particles, 70-90vol% fragmentation particles,>90vol% fragmentations Grain etc..Generally, it is inversely related to promote time needed for fragmentation and temperature, i.e. in higher temperature, fragmentation that chip is dominant It may require that the shorter period.
According to some embodiments of the present invention, the carrier material is in other processing procedures before load or polymerization Not fragmentation, i.e. the catalyst system of the load has such PSD, its after being handled with organo-metallic compound substantially It is maintained, and/or generates the fine powder for being less than 5vol% based on total carrier material volume, such as in the resistance to fragment of the carrier material In the case of change, or in selection loading condition come in the case of suppressing fragmentation.
According to some embodiments of the present invention, the caltalyst based material of load sufficiently large average PS or PS are kept Most probable value, is promoted to form the sufficiently large propylene polymerization composition granule rich in aperture, and it for example easily can be filled out with rubber Charge is filled, such as is filled during ICP or other heterophasic copolymers are prepared.On the other hand, excessive porous polypropylene Fine powder such as 5vol% or more fine powders for being less than 120 μm, typically by smaller particle such as carrier material agglomerate Either sub- primary granule chip or fine powder are formed primary granule, and it can cause reactor, pipeline or equipment porous poly- In the presence of propylene in rubber polymerization process (or vice versa), and/or in non-particulate polymer forming process fouling or Person blocks.
According in embodiment of the present invention, the catalyst of load, such as it is carried on SA>About 650m2/ g and PD<Greatly AboutSilica on, can polypropylene produce the iPP resins with unusual high rigidity, such as up to 2200MPa 1% Secant flexural modulus.In some embodiments according to the present invention, the catalyst of load, such as with balance On PS, SA, PV and PD silica, such as such as PS is 70-100 μm, and SA is 400-650m2/ g, PV be 1.1-1.6mL/g and PD isWith prepared under the conditions of low fragmentation, can polypropylene produce iPP resins, and/or there is phase To high porosity, 30% is greater than.In addition, high porosity can encompass active catalytic species to continue polymerization in addition Monomer form the second copolymer phase in heterophasic copolymer such as ICP (it has improved physical/chemical performance). It was found that as disclosed herein, by having the ICP of the MAO of limited fragmentation catalyst preparation on a support material based on load Resin shows improved ethylene-propylene (EP) rubber absorptivity (uptake).
(it can have conventional monomodal grit distribution) opposite with known catalyst carrier material, according to the present invention's Some embodiments, it is bimodal to be supported on the PSD of the mixture of fragmentation and the finished catalyst on non-fragmentation carrier, and And different Properties of Polypropylene is thus achieved, and result is that different Properties of Polypropylene can balance as needed.Separately Outside, in some embodiments, the PSD of the iPP resins formed changes according to the PSD of the catalyst system of load, i.e. with The larger iPP particles formed by larger more or less complete agglomerate are compared, and carrier fragment generates less iPP Particle.Generally, in the case of the propylene polymerization according to the various embodiments of the present invention, the carrier granular of non-fragmentation promotes greatly PS, high PV, low PD, the formation for the PP GRANULES that can be filled, and fragment can promote higher catalyst activity and be formed to have There are smaller PS and the polypropylene of higher stiffness, and therefore porosity, rubber filling content and rigidity can be by selecting fragmentation Appropriate mixture balances with non-fragmentation carrier.
The CiPP6 tools that the conventional catalyst with relatively wide unimodal PSD is obtained are used referring to Fig. 7, in embodiment 6 There is corresponding bell curve.Referring to Fig. 8-10 and embodiment 6, the finished catalyst being supported on non-fragmentation agglomerate obtains PSD (Fig. 8) in PiPP12 relatively large size area, the finished product being supported on the mixture of non-fragmentation agglomerate and fragment Catalyst generates the bimodal distribution (Fig. 9) of both big and small PiPP13 particles, and be supported on the fragment that chip is dominant into Product catalyst obtains the bell-shaped profile (Figure 10) that PiPP14 small grain size is dominant.In fig. 8, by the catalyst in reaction bar Part -20 is shown most for from non-fragmentation catalyst particles to the PSD that the PiPP12 prepared by 3 hours is carried out at 0 DEG C The bulky grain of grain；In fig.9, carry out 1 hour at 80 DEG C of reaction condition as the catalyst prepared by PiPP13 PSD tables Reveal two most probable values, i.e. come from less second most probable value of catalyst system fragment；In Fig. 10, by institute State catalyst the PSD of the PiPP14 prepared by 3 hours is carried out at 100 DEG C of reaction condition and show most for from catalysis The relative little particle of agent system fragment.In addition, the analysis of porosity based on oil filling micrology shows little particle iPP most probable values With low porosity, such as 2vol%, and bulky grain iPP most probable values have high porosity, such as 40vol%.So according to These embodiments, the such carrier prepared with low temperature processing or other gentle reaction conditions avoid catalyst debris Change and provide very high rubber load capacity, such as up to 76wt% or bigger, without obvious reaction fouling.
For the very first time, high porosity iPP resins can be based on carrier structure, independently of for obtaining iPP porositys Other systems (such as to produce low-molecular-weight resin, (it crystallizes and shunk to be formed polypropylene under high hydrogen polymerizing condition Limited hole) other systems) polymerizing condition used formed.The height according to the disclosure can be obtained in some embodiments Rigidity and high porosity iPP resins, but regardless of the hydrogen concentration in polymerization, and generate improved ICP.
In some embodiments of the present invention, the activator of the load is optionally with another organo-metallic compound (it is also selected as scavenger, preferably metal alkyl such as alkyl aluminum) is handled, to remove any hydroxyl or other reactivity (it can expose or otherwise retain species after being handled with the first organo-metallic compound, such as pass through fragmentation Hydroxyl on exposed surface can be contacted to react and thus remove by fragment with alkyl aluminum such as triisobutyl aluminium (TIBA) Go).Useful metal alkyl (it can be used to handle the carrier material according to some embodiments of the present invention) has logical Formula Rn- M, wherein R are C1-C40Alkyl such as such as C1-C12Alkyl, M are metals, and n is equal to M chemical valence, and can be included Oxytropism species such as diethyl zinc and alkyl aluminum, such as such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, Tri-n-octylaluminium etc., including its combination.Then activator/the carrier material contacts with the solution of catalyst precursor compounds. In some embodiments of the present invention, the activator of the load is caused by original position.In the selective embodiment of the present invention In, the slurry of the carrier material contacts about 0.5 hour-about 24 hours with catalyst precursor compounds first, and about 2 is small When-about 16 hours, or period of about 4 hours-about 8 hours, then the slurry of the MCN compounds of the load is with having Machine metal-activator solution and/or organic metal-removing agent solution contact.
Activator：Activator is used for by the way that neutral catalyst precursor compound is changed into catalytic activity catalyst compounds Thing cation activates the compound of any of the above-described catalyst precursor compounds.Nonrestrictive activator is for example including alumina Alkane, alkyl aluminum, Ionizing activators (it can be neutral or ion), and the co-catalyst of general type.It is preferable living Agent generally includes aluminium alkoxide compound, including modified alumoxane compounds, and ionizing anionic precursors compound, and it is captured The metal ligand of σ-bonding of reactivity, so that metal complex is cation, and provides the non-of charge balance and matches somebody with somebody Position or the anion of weak coordination.
Aikyiaiurnirsoxan beta be typically oligomeric partial hydrolysis alkyl aluminum compound (it contains-Al (R1)-O- subelements, wherein R1 is alkyl), and can be produced by the hydrolysis of respective trialkyl aluminium compound.The example of alumoxane activator includes MAO (MAO), ethylaluminoxane, butyla-luminoxane, isobutyl aluminium alkoxide, modified MAO (MMAO), halogenation MAO is (wherein The MAO can MAO load before or after halogenation), aluminum dialkyl cation enhancing MAO, surface bulky group be modified MAO etc..MMAO can be produced by the hydrolysis of trimethyl aluminium and the trialkylaluminium of higher level such as triisobutyl aluminium.It is different The mixture of aikyiaiurnirsoxan beta be also used as activator (one or more).
There is the method for the various preparation aikyiaiurnirsoxan betas for being applied to the present invention.Its nonrestrictive example description exists US4665208；US4952540；US5041584；US5091352；US5206199；US5204419；US4874734； US4924018；US4908463；US4968827；US5308815；US5329032；US5248801；US5235081； US5157137；US5103031；US5391793；US5391529；US5693838；US5731253；US5731451； US5744656；US5847177；US5854166；US5856256；US5939346；EP0561476；EP0279586；EP0594- 218；EP0586665；WO94/10180；In WO99/15534；Halogenation MAO is described in US7960488；US7355058；With In US8354485；The MAO of aluminum dialkyl cation enhancing is described in US2013/0345376；Change with surface bulky group Property load MAO describe in US8895465；Its is all entirely incorporated into herein by quoting.
When the activator is aikyiaiurnirsoxan beta, the selection of some embodiments relative to catalyst precursor compounds, (urge by pre-metal Change activated centre) maximum of 5000 times of molar excess Al/M activator.Minimum activator is 1 than catalyst compounds:1 rubs That ratio.Alternatively preferable scope includes 1:1-500:1, alternatively 1:1-200:1, alternatively 1:1-100:1, or Alternatively 1:1-50:1, such as 1:1-10:1 or 10:1-50:1.
In selective embodiment, using seldom or without using aikyiaiurnirsoxan beta in polymerization as described herein.It is excellent It is so that existing for 0mol%, alternatively aikyiaiurnirsoxan beta is with aluminium and catalyst precursor compounds transition metal mole ratio to select aikyiaiurnirsoxan beta Less than 500:1, or less than 300:1, or less than 100:1, or less than 1:Existing for 1.
It is within the scope of the invention that the activator of ionization or stoichiometry is used, it is neutral or ion, such as Before three (normal-butyl) four (pentafluorophenyl group) ammonium borate, three perfluorophenyl boron metalloid precursors or three perfluoronapthyl boron metalloids Body, more miscellaneous borane anions of halogenation (WO98/43983), boric acid (US5942459), or its combination.Also within the scope of the present invention Be using the neutral either activator of ion or non-coordinating anion activator, its be it is single or with it is alumoxane activated Agent is combined, such as in US8501655；US7897707；US7928172；US5153157；US5453410；EP0573120； WO94/07928；In WO95/14044；It is entirely incorporated into herein by quoting.On ionizing the activator with stoichiometry Further information can be in US8283428；US5153157；US5198401；US5066741；US5206197； US5241025；US5384299；US5502124；US5447895；US7297653；US7799879；WO96/04319； EP0570982；EP0520732；EP0495375；EP0500944；EP0277003；EP0277004；EP0277003；With Found in EP0277004；Its is all entirely incorporated into herein by quoting.
Optional scavenger or activator promotor：In addition to activator compound, scavenger can also be used or helped Activator.Suitable activator promotor can be selected from：Trialkylaluminium, dialkyl magnesium, alkyl halide magnesium and dialkyl group zinc.It may be used as Either the aluminium alkyl of activator promotor or organo-aluminum compound include such as trimethyl aluminium, triethyl aluminum, triisobutyl to scavenger Aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium etc..Other oxytropism species such as diethyl zincs can be used.As described above, for locating Manage calcining carrier material organo-metallic compound can be scavenger either activator promotor or can with scavenger or Activator promotor is identical or different.In one embodiment, activator promotor is selected from：Trimethyl aluminium, triethyl aluminum, triisobutyl Aluminium, tri-n-octylaluminium, three hexyl aluminium and diethyl zinc (are alternatively selected from：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three Hexyl aluminium, tri-n-octylaluminium, dimethyl magnesium, magnesium ethide, dipropyl magnesium, diisopropyl magnesium, dibutylmagnesium, diisobutyl magnesium, Dihexyl magnesium, dioctyl magnesium, methyl-magnesium-chloride, ethylmagnesium chloride, propyl group magnesium chloride, isopropylmagnesium chloride, butylmagnesium chloride are different Butylmagnesium chloride, hexyl magnesium chloride, octylmagnesium chloride, methyl magnesium fluoride, ethyl magnesium fluoride, propyl group magnesium fluoride, isopropyl fluorination Magnesium, butyl magnesium fluoride, isobutyl group magnesium fluoride, hexyl magnesium fluoride, octyl group magnesium fluoride, zinc methide, diethyl zinc, dipropyl zinc and Dibutyl zinc).
Metallocene catalyst precursors compound：According to some embodiments of the present invention, before the single site catalysts Body compound is shown in following formula：(Cp)mRA nM4Qk；Wherein each Cp is cyclopentadienyl moieties or by with 1-20 carbon The cyclopentadienyl moieties of one or more alkyl substitution of atom；RAIt is the structure bridge between two Cp rings；M4It is the 4th or 5 The transition metal of race；Q is alkyl of the hydrogen-based either with 1-20 carbon atom or the alkenyl with 2-20 carbon atom, or Halogen；M is 1,2 or 3, and if it is 2 or 3 to limit m, each Cp can be with identical or different；N is 0 or 1, and If limit m=1, n=0；It is so with k, i.e. so that k+m is equal to M4Oxidation state, and if limit k be more than 1, Each Q can be with identical or different.
According to some embodiments of the present invention, the single site catalysts precursor compound is shown in following formula：RA (CpR”p)(CpR*q)M5Qr；Wherein each Cp is cyclopentadienyl moieties or substituted cyclopentadienyl moieties；Each R* and R " is the alkyl for having 1-20 carbon atom, and can be with identical or different；P is 0,1,2,3 or 4；Q is 1,2,3 or 4； RAIt is the structure bridge between Cp rings, it assigns metallocene compound solid hardness；M5It is the 4th, 5 or 6 race's metal；Q is with 1- The alkyl or halogen of 20 carbon atoms；R is that s subtracts 2, and wherein s is M5Chemical valence；Wherein (CpR*q) there is two sides or vacation two Face symmetry；R*qAlkyl-substituted indenyl, or four-, three-or dialkyl group substitution cyclopentadienyl group；(CpR "p) bag Be contained in one of remote location and one of only in bulky group；Wherein the bulky group is formula ARw v；Wherein A is selected from Group-4 metal, oxygen or nitrogen, and RwIt is methyl or phenyl, and v is that A chemical valence subtracts 1.
According to some embodiments of the present invention, the single site catalysts precursor compound is shown in following formula：
Wherein M is the 4th, 5 or 6 race's metal；T is bridged group；Each X is independently anion leaving group；Each R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12And R13It is independently halogen atom, hydrogen, alkyl, substituted alkyl, halo carbon Base, substituted halocarbyl, silicyl is carbon-based, and substituted silicyl is carbon-based, and germyl is carbon-based, substituted germyl Carbon-based substituent or-NR'2,-SR' ,-OR' ,-OSiR'3Or-PR'2Group, wherein R' are halogen atoms, C1-C10Alkyl Or C6-C10One of aryl.
According to some embodiments of the present invention, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12And R13In at least One is cyclopropyl substituent shown in following formula：
Each R' wherein in the cyclopropyl substituent is independently hydrogen, substituted alkyl, unsubstituted alkyl or halogen Element.
According to some embodiments of the present invention, M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten；Each X is independently Selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substitute or do not take The C in generation6-C14Aryl, substituted or unsubstituted C6-C14Aryloxy group, substituted or unsubstituted C2-C10Alkenyl, substitution or unsubstituted C7-C40Aryl alkyl, substituted or unsubstituted C7-C40Alkylaryl and substituted or unsubstituted C7-C40Aryl alkenyl；Or Optionally it is joined together to C4-C40Alkane diyl, or conjugation C4-C40Diene ligand, it is matched somebody with somebody in the form of metal cyclopentene M is arrived in position；Or conjugated diene is optionally represented, it is optionally with independently selected from alkyl, trihydrocarbylsilyl groups and trialkyl first silicon One or more groups substitution of alkyl alkyl, described diene have at most 40 atoms (not including hydrogen) altogether and form π with M Complex compound；Each R2, R4, R8And R10Independently selected from hydrogen, halogen, substituted or unsubstituted C1-C10Alkyl, substitution or unsubstituted C6-C14Aryl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C7-C40Aryl alkyl, substitution or unsubstituted C7-C40Alkylaryl, substituted or unsubstituted C8-C40Aryl alkenyl, and-NR'2,-SR' ,-OR' ,-SiR'3,- OSiR'3With-PR '2Group, wherein each R' is independently selected from halogen, substituted or unsubstituted C1-C10Alkyl is with substitution or not Substituted C6-C14Aryl；R3, R5, R6, R7, R9, R11, R12And R13Each it is selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1- C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C6-C14Aryl, substituted or unsubstituted C6-C14 Aryloxy group, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C7-C40Aryl alkyl, substituted or unsubstituted C7- C40Alkylaryl and C7-C40Substituted or unsubstituted aryl alkenyl；It is selected from T：
—B(R14)-,-Al (R14)-,-Ge-,-Sn-,-O-,-S-,-SO-,-SO2-,-N (R14)-,-CO-,-P (R14)-and-P (O) (R14)-；Wherein R14, R15And R16Each independently selected from hydrogen, halogen, C1- C20Alkyl, C6-C30Aryl, C1-C20Alkoxy, C2-C20Alkenyl, C7-C40Aryl alkyl, C8-C40Aryl alkenyl and C7-C40Alkyl Aryl, optionally R14And R15Ring is formed together with connecting their atom (one or more)；And M3Selected from carbon, silicon, germanium and tin； Or T is shown in following formula：
Wherein R17, R18, R19, R20, R21, R22, R23And R24Each independently selected from hydrogen, halogen, hydroxyl, substitute or do not take The C in generation1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C6-C14Aryl, substitution or unsubstituted C6-C14Aryloxy group, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C7-C40Alkylaryl, substitute or do not take The C in generation7-C40Alkylaryl and substituted or unsubstituted C8-C40Aryl alkenyl；Optional two or more adjacent group R17, R18, R19, R20, R21, R22, R23And R24, including R20And R21, one or more rings are formed together with connecting their atom；And M2 Represent one or more carbon atoms, or silicon, germanium or tin atom.
In preferred embodiments, a kind of catalyst compounds are used in any method described herein, such as are being deposited In the case of first and second (and/or 3rd) catalyst systems, the catalyst compounds are not different.
In some embodiments, two kinds or more kinds of different catalyst compounds are present in catalysis used herein In agent system.In some embodiments, two kinds or more kinds of different catalyst systems are present in reaction zone, wherein Generation method described herein (one or more).When two kinds of transistion metal compound base catalyst are as hybrid catalyst system During for a reactor, two kinds of transistion metal compounds should be selected, make it that the two is compatible.People in the art Simple screening method known to member for example passes through1H or13Whether C NMR are determined for transistion metal compound compatible.
Two kinds of transistion metal compounds (pre-catalyst) can be used with any ratio.(A) transistion metal compound and (B) The preferable mol ratio of transistion metal compound falls into 1:1000-1000:1, alternatively 1:100-500:1, alternatively 1:10- 200:1, alternatively 1:1-100:1, alternatively 1:1-75:1 and alternatively 5:1-50:1 (A：B in the range of).It is specific Ratio will select depending on selected definite pre-catalyst, activation method and desired final product.Specific In embodiment, when using two kinds of pre-catalysts, wherein the two is activated with identical activator.Based on pre-catalyst Molecular weight, useful molar percentage is 10-99.9mol%A than 0.1-90mol%B, alternatively 25-99mol%A ratios 0.5-50mol%B, alternatively 50-99mol%A is than 1-25mol%B, and alternatively 75-99mol%A compares 1-10mol% B。
In any embodiment of the present invention, in any embodiment of any formula described herein, M is Zr or Hf.
In any embodiment of the present invention, in any embodiment of any formula described herein, each X is independently selected From the alkyl with 1-20 carbon atom, hydrogen-based, amino, alkoxy, sulfenyl, phosphorus base, halogen, diene, amine, phosphine, ether and its group Close, (two X ' can form a part for condensed ring or member ring systems), preferably each X independently selected from halogen and C1-C5 alkyl, It is preferred that each X is methyl.
In a preferred embodiment of the present invention, in any embodiment of any formula described herein, each R3, R5, R6, R7, R9, R11, R12Or R13It is independently hydrogen either substituted alkyl or unsubstituted alkyl, or hetero atom, preferably Hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl or its isomers.
In the preferred embodiment of any formula described herein, each R3, R4, R5, R6, R7, R9, R10, R11, R12Or R13Independently selected from hydrogen, methyl, ethyl, phenyl, benzyl, cyclobutyl, cyclopenta, cyclohexyl, naphthyl, anthryl, carbazyl, indoles The isomers of base, pyrrole radicals, cyclopenta [b] thienyl, fluorine, chlorine, bromine, iodine and following group：Propyl group, butyl, amyl group, Hexyl, heptyl, octyl group, nonyl, decyl, aminomethyl phenyl, 3,5-dimethylphenyl, ethylphenyl, diethyl phenyl, propyl group phenyl, two Propyl group phenyl, butyl phenyl, dibutylphenyl, methyl-benzyl, methylpyrrole base, dimethyl pyrrole, methyl indol base, diformazan Base indyl, methyl carbazole base, Dimethylcarbazole base, methyl cyclopentadiene simultaneously [b] thienyl, dimethyl cyclopenta [b] Thienyl.
In a preferred embodiment of the present invention, in any embodiment of any formula described herein, T is bridging group Group, and comprising Si, Ge or C, preferably T is dialkyl group silicon or dialkyl Germanium, and preferably T is dimethyl-silicon.
In a preferred embodiment of the present invention, in any embodiment of any formula described herein, T is bridging group Group, and be shown in following formula：R'2C, R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R'C= CR', R'C=CR'CR'2, R'2CCR'=CR'CR'2, R'C=CR'CR'=CR', R'C=CR'CR'2CR'2, R'2CSiR'2, R'2SiSiR'2, R2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2, R'2CGeR'2, R'2GeGeR'2, R'2CGeR'2CR'2, R'2GeCR'2GeR'2, R'2SiGeR'2, R'C=CR'GeR'2, R'B, R'2C-BR', R'2C-BR'-CR'2, R'2C-O-CR'2, R'2CR'2C-O-CR'2CR'2, R'2C-O-CR'2CR'2, R'2C-O-CR'=CR', R'2C-S-CR'2, R'2CR'2C-S-CR'2CR'2, R'2C-S-CR'2CR'2, R'2C-S-CR'=CR', R'2C-Se-CR'2, R'2CR'2C-Se-CR'2CR'2, R'2C-Se-CR2CR'2, R'2C-Se-CR'=CR', R'2C-N=CR', R'2C-NR'-CR'2, R'2C-NR'-CR'2CR'2, R'2C-NR'-CR'=CR', R'2CR'2C-NR'-CR'2CR'2, R'2C-P=CR', or R'2C-PR'-CR'2, wherein Each R' is independently hydrogen or contains C1-C20Alkyl, substituted alkyl, halocarbyl, substituted halocarbyl, monosilane Base is carbon-based or the carbon-based substituent of germyl and optionally two or more adjacent R' can engage formed substitution or It is unsubstituted, saturation, part is undersaturated or aromatics, ring-type or polycyclic substituent.Preferably, T is CH2, CH2CH2, C (CH3)2, SiMe2, SiPh2, SiMePh, silicyl cyclobutyl (Si (CH2)3), (Ph)2C, (p- (Et)3SiPh)2C, the silicylene of ring penta (Si (CH2)4), or Si (CH2)5。
In embodiments of the invention, in any formula as described herein, each R2And R8It is independently C1-C20Alkyl, Or C1-C20Substituted alkyl, C1-C20Halocarbyl, C1-C20Substituted halocarbyl, C1-C20Silicyl is carbon-based, C1-C20 Substituted silicyl is carbon-based, C1-C20Germyl is carbon-based, or C1-C20The carbon-based substituent of substituted germyl.It is preferred that Ground, each R2And R8It is independently methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, hendecane Base, dodecyl or its isomers, preferably cyclopropyl, cyclohexyl, (1- cyclohexyl methyls) methyl, isopropyl etc..
In embodiments of the invention, in any embodiment of any formula described herein, R4And R10It is independently Substituted or unsubstituted aryl.The aryl preferably substituted includes such aryl, and wherein hydrogen is by alkyl, or substitution Alkyl, halocarbyl, substituted halocarbyl, silicyl is carbon-based, and substituted silicyl is carbon-based, and germyl is carbon-based, or Person substitution the carbon-based substituent of germyl, hetero atom or containing heteroatomic group substitute.
In a preferred embodiment of the present invention, in any embodiment of any formula described herein, R2And R8It is C1-C20Alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, 12 Alkyl or its isomers, preferably cyclopropyl, cyclohexyl, (1- cyclohexyl methyls) methyl, or isopropyl；And R4And R10It is independent Ground is selected from phenyl, naphthyl, anthryl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2,3- 3,5-dimethylphenyls, 2,4- diformazans Base phenyl, 2,5- 3,5-dimethylphenyls, 2,6- 3,5-dimethylphenyls, 3,4- 3,5-dimethylphenyls, 3,5- 3,5-dimethylphenyls, 2,4,5- front threes Base phenyl, 2,3,4,5,6- pentamethyl phenyl, 2- ethylphenyls, 3- ethylphenyls, 4- ethylphenyls, 2,3- diethyl phenyls, 2,4- diethyl phenyls, 2,5- diethyl phenyls, 2,6- diethyl phenyls, 3,4- diethyl phenyls, 3,5- diethyl phenyls, 3- Isopropyl phenyl, 4- isopropyl phenyls, 3,5- diisopropyl phenyls, 2,5- diisopropyl phenyls, 2- tert-butyl-phenyls, the tertiary fourths of 3- Base phenyl, 4- tert-butyl-phenyls, 3,5- di-tert-butyl-phenyls, 2,5- di-tert-butyl-phenyls, cyclopropyl, cyclobutyl, cyclopenta, ring Hexyl, carbazyl, indyl, pyrrole radicals, or cyclopenta [b] thienyl.In preferred embodiments, R2, R8, R4 And R10It is and the R as described in preceding sentence3, R5, R6, R7, R9, R11, R12And R13It is hydrogen.
According in embodiment of the present invention, suitable MCN compounds are shown in formula (1)：
AeMXn-e；
Or shown in formula (1c)：
TA2MXn-2；
Wherein：E is 1 or 2；T is the bridged group between two A groups；Each A is that the monocyclic or polycyclic of substitution is matched somebody with somebody Body, its π-be bonded on M and optionally comprising being selected from boron, the 14th race's atom (it is not carbon), the 15th race's atom or the 16th race Atom one or more ring hetero atom, and when e is 2, each A can be with identical or different, and it is to use at least one to limit at least one A Individual cyclopropyl substituent substitution, the cyclopropyl substituent is bonded directly to any sp on the bonding ring position of the part2 On carbon atom,
Wherein the cyclopropyl substituent is shown in following formula：
Wherein each R' is independently hydrogen, substituted or unsubstituted alkyl, or halogen；M is the transition for having ligancy n Metallic atom, and it is selected from the periodic table of elements the 3rd, 4 either 5 races or lanthanide metals atom, or actinide metal Atom；N is 3,4 or 5；It is univalent anionic ligand with each X, or two X ' engagements and is attached to shape on metallic atom Cheland, diene ligand or alkylene ylidene ligands are formed into metal ring ring, or two X ' engagements.
According in embodiment of the present invention, MCN compounds can be shown in following formula：
Ty(A)e(E)MXn-e-1
Wherein E is J-R "x-1-y, the ligancy that J comes from the race of the periodic table of elements the 15th is 3 hetero atom, or comes from In the hetero atom of the ligancy 2 of the 16th race；R " is C1-C100Substituted or unsubstituted alkyl；X is hetero atom J ligancy, its In " x-1-y " represent to be attached to the number of R " substituents on J；T is the bridged group between A and E, and A and E are attached on M, y It is 0 or 1；And A, e, M, X and n are as defined above.
According in embodiment of the present invention, the MCN compounds can be shown in one of following formula：
Wherein M, T, X are as defined in claim 1；J, R " and n are as defined above, and
Each R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13Or R14It is independently hydrogen, substituted alkyl, Unsubstituted alkyl, or halogen, it is limited in formula 1a and 1b, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13Or Person R14In it is at least one be cyclopropyl substituent and in formula 2a and 2b, R1, R2, R3, R4, R5, R6Or R7In at least one Individual is cyclopropyl substituent；With any adjacent R of restriction1-R14Group (it is not cyclopropyl substituent) can be formed condensed ring or Person's multicenter fused ring system, the wherein ring can be aromatics, fractional saturation or saturation.
According in embodiment of the present invention, at least one A is monocyclic part, and it is selected from substituted or unsubstituted ring penta Dialkylene, heterocyclic pentylene base, and miscellaneous phenyl ligands, limit when e is 1, the monocyclic part is taken with least one cyclopropyl For base substitution, at least one A is polycyclic part, and it is selected from substituted or unsubstituted indenyl, fluorenyl, cyclopenta [a] naphthalene Base, cyclopenta [b] naphthyl, miscellaneous pentalene base, heterocyclic pentylene pentalene base, miscellaneous indenyl, miscellaneous fluorenyl, heterocycle Pentadiene and naphthyl, heterocyclic pentylene and indenyl, and miscellaneous benzo cyclopenta indenyl ligands.
Following one or more are may further include suitable for this paper MCN compounds：Dimethylated methylene silylation- Double (2- cyclopropyl -4- phenyl indenyls) zirconium dichlorides；Dimethylated methylene silylation-bis- (2- cyclopropyl -4- phenyl indenyls) dichloro Change hafnium；Dimethylated methylene silylation-bis- (2- methyl 4-phenyls indenyl) zirconium dichloride；Dimethylated methylene silylation-bis- (2- first Base -4- phenyl indenyls) hafnium dichloride；Dimethylated methylene silylation-bis- (2- methyl -4- neighbour's xenyls indenyl) hafnium dichloride；Two Methyl silicylene-bis- (2- methyl -4- neighbour's xenyls indenyl) zirconium dichloride；Dimethylated methylene silylation-(2- cyclopropyl- 4- neighbour's xenyl indenyl) (2- methyl -4-3', 5'- di-t-butyl phenyl indenyl) hafnium dichloride；Dimethylated methylene silylation- (2- cyclopropyl -4- neighbour's xenyls indenyl) (2- methyl -4-3', 5'- di-t-butyl phenyl indenyl) zirconium dichloride；Dimethyl is sub- Silicyl-(2- isopropyls -4 (the 4- tert-butyl groups) phenyl) indenyl) (2- methyl 4-phenyls indenyl) zirconium dichloride；Dimethyl is sub- Silicyl-(2- isopropyls -4 (the 4- tert-butyl groups) phenyl) indenyl) (2- methyl 4-phenyls indenyl) hafnium dichloride；Dimethyl is sub- Silicyl-(2- isopropyls -4 (the 4- tert-butyl groups) phenyl) indenyl) (2- methyl, 4- tert-butyl groups indenyl) zirconium dichloride；Dimethyl Silicylene-(2- isopropyls -4 (the 4- tert-butyl groups) phenyl) indenyl) (2- methyl, 4- tert-butyl groups indenyl) hafnium dichloride；Diformazan Base silicylene-(2- isopropyls -4 (the 4- tert-butyl groups) phenyl) indenyl) (2- methyl 4-phenyls indacene base) zirconium dichloride； Dimethylated methylene silylation-(2- isopropyls -4 (the 4- tert-butyl groups) phenyl) indenyl) (2- methyl 4-phenyls indacene base) dichloride Hafnium；Dimethylated methylene silylation (4- neighbour's xenyl -2- (1- methylcyclohexyls) methyl-indenyl) (4- (3,5- di-t-butyl benzene Base) -2- methyl-indenyls) zirconium dichloride；With dimethylated methylene silylation (4- neighbour's xenyl -2- (1- methylcyclohexyls) methyl - Indenyl) (4- (3,5- di-t-butyls phenyl) -2- methyl-indenyls) hafnium dichloride；Wherein in selective embodiment, with On dichloride base in any compound enumerated can use dialkyl group (such as dimethyl), two alkaryls, two is fluorine-based, two iodos or The bromo of person two or its combination substitution.
In a kind of preferred embodiment of the present invention, racemic and mole of meso in catalyst precursor compounds Than being 1:1-100:1, preferably 5:1-90:1, preferably 7:1-80:1, preferably 5:1 is either bigger or 7:1 it is either bigger or 20:1 is either bigger or 30:1 is either bigger or 50:1 or bigger.In one embodiment of the present invention, the MCN Catalyst includes the racemic isomer more than 55mol%, either the racemic isomer more than 60mol% or is more than 65mol% racemic isomer, the either racemic isomer more than 70mol% or different more than 75mol% racemic Structure body, the either racemic isomer more than 80mol% or the racemic isomer more than 85mol%, or be more than 90mol% racemic isomer, the either racemic isomer more than 92mol% or different more than 95mol% racemic Structure body, or the racemic isomer more than 98mol%, based on formed racemic and mesoisomer (if Words) total amount.In the specific embodiment of the present invention, double (indenyl) metaliocene transition metal compounds of the bridging formed Thing is substantially made up of racemic isomer.
Racemic and the amount of mesoisomer are determined by proton NMR.1H NMR datas are to be visited at 23 DEG C in 5mm In pin, using 400MHz Bruker spectrophotometers, collected with the dichloromethane of deuterate.(it should be noted that the one of this paper A little embodiments have used the benzene of deuterate, but for the purpose of claims, should use dichloromethane).Data are to make With 45 ° of maximum pulse, the signal of 5 seconds pulse spacings and average 16 transient states records.Dichloro by wave spectrum to deuterate Dichloromethane (it is it is contemplated that 5.32ppm shows appearance) standardization of protonation in methane.
In some embodiments, two kinds or more kinds of different MCN catalyst precursor compounds are present in this paper institutes In catalyst system.In some embodiments, two or more different MCN catalyst precursor compounds are present in In such reaction zone, there occurs method described herein (one or more) wherein.When two kinds of transistion metal compound bases When catalyst is used for a reactor as the catalyst system of mixing, two kinds of transistion metal compounds should be selected, so that It is compatible to obtain the two.Can for example it be passed through using simple screening method well known by persons skilled in the art1H or13C NMR come It is compatible to determine which transistion metal compound.Identical activator is preferably used for the transistion metal compound, so And two kinds of different activators (such as two kinds of non-coordinating anion, non-coordinating anion activator and aikyiaiurnirsoxan beta, or two kinds Different aikyiaiurnirsoxan betas) it can be applied in combination.If it is not hydrogen-based that one or more transistion metal compounds, which include, alkyl or take The X parts of the alkyl in generation, then the aikyiaiurnirsoxan beta (or other alkylating reagents) generally add non-coordinating anion activator it Before, contacted with transistion metal compound.
Two kinds of transistion metal compounds (pre-catalyst) can be used with any ratio.(A) transistion metal compound with (B) the preferable mol ratio of transistion metal compound falls into 1:1000-1000:1, alternatively 1:100-500:1, alternatively 1: 10-200:1, alternatively 1:1-100:1, alternatively 1:1-75:1, and alternatively 5:1-50:1 (A：B in the range of). Specific ratio will select depending on selected definite pre-catalyst, activation method and desired final product.In spy In fixed embodiment, when using two kinds of pre-catalysts, wherein the two is activated with identical activator, based on urging in advance The molecular weight of agent, useful molar percentage are 10-99.9mol%A than 0.1-90mol%B, alternatively 25-99mol% A is than 0.5-50mol%B, and alternatively 50-99mol%A is than 1-25mol%B, and alternatively 75-99mol%A compares 1- 10mol%B.
Chain-transferring agent：The invention further relates to use above-mentioned complex compound polymerizable alkenyl in the presence of chain-transferring agent (" CTA ") The method of hydrocarbon.The CTA can be it is any it is desirable that chemical compound, such as those disclosed in WO2007/130306. Preferably, the CTA is selected from the 2nd, 12 either 13 race's alkyl or aryl compound；It is preferred that alkyl or aryl zinc, alkyl or Aryl magnesium either alkyl or aryl aluminium；The alkyl is C preferably wherein1-C30Alkyl, alternatively C2-C20Alkyl, alternatively C3-C12Alkyl, it is mostly independently selected from methyl, ethyl, propyl group, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, cyclohexyl, Phenyl, octyl group, nonyl, decyl, undecyl and dodecyl；Such as dialkyl zinc compounds, the wherein alkyl independently select From methyl, ethyl, propyl group, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, cyclohexyl and phenyl, wherein diethyl zinc is special Preferably；Such as trialkyl aluminium compound, the wherein alkyl is independently selected from methyl, ethyl, propyl group, butyl, isobutyl group, The tert-butyl group, amyl group, hexyl, cyclohexyl and phenyl；Such as diethyl aluminum chloride, diisobutyl aluminium hydride, diethyl hydrogenation Aluminium, di-n-octyl aluminum hydride, dibutylmagnesium, magnesium ethide, dihexyl magnesium and boron triethyl.
Useful CTA is generally with 10, either 20 or 50, either 100 equivalents to 600 or 700, either 800 or 1000 equivalents are present, relative to catalytic component.Alternatively the CTA is about 1 with catalyst complex and CTA mol ratios: 3000-10:1；Alternatively 1:2000-10:1；Alternatively 1:1000-10:1；Alternatively 1:500-1:1；Alternatively 1:300-1:1；Alternatively 1:200-1:1；Alternatively 1:100-1:1；Alternatively 1:50-1:1；Or/and alternatively 1:10-1:1 is present.
Monomer：Useful monomer includes substituted or unsubstituted C herein2-C40Alhpa olefin, preferably C2-C20Alhpa olefin, it is excellent Select C2-C12Alhpa olefin, optimal ethylene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, endecatylene, 12 carbon Alkene and its isomers.In preferred embodiments, the monomer includes propylene and optional comonomer (one or more), its Ethene or C comprising one or more4-C40Alkene, preferably C4-C20Alkene, or preferred C6-C12Alkene.The C4-C40Alkene Monomer can be it is linear, it is branched or ring-type.The C4-C40The alkene of ring-type can be tensioning (strained) or not open Tight (unstrained), it is monocyclic or polycyclic, and can optionally include hetero atom and/or one or more functional groups. In a preferred embodiment of the present invention, the monomer is propylene, and comonomer is not present.
Exemplary C2-C40Olefinic monomer and optional comonomer include ethene, propylene, butylene, amylene, hexene, heptan Alkene, octene, nonene, decene, endecatylene, dodecylene, ENB, norbornadiene, bicyclopentadiene, cyclopentene, ring Heptene, cyclo-octene, cyclo-octadiene, cyclododecene, 7- oxanorbornenes, 7- oxanorbornadienes, its derivative substituted Thing and its isomers, preferably hexene, heptene, octene, nonene, decene, dodecylene, cyclo-octene, 1,5- cyclo-octadiene, 1- hydroxyls Base -4- cyclo-octene, 1- acetoxyl group -4- cyclo-octene, 5- methyl cyclopentenes, cyclopentene, bicyclopentadiene, ENB, ice drops Piece diene and their respective homologue and derivative, preferably ENB, norbornadiene and bicyclopentadiene.
In preferred embodiments, the amount in the polymer that one or more diene produce herein is at most 10 Weight %, preferably 0.00001-1.0 weight %, preferably 0.002-0.5 weight %, even more preferably 0.003-0.2 weight %, base In the gross weight of said composition.In some embodiments, 500ppm or less diene are added in polymerization, preferably 400ppm is less, preferably either 300ppm or less.In other embodiments, at least 50ppm diene is added In polymerization, either 100ppm or more, either 150ppm or more.
Preferable diolefinic monomer available for the present invention includes any hydrocarbon structure with least two unsaturated bonds, excellent Select C4-C30, wherein at least two in the unsaturated bond are (a kind of easily by stereotaxis or non-cubic directional catalyst Or a variety of) be introduced into polymer.Further preferably the diolefinic monomer is selected from α, ω-diene monomers (that is, divinyl lists Body).It is highly preferred that the diolefinic monomer is linear di-vinyl monomers, most preferably 4-30 carbon atom those.It is preferred that The example of diene include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon diene, oleatridecadiene, 14 carbon diene, 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, two 15 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene are special Not preferable diene includes 1,6- heptadiene, 1,7- octadiene, 1,8- nonadiene, 1,9- decadinene, 1,10- ten one carbon diene, 1,11- ten two carbon diene, 1,12- oleatridecadiene, 1,13- ten four carbon diene, and (Mw is less than low molecular weight polybutadiene 1000g/mol).Preferable cyclic diene includes cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene Alkene, divinylbenzene, bicyclopentadiene or the alkadienes containing higher level ring, it has or not on different ring positions With substituent.
Preferably, the polymerization or copolymerization are to use alkene such as ethene, propylene, 1- butylene, 1- hexenes, 4- methyl-l- What amylene, and 1- octenes, vinyl cyclohexane, ENB and norbornadiene were carried out.Especially, polypropylene and ethene.
In some embodiments, wherein butylene is comonomer, and the butylene source can include different butylene isomeries The mixed butene stream of body.1- butene monomers are expected preferentially to be consumed by polymerization.Will using such mixed butene stream Economic benefits are provided, because these mixture flows often come from the waste streams of method of refining, such as C4Residual oil stream, and because This can be expensive apparently without pure 1- butylene.
In preferred embodiments, in any stage, preferably in all stages, the monomer includes the two of 0wt% Alkene monomer.
Preferably, amount of the comonomer (one or more) in final prolylene polymer composition is less than 50mol%, preferably 0.5-45mol%, preferably 1-30mol%, preferably 3-25mol%, preferably 5-20mol%, preferably 7- 15mol%, and the surplus of the copolymer is made up of principal monomer (such as propylene), based on the molecule.
In a preferred embodiment of the present invention, stage A (and/or stage A1 and A2, such as when polymer A is bimodal When) produced in polymer be iPP, preferably isotaxy homo-polypropylene and include propylene in polymer caused by stage B With 0.5-50mol% (preferably 0.5-45mol%, preferably 1-30mol%, preferably 3-25mol%, preferably 5-20mol%, preferably 7-15mol%, and the surplus of the copolymer is made up of propylene) ethene or C4-C20Alhpa olefin, optimal ethylene and butylene, oneself Alkene and/or octene.
In preferred embodiments, stage A can include multiple sub-stages, such as stage A1, stage A2 etc..As herein Used, stage A refers to whole sub-stages.In a preferred embodiment of the present invention, the polymerization produced in stage A1 Thing is iPP, and preferably the polymer produced in isotaxy homo-polypropylene, and stage A2 is iPP.
In a preferred embodiment of the present invention, the polymer produced in stage A1 is iPP, and preferably isotaxy is equal Polymer produced in polypropylene, and stage A2 is that the polymer produced in iPP, and stage B includes propylene and 0.5- 50mol% (preferably 0.5-45mol%, preferably 1-30mol%, preferably 3-25mol%, preferably 5-20mol%, preferably 7- 15mol%, and the surplus of the copolymer is made up of propylene) ethene and butylene, either ethene and hexene or ethene and pungent Alkene.
Sequential polymerization：Prolylene polymer composition according to embodiments of the present invention can use conventional polymerization example Prepared such as dual stage process in two reactors or three stage methods in three reactors, although can also be These compositions are produced in single reactor.In embodiments, each stage can be independently in gas phase, solution or liquid Carried out in slurry phase.For example, the first stage can carry out carrying out in liquid slurry with second stage in the gas phase, or it is on the contrary Phase III as the same and optional is carried out in gas phase or slurry phase.Alternatively, each phase can be in different phases It is identical.The prolylene polymer composition of the present invention can be in multiple reactors of series operation, preferably at two or three Produced in individual reactor, wherein component A1 preferably polymerize in gas phase, liquid slurry or solution polymerization process first.Component B (polymeric material produced in the presence of component A) gathers preferably in second reactor such as gas phase or sludge phase reactor Close.In selective embodiment, component A can be prepared at least two reactors, to obtain with different performance (example Such as different molecular weight, polydispersity, melt flow rate (MFR) etc.) part.
As used herein, " stage " is defined as the part of polymerization, produces in reactor and combines during it A kind of component of thing, component A (or component A1 and A2, if present) either component B (or component C, if there is another If one stage).One or more reactor can be used in each phase process.Identical or different polymerization can For in each stage.For example, clear and convenient purpose, component A and/or stage A can be hereinafter referred to as iPP and The polyacrylic stage is produced, component A1 and/or stage A1 can be hereinafter referred to as the first iPP most probable values and production first poly- third The stage of alkene most probable value, component A2 and/or stage A2 can be hereinafter referred to as the 2nd iPP most probable values and production second poly- third The stage of alkene most probable value, and component B and/or stage B can be hereinafter referred to as rubber and produce the stage of rubber, it is understood that It is that polymer can produce in any order or in same reactor and/or series reaction device.
The stage of the inventive method can connect in solution, suspension or gas phase in any manner known in the art It is continuous either intermittently or its any combination, carry out in one or more steps.Homogeneous polymerization method is useful.With regard to herein Purpose for, homogeneous polymerization method is defined as such method, and wherein at least 90wt% product dissolves in reaction medium In.Body homogeneous process is also useful, wherein bulk process is defined as such method for this paper purpose, wherein The monomer concentration being sent in all feed of reactor is 70 volume % or bigger.Alternatively, in embodiments, instead Solvent or diluent can be not present or be added without by answering in medium, except the load as catalyst system or other additives The amounts that are a small amount of, or generally being found together with monomer of body；Such as the propane known in the art in propylene.Term " gas phase Polymerization " refers to the state of monomer in the course of the polymerization process, wherein " gas phase " refers to the vaporous of monomer.In another embodiment In, slurry process was used in one or more stages.As used herein, term " slurry phase polymerisation process " represents such polymerization Method, wherein using the catalyst of load, and monomer is polymerize on the catalyst granules of load, and derived from load At least 95wt% polymer product of catalyst is the pellet form as solid particle (not dissolving in diluent).Gas phase is gathered Conjunction method is particularly preferred, and be can be used in one or more stages.
In embodiments of the invention, stage A1 produces hPP, and stage B produces propylene copolymer, such as third Alkene-ethylene copolymer.In the selective embodiment of the present invention, stage A produces hPP and stage B produces hPP. In the selective embodiment of the present invention, stage A1 and stage A2 produces hPP and stage B produces propylene copolymer, example Such as propylene-ethylene copolymers.In the selective embodiment of the present invention, stage B produces hPP, and stage A produces third Alkene copolymer, such as propylene-ethylene copolymers.In the selective embodiment of the present invention, stage A1 and stage A2 productions HPP.
In embodiments of the invention, can be with if polymerization is carried out as suspension or polymerisation in solution Using atent solvent, such as the polymerization can be carried out in suitable diluent/solvent.For polymerization suitable diluent/ Solvent includes noncoordinating inert fluid.Example includes straight chain and branched-chain hydrocarbons, such as iso-butane, butane, pentane, isopentane, oneself Alkane, isohexane, heptane, octane, dodecane and its mixture；Ring-type and clicyclic hydrocarbon, such as hexamethylene, cycloheptane, methyl Hexamethylene, methylcycloheptane and its mixture, such as can be commercially available (IsoparTM)；Perhalogenation hydrocarbon, such as perfluor Change C4-10Alkane, chlorobenzene, and aromatics and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene and dimethylbenzene.Close Suitable diluent/solvent also includes liquid olefin, and it can serve as monomer or comonomer, including ethene, propylene, 1- fourths Alkene, 1- hexenes, 1- amylenes, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 1- octenes, 1- decene and its mixture.Preferable In embodiment, aliphatic hydrocarbon solvent is used as solvent, such as iso-butane, butane, pentane, isopentane, hexane, isohexane, heptane, Octane, dodecane and its mixture；Ring-type and clicyclic hydrocarbon, such as hexamethylene, cycloheptane, hexahydrotoluene, methyl cycloheptyl Alkane and its mixture.In another embodiment, the solvent is not aromatics, and amount of the preferred aromatic hydrocarbons in the solvent is less than 1wt%, preferably smaller than 0.5wt%, preferably smaller than 0wt%, the weight based on the solvent.Rosin or hydrogenation can also be used Diesel oil distillate is as solvent.Toluene can also be used.The polymerization is preferably carried out in liquid monomer (one or more).If make With atent solvent, then monomer (one or more) is typically to be measured with gas or liquid form.
In embodiments of the invention, it is 60vol% solvents for the monomer of polymerization and the feed concentration of comonomer Either lower or 40vol% is lower, either 20vol% or lower, the cumulative volume based on feed streams.In embodiment party In case, the polymerization is run in bulk process.
In embodiments of the invention, polymerization can be in any temperature and/or pressure suitable for obtaining desired polymer Power is run.Common temperature and/or pressure are greater than 30 DEG C including temperature in any stage, or more than 50 DEG C, Huo Zhe great In 65 DEG C, either more than 70 DEG C or more than 75 DEG C, alternatively less than 300 DEG C, either less than 200 DEG C or less than 150 DEG C, or less than 140 DEG C；And/or pressure is 100kPa-20MPa, about 0.35MPa- about 10MPa, or about 0.45MPa- about 6MPa, or about 0.5MPa- about 5MPa.
In embodiments, the polymerization in any stage can include at most 300 minutes, or about 5-250 minutes, or The reaction run time of person's about 10-120 minutes.In embodiments of the invention, in a continuous process, all stages is poly- It is 1-600 minutes, either 5-300 minutes or about 10-120 minutes to close the time.
Hydrogen and/or other CTA can add one, in two or more reactor or reaction zone.In embodiment party In case, hydrogen is added to control the molecular weight of produced polymer and MFR.In embodiments, in the polymerization in each stage Integral pressure is at least about 0.5bar, either at least about 2bar or at least about 5bar.In embodiments, it is impossible to Using higher than about 100bar, such as higher than about 80bar and especially greater than about 64bar pressure.In some embodiment party In case, hydrogen is in polymerization zone with partial pressure 0.001-100psig (0.007-690kPa), or 0.001-50psig (0.007-345kPa), either 0.01-25psig (0.07-172kPa) or 0.1-10psig (0.7-70kPa) are present. In embodiment of the present invention, hydrogen and/or CTA can add first reactor, and second either the 3rd or subsequent reactor Or its any combination.Equally, in three stage methods, hydrogen can add first stage and/or second stage and/or the 3rd rank Section.In embodiments of the invention, hydrogen is with higher than in the concentration of first stage addition second stage.In the selective of the present invention Embodiment in, hydrogen with higher than the concentration of second stage add the first stage in.On sublevel in being produced in impact copolymer Section is hydrogenated with further information, and referring to the USSN61/896291 submitted on October 28th, 2013, it is as US2015- Disclosed in 0119537, it is incorporated herein by reference.
The polymerization of the present invention can be carried out with interval, semi-batch or continuous mode in each stage.If Using two or more reactors (or reaction zone), then preferably they are combined to form continuation method.In the reality of the present invention Apply in scheme, polymerization can be in any temperature and/or the pressure operation suitable for obtaining desired polymer.In the implementation of the present invention In scheme, the method for producing prolylene polymer composition is continuous.
In embodiments of the invention, in the first stage in A, propylene and about 0wt%-15wt%C2And/or C4-C20 Alhpa olefin (alternatively 0.5-10wt%, alternatively 1-5wt%) is (based on monomers/comonomers feed (and optional H2) Weight) contacted under polymerization conditions with MCN catalyst (one or more) as described herein to form component A.This first In stage, monomer preferably comprises propylene and optional comonomer, and it includes one or more ethene and/or C4-C20Alkene, It is preferred that C4-C16Alkene, or preferred C6-C12Alkene.The C4-C20Olefinic monomer can be it is linear, it is branched or ring-type.Should C4-C20Cyclic olefin can be tensioning or not be tensioned, monocyclic or polycyclic, and can optionally include hetero atom And/or one or more functional groups.In a preferred embodiment of the present invention, the monomer in stage A is propylene, and is not deposited In comonomer.
In embodiments of the invention, in second stage B, propylene and about 0wt%-15wt%C2And/or C4-C20 Alhpa olefin (alternatively 0.5-10wt%, alternatively 1-5wt%) (weight based on monomers/comonomers feed) and this MCN catalyst (one or more) described in text contacts to form component B under polymerization conditions.In the second stage, the list Body preferably comprises propylene and optional comonomer, and it includes one or more ethene and/or C4-C20Alkene, preferably C4-C16 Alkene, or preferred C6-C12Alkene.The C4-C20Olefinic monomer can be it is linear, it is branched or ring-type.The C4-C20Ring-type alkene Hydrocarbon can be tensioned or not be tensioned, monocyclic or polycyclic, and can optionally include hetero atom and/or one or more Functional group.In a preferred embodiment of the present invention, the monomer in stage B is propylene and comonomer be present.
Alternatively, in second stage, component A, propylene and the optional weight based on monomers/comonomers feed Count about 1wt%-15wt% (preferably 3wt%-10wt%) one or more comonomers (such as ethene or C4-C20α alkene Hydrocarbon) in the presence of MCN catalyst systems as described herein (a kind of and a variety of) and optional hydrogen, contact under polymerization conditions carrys out shape Into the component B closely mixed with component A, this results in prolylene polymer composition.In the second stage, optional copolymerization list Body can include one or more ethene and C3-C20Alkene, preferably C4-C16Alkene, or preferred C6-C12Alkene.The C4-C20 Olefinic monomer can be it is linear, it is branched or ring-type.The C4-C20Cyclic olefin can be tensioned or not be tensioned, monocyclic Or it is polycyclic, and can optionally include hetero atom and/or one or more functional groups.
Alternatively, in second stage, component A and propylene are (a kind of or more in MCN catalyst systems as described herein Kind) and hydrogen in the presence of, contact under polymerization conditions forms the component B closely mixed with component A, and this results in acrylic polymers Composition.
Alternatively, in second stage, component A and ethene are (a kind of or more in MCN catalyst systems as described herein Kind) and hydrogen in the presence of, contact under polymerization conditions forms the component B closely mixed with component A, and this results in acrylic polymers Composition.
Catalyst system used in the stage can be with identical or different, and preferably identical.In the reality of the present invention Apply in scheme, catalyst system used is transferred to stage B with polymerizate (such as component A) together with stage A, wherein it and Other monomer is contacted to form component B and thus final prolylene polymer composition.In other embodiments of the present invention In, by catalyst provide to 1,2 or all 3 reaction zones.
In embodiments of the invention, stage A produces homo-polypropylene, and stage B produces Ethylene/Butylene, and ethene- Hexene, ethylene-octene, ethylene-propylene, ene-propylene-butene, ethylene-butene-hexene, or ethylene-propylene-octene are total to Polymers.
In one embodiment of the present invention, using seldom or without using scavenger next life in the polymerization in any stage Produce polymer, i.e. scavenger (such as trialkylaluminium) is using scavenger metal and transition metal mole ratio as 0:1, alternatively Less than 100:1, or less than 50:1, or less than 15:1, or less than 10:1, or less than 1:1, or less than 0.1:1 deposits .
Other additives can also be used in the polymerization in any stage as needed, such as one or more scavengers, promote Enter agent, modifying agent, hydrogen, as the replacement of hydrogen or the CTA (such as diethyl zinc) of supplement, reducing agent, oxidant, alkyl aluminum or Silane etc..
In one embodiment of the present invention, the single stage or in all Assembly Phases catalyst system life Yield is at least 50g (polymer)/g (catalyst)/hour, preferably 500 or bigger g (polymer)/g (catalyst)/hour, It is preferred that 800 or bigger g (polymer)/g (catalyst)/hour, preferably 5000 or bigger g (polymer)/g (catalyst)/ Hour, preferably 50000 or bigger g (polymer)/g (catalyst)/hour.
In one embodiment of the present invention, the single stage or in all Assembly Phases catalyst system work Property is at least 50kg P/mol cat, preferably 500 or bigger kg P/mol cat, preferably 5000 or bigger kg P/mol Cat, preferably 50000 or bigger kg P/mol cat.According to some embodiments of the present invention, in the single stage or in institute The catalyst activity for having the catalyst system in Assembly Phase to provide is at least 800, either at least 1000 or at least 1500, Or acrylic polymers/g catalyst precursor compounds/hour that at least 2000g is produced.
In another embodiment of the present invention, the conversion ratio of olefinic monomer is at least 10%, based on polymer yield and Into the weight of the monomer of reaction zone, either 20% or bigger, either 30% or bigger, either 50% or bigger, or Person 80% is bigger." reaction zone ", also referred to as " polymeric area ", be wherein carry out polymerization container or its part or The combination of person's container, such as batch reactor.When multiple reactors are come in use, each reactor with construction in series or in parallel It is considered as the polymeric area of difference.For the multistage polymerization in both batch reactor and flow reactor, each Polymerization stage is considered as the polymeric area of difference.In preferred embodiments, 2,3,4 are aggregated in or more are anti- Answer in area and occur.In another embodiment of the present invention, the conversion ratio of olefinic monomer is at least 10%, based on polymer yield With the weight of the monomer that enters all reaction zones, either 20% or bigger, either 30% or bigger, either 50% or more Greatly, either 80% or bigger.
In embodiments of the invention, using single MCN Catalyst Productions polymer composition such as heterophasic copolymer And/or the method for impact copolymer (ICP) can include polymerising ethylene first, then using identical or different catalyst, Polypropylene in the presence of the polyethylene.Generally, polypropylene first, then with ethene, ethene polymers is by being blended and/or leading to Cross with ethylene/propene copolymer modification to be modified.By inverting aggregation order and by selecting appropriate catalyst, realizing second Alkene content is more than 30wt% ICP.
In embodiments of the invention, methods described can include in the first phase by ethene and optional C2-C12 Alpha-olefin comonomer under polymerization conditions, is contacted to form component A in the presence of the first MCN catalyst systems；In second-order By step a) component A and C in section3-C12'alpha '-olefin monomers under polymerization conditions, connect in the presence of the 2nd MCN catalyst systems Touch to form component B, wherein the first MCN catalyst systems are present in MCN catalyst in both step a and b and/or other Added between step a and b in reactant mixture, and the first MCN catalyst systems can be with the 2nd MCN catalyst systems It is identical；, wherein should the reactor based on ethene with composition in the reactor based on ethene of the acquisition comprising component A and component B Interior composition have more than 20mol% ethene, based on this in reactor based on ethene composition molecular weight.In the present invention Embodiment in, multimodal fusing point should can be had based on composition in the reactor of ethene.In embodiments of the invention, ICP as offer, its ethylene contents is more than 20mol%, either more than 30mol% or more than about 40mol%, or More than about 50mol%, either more than about 65mol% or more than 85mol%, the molecular weight based on the ICP.
In another further aspect, the reaction sequence of step 1 and step 2 can be carried out immediately.Alternatively, produce polyethylene and The polyethylene and propylene further may have 1 second between reaction or bigger, alternatively 30 seconds or bigger, alternatively 1 minute or bigger, alternatively 15 minutes or bigger, alternatively 30 minutes or bigger, alternatively 1 hour or It is bigger, alternatively 2 hours or bigger, alternatively 1 day or bigger a period of time.
High porosity acrylic polymers product：This paper polymer product can include polypropylene, such as such as iPP, height Isotactic polypropylene, sPP, hPP and RCP.
In any embodiment of the present invention, prepared acrylic polymers is that iPP or height are complete same in stage A1 Vertical structure polypropylene, preferably homo-polypropylene.In any embodiment of the present invention, prepared acrylic polymers is in stage A2 Propylene copolymer, preferably propylene and C2Or C4-C20The copolymer of alkene (optimal ethylene).In a kind of embodiment of the present invention In, prepared acrylic polymers is isotaxy homo-polypropylene or height isotaxy homo-polypropylene in stage A1.At this In a kind of embodiment of invention, prepared acrylic polymers is ethylene-propylene rubber in stage A2.
According to some embodiments of the present invention, the porosity of the propylene polymer matrix is 15% or bigger, such as 20%, either 25% or 30%, either 35% or 40%；Height to 85%, 80%, 75%, 70%, 60%, or 50%, the cumulative volume based on propylene polymer matrix, it is measured by mercury injection method.
According to some embodiments of the present invention, the intermediate value PD of the propylene polymer matrix is less than 165 μm, is greater than 6- Less than 160 μm, it is determined by mercury injection method.In other or selective embodiment, the propylene polymer matrix Intermediate value PD be greater than 0.1, more than 1, either more than 2 or more than 5, either more than 6 or more than 8, or more than 10, or Person is more than 12, either more than 15 or more than 20 μm；Height, which arrives, is less than 50, either less than 60 or less than 70, or less than 80, Either less than 90 or less than 100, either less than 120 or less than 125, either less than 140 or less than 150, Huo Zhe little In 160, or less than 165 μm.
According to some embodiments of the present invention, the acrylic polymers, which has, is more than 5, either more than 10 or more than 15 Individual area defects/10000 propylene units, it is to pass through13C NMR measure.
According to some embodiments of the present invention, 1% Secant flexural modulus of the acrylic polymers is at least 1000MPa, For example, at least 1300MPa, either at least 1500MPa or at least 1700MPa, either at least 1800MPa or at least 1900MPa, or at least 2000MPa, it is determined according to ASTM D790 (A, 1.0mm/min).
According to some embodiments of the present invention, the acrylic polymers has multimodal MWD.According to some implementations of the present invention Scheme, the acrylic polymers have multimodal PSD.
According to some embodiments of the present invention, the acrylic polymers further includes second polymer, its at least part Hole in ground filling substrate.For example, the second polymer can be rubber filling material, it fills the hole at least in part, Such as such as ethylene-propylene copolymer, such as ethene and about 3wt%-75wt% one or more C3-C20The copolymerization of alhpa olefin Thing, the weight based on the ethylene copolymer.In some embodiments, wherein forming the acrylic polymers in hole can easily exist Referred herein as " first polymer ", it is not intended that what second polymer was necessarily present, or if there is, it is not intended to The first polymer is formed before second polymer.
According in embodiment of the present invention, the acrylic polymers is multiphase and/or impact copolymer, such as comprising Second polymer, such as filled rubber, it is arranged in hole with following amount：At least 20, either at least 30 or at least 40, Either at least 50 or at least 60, either at least 70 or at least 80, either at most 85vol% or bigger, based on impact The cumulative volume of copolymer.In other or selective embodiment, the second polymer is substantially completely arranged in described Kong Zhong, i.e. the outer surface of the polymer beads there is no second polymer, to cause the polymer beads to keep free flow It is dynamic, and not agglomeration and block process equipment such as reactor used in their production, pipeline, pipe fitting and/or valve.
According to some embodiments of the present invention, the acrylic polymers is particle form, such as such as wherein at least 95 weights Measure % and have and be more than about 120 μm, such as from 150,200,300,400 or 500 μm of height to 10,5 or 1mm granularity.
According to some embodiments of the present invention, the polymer is prepared with single site catalysts system, such as It has such performance or combining properties, and (it is commonly due to opposite with Z-N (ZN) catalyst system Single site catalysts polymerization-filling and/or its can be obtained by such polymerization), such as higher molecular weight, compared with Low polydispersity index, relatively low cold xylene extractable, the solid irregular being evenly distributed, copolymerization wherein be present Higher composition Distribution Breadth Index (CBDI) in the case of monomer, 5-200 area defects/10000 propylene units etc.. In other or selective embodiment, the polymer further includes active single site catalysts system, single activity The residue of site catalyst system or its combination, wherein the single site catalysts system includes single-site catalyzed Agent precursor compound, for the activator of precursor compound, and carrier.
According to some embodiments of the present invention, the acrylic polymers further includes active catalyst system, and it is included Single site catalysts precursor compound, for the activator of precursor compound, and carrier, it is distributed in acrylic polymers In porous matrix.
According to some embodiments of the present invention, the matrix of the acrylic polymers includes multiple polymer bulbec bodies, and it is limited Clearance space is determined, the clearance space forms the hole in polymer spheres., should in other or selective embodiment Matrix further includes the scattered microparticle of catalyst system, and it is precursor that the catalyst system includes single site catalysts Compound, activator and carrier.In other or selective embodiment, the carrier includes (1) silica agglomerate, its Average PS is greater than 30 μm of height to 200 μm, and it includes multiple primary with many smaller average PS (1nm-50 μm) Grain, the surface area of the wherein silica agglomerate is 400m2/ g is bigger, and pore volume is 0.5-2mL/g and average Kong Zhi Footpath is 1-20nm, and it is by BET nitrogen adsorption assays；Or (2) be spaced apart from each other in polymer bulbec body it is multiple Free primary granule, the wherein primary granule include the one or more primary granules disintegrated from silica agglomerate；Or (3) it is combined.
Multimodal propylene polymer product：In a preferred embodiment of the present invention, the acrylic polymers group produced herein Compound can have multimodal MWD polymer species, and it is determined by GPC-DRI.GPC-DRI marks are represented with multimodal MWD Line, which has, is more than a peak or flex point.In a preferred embodiment of the present invention, the propylene polymer composition produced herein Thing can have bimodal MWD polymer species, and it is determined by GPC-DRI.In the preferred embodiment of the present invention In, the prolylene polymer composition produced herein can have unimodal MWD polymer species, and it is surveyed by GPC-DRI Fixed.
In the other or selective preferred embodiment of the present invention, the prolylene polymer composition that produces herein There can be multimodal PSD, it is determined by laser diffraction.Represent that the PSD curves on volume have greatly with multimodal PSD In a peak or flex point.In a preferred embodiment of the present invention, the prolylene polymer composition that is produced can be with herein With bimodal PSD, it is by determination of laser diffraction.In another preferred embodiment of the present invention, produced herein Prolylene polymer composition can have unimodal PSD, it is by determination of laser diffraction.
In any embodiment of the present invention, the acrylic polymers (A1 components), which advantageously has, is less than 200 regions Defect (being defined as 2,1- erythro forms and the formula insertion of 2,1- Soviet Union, and 3,1- isomerization sum)/10000 propylene units, alternatively More than 5,10 or 15 and it is less than 200 area defects/10000 propylene units, alternatively more than 17 and is less than 175 areas Domain defect/10000 propylene units, either 30 or 40, but be less than 200 area defects alternatively more than 20, for choosing It is less than 150 area defects/10000 propylene units with selecting.The area defects are determined using 13C NMR spectras method, such as It is lower described.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 Have with the composition (A1 the and A2 components of combination) produced after stage A2 and (be defined as 2,1- less than 200 area defects Erythro form and 2,1- Soviet Union formula insertion, and 3,1- isomerization sum)/10000 propylene units, alternatively less than 150 regions lack / 10000 propylene units are fallen into, alternatively more than 5 and are less than 200 area defects/10000 propylene units, alternatively More than 15 and be less than 175 area defects/10000 propylene units, alternatively more than 17 and less than 175 area defects/ 10000 propylene units.
In any embodiment of the present invention, (Tm, DSC peak are secondary molten for the fusing point of acrylic polymers (A1) component Melt) can be at least 145 DEG C, either at least 150 DEG C or at least 152 DEG C, either at least 155 DEG C or at least 160 DEG C, or At least 165 DEG C of person, preferably approximately 145 DEG C-about 175 DEG C, about 150 DEG C-about 170 DEG C, or about 152 DEG C-about 165 ℃。
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 Fusing point (Tm, DSC peak second melting) with the composition (A1 the and A2 components of combination) produced after stage A2 can be to It is few 145 DEG C, either at least 150 DEG C or at least 152 DEG C, either at least 155 DEG C or at least 160 DEG C, or at least 165 DEG C, preferably approximately 145 DEG C-about 175 DEG C, about 150 DEG C-about 170 DEG C, or about 152 DEG C-about 165 DEG C.
In any embodiment of the present invention, 1% Secant flexural modulus of acrylic polymers (A1) component can be with It is from low spot about 1000MPa, about about 1100MPa, about 1200MPa, about 1250MPa, 1300MPa, about 1400MPa, or about 1500MPa is to high point about 1800MPa, about about 2100MPa, 2600MPa, or about 3000MPa, it is determined according to ASTM D790 (A, 1.0mm/min), preferably approximately 1100MPa- about 2200MPa, about 1200MPa- about 2000MPa, about 1400MPa- about 2000MPa, either about 1500MPa or bigger.1% secant is scratched Bent modulus is to pass through Instron by using the rod of ISO37- types 3 with crosshead speed 1.0mm/min and support span 30.0mm Machine is according to ASTM D790 (A, 1.0mm/min) come what is determined.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 About 1000MPa- is preferably with composition (A1 the and A2 components of combination) 1% Secant flexural modulus produced after stage A2 About 3000MPa, about 1500MPa- about 3000MPa, about 1800MPa- about 2500MPa, or about 1800MPa- About 2000MPa.
In any embodiment of the present invention, the melt flow rate (MFR) of acrylic polymers (A1) component (MFR, ASTM1238,230 DEG C, 2.16kg) can be from low spot about 0.1dg/min, about about 0.2dg/min, 0.5dg/min, About 1dg/min, about 15dg/min, about 30dg/min or about 45dg/min to high point about 75dg/min, about 100dg/min, about about 200dg/min or 300dg/min.For example, the MFR of the polymer can be about 0.5dg/ Min- about 300dg/min, about 1dg/min- about 300dg/min, about 5dg/min- about 150dg/min, about 10dg/min- about 100dg/min, or about 20dg/min- about 60dg/min.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 Can be with the MFR of the composition (A1 the and A2 components of combination) that is produced after stage A2 (ASTM1238,230 DEG C, 2.16kg) It is about 1dg/min- about 300dg/min, about 5dg/min- about 150dg/min, about 10dg/min- about 100dg/ Min, or about 20dg/min- about 60dg/min, preferably approximately 50- about 200dg/min, preferably approximately 55- is about 150dg/min, preferably approximately 60- about 100dg/min.
In any embodiment of the present invention, (it is surveyed by GPC-DRI to the Mw of acrylic polymers (A1) component Amount) can be 50000-1000000g/mol, alternatively 80000-1000000g/mol, alternatively 100000- 800000g/mol, alternatively 200000-600000g/mol, alternatively 300000-550000g/mol, or selective Ground 330000-500000g/mol.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 Mw (it is measured by GPC-DRI) with the composition (A1 the and A2 components of combination) produced after stage A2 can be 50000-1000000g/mol, alternatively 80000-1000000g/mol, alternatively 100000-800000g/mol, for choosing Select ground 200000-600000g/mol, alternatively 300000-550000g/mol, or alternatively 330000-500000g/ mol。
In any embodiment of the present invention, (it is to pass through GPC- to the Mw/Mn of acrylic polymers (A1) component DRI measurements) 1-20 is may be greater than, either 1.1-15 or 1.2-10, either 1.3-5 or 1.4-4.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 Mw/Mn (it is measured by GPC-DRI) with the composition (A1 the and A2 components of combination) produced after stage A2 can To be greater than 5-50, either 5.5-45 or 6-40, either 6.5-35 or 7-30.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 Total propylene content with the composition (A1 the and A2 components of combination) produced after stage A2 can be at least 75wt%, at least 80wt%, at least 85wt%, at least 90wt%, either at least 95wt% or 100wt%, based on the propylene polymer composition The weight of thing.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 Total comonomer content with the composition (A1 the and A2 components of combination) produced after stage A2 can be about 1wt%- About 35wt%, about 2wt%- about 30wt%, about 3wt%- about 25wt%, or about 5wt%- is about 20wt%, the gross weight based on the prolylene polymer composition, and surplus is propylene.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 The tuple content of propylene meso two with the composition (A1 the and A2 components of combination) produced after stage A2 can be 90% Or it is bigger, 92% or bigger, about 94% is either bigger or about 96% or bigger.Polypropylene micro-structural is root According to following13C NMR program determinations.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 With the fusing point (T of composition (A1 the and A2 components of combination) produced after stage A2m, DSC peaks second melting) can be to It is few 100 DEG C-about 175 DEG C, about 105 DEG C-about 170 DEG C, about 110 DEG C-about 165 DEG C, or about 115 DEG C-about 155℃。
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 Crystalline temperature (Tc, DSC) with the composition (A1 the and A2 components of combination) produced after stage A2 can be 115 DEG C or more Greatly, preferably at least 100 DEG C-about 150 DEG C, about 105 DEG C-about 130 DEG C, about 110 DEG C-about 125 DEG C, or about 115 DEG C-about 125 DEG C.
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 CDBI with the composition (A1 the and A2 components of combination) produced after stage A2 can be 50% or bigger (preferably 60% Or it is bigger, alternatively 70% or bigger, alternatively 80% or bigger, alternatively 90% or bigger, for choosing Select ground 95% or bigger).
In any embodiment of the present invention, the prolylene polymer composition that is produced herein, particularly in stage A1 There can be multimodal (such as bimodal) molecular weight distribution with the composition (A1 the and A2 components of combination) produced after stage A2 (Mw/Mn) polymer species of distribution.
In one embodiment, the prolylene polymer composition produced herein has：
A) at least 50mol% propylene (either 50-100mol% or 60-97mol%, either 65-95mol% or 70-90mol%, either at least 90mol% or 50-99mol%) and optional at least 1mol% comonomer (or 1- 50mol%, either 3-40mol% or 5-35mol%, or 10-30mol%), based on the prolylene polymer composition Weight；And/or
B) 1% Secant flexural modulus is at least 1000MPa (either at least 1300MPa or at least 1500MPa, Huo Zhezhi Few 1600MPa, either at least 1800MPa or at least 1900MPa, either at least 2000MPa or at least 2100MPa, or Person at least 2200MPa)；
C) it is less than 200 area defects (2,1- erythro forms and the formula insertion of 2,1- Soviet Unions and 3,1- isomerization sum)/10000 third Alkene unit, it is to pass through13(the either 5-200 or 10-200, either 15-200 or 17-175 of C NMR spectras method measure Individual area defects/10000 propylene units, alternatively more than 5, either 10 or 20, either 30 or 40, but be less than 200 area defects, alternatively less than 150 area defects/10000 propylene units)；And/or
D) porosity is more than or equal to about 15%, the gross weight based on acrylic polymers base resin or matrix, It is to determine that (or more than or equal to 20,25,30,35,40,45%, height arrives about 50,60,70,80 by mercury injection method Either 85% or higher)；And/or
E) the intermediate value PD determined by mercury injection method be less than 165 μm either less than 160 μm (or from 1, either 2 or 5, or 10 μm of height of person are to 50, and either 60 or 70, either 80 or 90, either 100 or 120, either 125 or 150, or 160, or 165 μm)；And/or
F) Mw/Mn is at least 2, at least 3, at least 4, or at least 5, its be determined by GPC-DRI (or 5-40, Either 6-20 or 7-15)；And/or
G) melt flow rate (MFR) is 50dg/min or bigger, and it is 230 DEG C by ASTM D1238,2.16kg measure (either 60dg/min or bigger, either 75dg/min or bigger)；And/or
H) multimodal Mw/Mn, it is determined by GPC-DRI, the composition especially produced after stage A and stage B (A and B component of combination), or (ii) Mw/Mn are greater than 1-5 (alternatively 1.1-3, alternatively 1.3-2.5), particularly The composition produced after stage A；
I) multimodal PSD；And/or
J) if there is comonomer, then CDBI is 50% either bigger by (or 60% or bigger, alternatively 70% Or it is bigger, alternatively 80% or bigger, alternatively 90% or bigger, alternatively 95% or bigger).
In any embodiment as described herein, the fusing point (Tm, DSC peak second melting) of propylene copolymer compositions can To be at least 100 DEG C-about 175 DEG C, about 105 DEG C-about 170 DEG C, about 110 DEG C-about 165 DEG C, or about 115 DEG C-about 155 DEG C, and crystalline temperature (Tc, DSC peak second melting) can be 115 DEG C or bigger, preferably at least 100 DEG C-about 150 DEG C, about 105 DEG C-about 130 DEG C, about 110 DEG C-about 125 DEG C, or about 115 DEG C-about 125 DEG C.
Heterophasic copolymer：In some embodiments of the present invention, acrylic polymers is multiphase.In some of the present invention In other embodiments, acrylic polymers is impact copolymer (ICP).In some embodiments, the ICP include iPP (on State the component A produced after stage A1 and optional stage A2 or composition (A1 the and A2 components of combination), preferably its Tm120 DEG C or bigger) with acrylic polymers (its glass transition temperature (Tg) be -30 DEG C or lower) and/or ethene gather The blend of compound (component B).In ICP embodiments below the present invention, component A is referred in polymer product above The composition produced after stage A discussed in embodiment, and it is above-mentioned in stage A1 and stage A1 and stage A2 The composition (A1 the and A2 components of combination) produced afterwards.
In some embodiments, component A (or A1 and A2 components of combination, if present) accounts for ICP 60- 95wt%, and component B account for 5-40wt%, and based on component A (or A1 and A2 components of combination, if present) and B's is total Weight, or the gross weight based on ICP.Component A (or A1 and A2 components of combination, if present) iPP can have There are any one of performance of any iPP embodiments disclosed herein, combination or whole, and/or can pass through herein It is prepared by the described any method for being used to produce iPP.In some embodiments of the present invention, component B is ethylene copolymer Or EP rubber, preferably TgIt it is -30 DEG C or lower.In some embodiments of the present invention, discrete phase mainly includes component A (or A1 and A2 components of combination, if present), and component (B) is mainly either co-continuous comprising dispersed phase. In some embodiments of the present invention, ICP only includes two kinds of monomers：Propylene and single comonomer, it is selected from ethene and C4- C8Alpha-olefin, optimal ethylene, butylene, hexene or octene, more preferably ethene.Alternatively or additionally, the ICP includes three Kind monomer：Propylene and two kinds of comonomers, it is selected from ethene and C4-C8Alpha-olefin, it is preferably selected from ethene, butylene, hexene and octene Two kinds.Preferably, component A (or A and B component of combination, if present) TmBe it is 120 DEG C either bigger or It is 130 DEG C either bigger or 140 DEG C or bigger, either 150 DEG C or bigger, either 160 DEG C or it is bigger).Preferably, Component C TgIt is -30 DEG C either lower or -40 DEG C or lower, either -50 DEG C or lower.
In one embodiment of the present invention, the heat of fusion (Hf) of (B) component is 90 DEG C or lower (it is to pass through DSC measure).It is preferred that the Hf of (B) component is 70 DEG C or lower, preferably 50 DEG C or lower, preferably 35 DEG C or lower.
It is preferred that by stage A, the A1 and A2 of combination, and/or the ICP that B is produced is multiphase, particularly wherein iPP is to connect Continuous phase, and filled rubber is dispersed phase or co-cable transmission.
In some embodiments, the impact copolymer has discrete phase, and it mainly includes fusing point (Tm) be 100 DEG C or Person is bigger, and MWD is 5 or bigger and multimodal MWD prolylene polymer composition, and disperses or fill phase, and it is included (preferably Mainly include) TgIt it is -20 DEG C or lower polyolefin.Preferably, the discrete phase mainly includes homopolymer polypropylene (hPP) And/or random copolymer polypropylene (RCP) (it has relatively low co-monomer content (being less than 5wt%)), and fusing point is It is 110 DEG C either bigger (preferably 120 DEG C or bigger, preferably 130 DEG C or bigger, preferably 140 DEG C or bigger, preferably 150 DEG C Or it is bigger, preferably 160 DEG C or it is bigger).Preferably, the dispersed phase is mainly copolymerized comprising one or more ethene or propylene Thing (it has relatively high co-monomer content (at least 5wt%, preferably at least 10wt%))；And TgIt is -30 DEG C or more Low (preferably -40 DEG C or lower, preferably -50 DEG C or lower).
" ICP " in situ is a kind of certain types of ICP, and it is the reactor mixture of ICP (A) and (B) component, this meaning Taste in the reactor (or reaction zone) that (A) optional (A1 and A2) and (C) is the difference connected in series and prepared, And effect is that the final product closely mixed is obtained in the product for leaving last reactor (or reaction zone).Generally, The component is prepared in sequential polymerization processes, wherein (A1) is produced in first reactor, and is transferred to Two reactors, wherein optional (A2) be produced in second reactor (or combination A1 and A2 components can be one Produced in individual reactor), and the product is transferred to another reactor, (B) is produced wherein, and be incorporated into (A or A1 And A2) in matrix.There can also be a small amount of component (C), it is produced as accessory substance during this method, main bag Containing non-propylene co-monomer (for example, if ethene is used as comonomer, then (C) will be ethene polymers).In the literature, especially Be in the patent literature, ICP in situ be sometimes identified as " reactor blend ICP " or " block copolymer ", although after A kind of term is not strict accurate, because at most only existing very small part of such molecule, it is (A)-(C) copolymerization Thing.In a preferred embodiment of the present invention, the polymer composition produced herein is ICP in situ.
" ex situ ICP " is a kind of certain types of ICP, and it is (A) and optional (A1 and A2) and (B) physical blending Thing, it means that (A) (A1 and A2) and/or (B) are separately synthesized, and are then followed by usually using melting mixing method (example Such as extruder) it is blended.Ex situ ICP is characterised by the fact, i.e. (A) and or (A1 and A2), and (B) be Leave what their own synthetic method was collected in solid form afterwards, be then combined with；And for ICP in situ, (A) is optional (A1 and A2) and (B) merges in conventional synthetic method, and only blend is collected in solid form.
In one or more embodiments, impact copolymer (A, the combination of optional A1 and A2 and B component) is advantageously With more than 15 and less than 200 area defects (being defined as 2,1- erythro forms and the formula insertion of 2,1- Soviet Union, and 3,1- isomerization sum)/ 10000 propylene units, alternatively more than 17 and it is less than 175 area defects/10000 propylene units, alternatively greatly In 20, either 30 or 40, but be less than 200 area defects, alternatively less than 150 area defects/10000 third Alkene unit.The area defects are to use13C NMR spectra methods determine as described below.
The impact polymer produced generally has more phase morphologies, make it that discrete phase is mainly that Tm is 120 DEG C or more Big acrylic polymers, and dispersed phase is mainly ethylene copolymer (such as EP rubber) or acrylic polymers, its Tg is typically- 30 DEG C or lower.
Total propylene content of the impact copolymer produced herein is preferably at least 50wt%, at least 75wt%, at least 80wt%, at least 85wt%, at least 90wt%, either at least 95wt% or 100wt%, based on the propylene polymer composition The weight of thing.
The total comonomer content of the impact copolymer produced herein is preferably about 0.1wt%- about 75wt%, greatly About 1wt%- about 35wt%, about 2wt%- about 30wt%, about 3wt%- about 25wt%, or about 5wt%- is big About 20wt%, the gross weight based on prolylene polymer composition, and surplus is propylene.
In embodiments, impact copolymer includes iPP (typically from stage A or A1 and A2) and ethylene copolymer (typically from stage B) and its ethylene copolymer (optimal ethylene propylene copolymer, preferably EP rubber) content be typically from Low spot about 5wt%, about about 8wt%, 10wt%, either about 15wt% or about 20wt%, or about 30wt%, either about 40wt% or about 50wt%, to any higher upper limit about 25wt%, about 30wt%, greatly About 35wt%, either about 40wt% or about 50wt%, either about 60wt% or about 70wt%, or about 75wt%, either about 80wt% or about 85wt% or higher.For example, the ethylene copolymer of the impact polymer contains Amount can be about 15wt%- about 85wt%, about 30wt%- about 75wt%, about 35wt%- about 70wt%, or Person about 40wt%- about 60wt%.In some preferred embodiments of the present invention, the ethylene copolymer content of the ICP It is at least about 25wt%, at least about 30wt%, at least about 35wt%, or at least about 40wt%, height are big to high point About 50wt%, 60wt%, 70wt%, 80wt% are higher.
In embodiments, impact copolymer includes iPP (coming from stage A or A1 and A2) and ethylene copolymer (comes From in stage B), the propylene content in ethylene copolymer component of the impact copolymer can be from low spot about 25wt%, About 85wt% or higher, either to about 37wt% or about 46wt% to high point about 73wt%, or about 77wt%, or about 80wt%, the weight based on the ethylene copolymer.For example, the ethylene copolymer group of the impact copolymer Propylene content in point can be about 25wt%- about 80wt%, and about 10wt%- about 75wt%, about 35wt%- is big About 70wt%, or at least 40wt%- about 80wt%, the weight based on the ethylene copolymer.
The heat of fusion (Hf, DSC reheating) of the impact copolymer produced herein is preferably 60J/g or bigger, 70J/g is bigger, 80J/g or bigger, 90J/g or bigger, about 95J/g either bigger or about 100J/g or Person is bigger.
In embodiments, 1% Secant flexural modulus of the impact polymer produced herein is greater than about 300MPa, Either 500MPa or 700MPa, either 1000MPa or 1500MPa, either 2000MPa or about 300MPa- be about 3000MPa, about 500MPa- about 2500MPa, about 700MPa- about 2000MPa, or about 900MPa- is about 2000MPa, it is measured according to ASTM D790 (A, 1.0mm/min).
In embodiments, the Mw (it is measured by GPC-DRI) for the impact polymer that this paper is produced can be 50000-1000000g/mol, alternatively 80000-1000000g/mol, alternatively 100000-800000g/mol, for choosing Select ground 200000-600000g/mol, alternatively 300000-550000g/mol, or alternatively 330000-500000g/ mol。
Polyolefin is carried out13C-NMR spectral methods：Polypropylene micro-structural is to pass through13C-NMR spectral methods measure, including Isotaxy and the unit group of syndiotaxy two ([m] and [r]), three unit groups ([mm] and [rr]), and five unit groups ([mmmm] and [rrrr]) concentration.Symbol " m " or " r " describe the spatial chemistry of paired neighbouring propylene group, and " m " refers to meso " r " refers to racemic.Sample is dissolved in d2-1 at 120 DEG C, in 1,2,2- tetrachloroethanes, and wave spectrum is to use 10-mm What broadband probe obtained, it is using 400MHz (or higher) NMR spectrophotometers (such as Varian Inova at 120 DEG C 700 or Unity Plus 400, it should use what is 700) recorded in the case of a conflict.Polymer formant refers to mmmm= 21.83ppm.Polymer calculating included in being characterized by NMR is described in Polymer Conformation by F.A.Bovey And Configuration (Academic Press, New York 1969) and by J.Randall describe in Polymer Sequence Determination,13C NMR Method (Academic Press, New York, 1977) in.
Pass through13C NMR mensuration region defect densities：13Carbon NMR spectra method is used to measure solid and the region in polypropylene Defect density.13Carbon NMR spectra is to be divided with 10-mm broadband probes in Varian Inova 700 or Unity Plus 400 (700 should be used in the case of a conflict) obtained on photometer.The sample is in 1,1,2,2- tetrachloroethanes-d2 (TCE) prepared in.Sample preparation (polymer dissolving) is in 120 DEG C of progress.In order to optimize chemical shift parsing, the sample Product are prepared in the case of no pentanedione chromium relaxant.Signal to noise ratio is strengthened by the way that wave spectrum is obtained as below： Strengthened 10 seconds using core Ovshinsky before obtaining pulse, and 3.2 seconds obtain the time, for aggregation pulse repetition delay 14 seconds. 120 DEG C of temperature obtains the free induction decay that 3400-4400 adds (coadded) transient state altogether.In Fourier transformation, (256K is individual Point and 0.3Hz exponential lines are widened) after, the wave spectrum is by the way that main mmmm mesos methyl resonance is set as into 21.83ppm Come what is referred to.
Chemical shift to stereo defects point out and (provided as three-dimensional five unit groups) can document [L.Resconi, L.Cavallo, A.Fait and F.Piemontesi, Chem.Rev.2000,100, the 1253-1345 pages] in find.Solid five Unit group (such as mmmm, mmmr, mrrm etc.) can suitably sum to provide three-dimensional three unit component cloth (mm, mr and rr) and stand The molar percentage of the unit group of body two (m and r).Quantify the area defects of three types：2,1- erythro forms, 2,1- Soviet Union's formulas, and 3,1- Isomerization.These structure and peak is pointed out also in Chem.Rev.2000,100, provided in the 1253-1345 pages.All defect Concentration provided with defect/10000 monomeric unit.
The area defects each generate multiple peaks in carbon NMR spectra, and by these whole integrations and averagely (only Them are wanted to parse from other peaks in wave spectrum), to improve measurement accuracy.The chemical potential for parsing resonance used in the analysis Shifting amount list is shown in following.The function that accurate peak position can select as NMR solvents carrys out displacement.
Area defects Chemical shift range (ppm)
2,1- erythro forms 42.3 38.6,36.0,35.9,31.5,30.6,17.6,17.2
2,1- Soviet Unions formula 43.4,38.9,35.6,34.7,32.5,31.2,15.4,15.0
3,1 insertions 37.6,30.9,27.7
Average integral divided by main propylene signal (CH to each defect3, CH, CH2) one of integration, and be multiplied by 10000 To determine defect density/10000 monomeric unit.
Ethylene contents in ethylene copolymer are determined by ASTM D5017-96, except minimum signal to noise ratio should be 10000:Outside 1.Propylene content in propylene copolymer be by according to Di Martino and Kelchermans, J.Appl.Polym.Sci., page 56,1781, the scheme of the method 1 in (1995), and use come from Zhang, Polymer, page 45,2651 (2004) are pointed out to determine for the peak of higher alkene comonomer.
Composition Distribution Breadth Index (CDBI) is the measurement of the composition distribution of monomer in polymer chain.It is such as WO93/ 03093, specifically the 7th and 8 columns and in Wild et al., J.Poly.Sci., Poly.Phys.Ed., volume 20, page 441, (1982) measure and described in US5008204, including when determining CDBI, ignore weight average molecular weight (Mw) and be less than 15000g/mol fraction.
Unless otherwise directed, otherwise Tg be by DMA, it is (including wherein cited according to US2008/0045638 pages 36 Any bibliography) described program measures.
Embodiment list
Present invention also offers following embodiment, each of which, which may be considered that, optionally includes any selective reality Apply scheme.
E1. acrylic polymers, it is included：
At least 50mol% propylene；
1% Secant flexural modulus is at least 1000MPa, and it is determined according to ASTM D790 (A, 1.0mm/min)；
Less than 200 area defects (alternatively more than 5 to less than 200 area defects)/10000 propylene units, It is to pass through13C NMR measure；
If there is comonomer, then it is 50% or bigger to form Distribution Breadth Index (CDBI)；
Matrix, its include porosity be 15% or bigger and median pore size diameter be less than 165 μm (alternatively more than 6 with/ Or less than 160 μm), it is determined by mercury injection method.
E2. embodiment E1 acrylic polymers, the wherein porosity be 20% either more it is big (alternatively 25% or It is bigger, either 30% or bigger, either 35% or bigger, either 40% or bigger；At most 85%, or at most 80%, either at most 75% or at most 70%, either at most 60% or at most 50%).
E3. embodiment E1 or embodiment E2 acrylic polymers, the wherein median pore size diameter (PD) are more than 0.1 μm (alternatively more than 1 μm, either more than 2 μm or more than 5 μm, either more than 6 μm or more than 8 μm, or more than 10 μ M, either more than 12 μm or more than 15 μm, either more than 20 μm) and/or less than 160 μm (alternatively less than 50 μm or Less than 60 μm, either less than 70 μm or less than 80 μm, either less than 90 μm or less than 100 μm, or less than 120 μm, Either less than 125 μm or less than 140 μm, or less than 150 μm) (alternatively from 8 μm of height to 150 μm).
E4. the acrylic polymers of any one of foregoing embodiments, it includes multimodal (alternatively bimodal) molecular weight distribution.
E5. the acrylic polymers of any one of foregoing embodiments, the wherein polymer are particle form.
E6. the acrylic polymers of any one of foregoing embodiments, wherein at least 90 volume % (alternatively at least 95 bodies Product %, either at least 98 volume % or at least 99 volume %) have be more than about 120 μm (alternatively 150,200,300, 400 or 500 μm of height are to 10,5 or 1mm) granularity (PS).
E7. the acrylic polymers of any one of foregoing embodiments, it includes multimodal (alternatively bimodal) size distribution.
E8. the acrylic polymers of any one of foregoing embodiments, it includes heterophasic copolymer, and the heterophasic copolymer includes extremely The partially filling phase in the hole in filling substrate.
E9. embodiment E8 acrylic polymers, the wherein filling mutually include ethylene propylene rubber.
E10. embodiment E8 or embodiment E9 acrylic polymers, the ethene that wherein acrylic polymers includes are total to Copolymer content is from about 5wt% (alternatively about 8wt%, about 10wt%, either about 15wt% or about 20wt%, either about 30wt% or about 40wt%, or about 50wt%) it is high (alternatively big to about 25wt% About 30wt%, about 35wt%, either about 40wt% or about 50wt%, either about 60wt% or about 70wt%, either about 75wt% or about 80wt%, or about 85wt%), the gross weight based on the acrylic polymers Amount.
E11. the acrylic polymers of any one of foregoing embodiments, the wherein polymer are to use single site catalysts body Prepared by system.
E12. embodiment E11 acrylic polymers, the wherein polymer are further in the activity comprising catalyst system The heart, the residue of catalyst system or its combination.
E13. embodiment E11 or embodiment E12 acrylic polymers, wherein the single site catalysts system Comprising single site catalysts precursor compound, for the activator of precursor compound, and carrier.
E14. the acrylic polymers of any one of foregoing embodiments, it is further comprising the active catalytic being dispersed in matrix Agent system.
E15. embodiment E13 or embodiment E14 acrylic polymers, the wherein catalyst system include single activity Site precatalyst compound, for the activator of precursor compound, and carrier, the specific surface area (SA) of the carrier is 400m2/ g or bigger (alternatively 400-1000m2/ g, or 400-650m2/ g, or 650-1000m2/ g), pore volume (PV) it is 0.5-2mL/g (alternatively 0.5-1.5mL/g), and average PD is 1-20nm(alternatively 1- 7nm, or 7-20nm).
E16. the acrylic polymers of any one of foregoing embodiments, the wherein matrix include the nearly spheroid of multiple polymer, its Define the clearance space in the hole to be formed in polymer spheres.
E17. the acrylic polymers of any one of foregoing embodiments, it further includes at least 75wt% (alternatively extremely Few 80wt%, at least at least 85wt%, 90wt%, either at least 95wt% or 100wt%) total propylene content, based on this The weight of prolylene polymer composition.
E18. the acrylic polymers of any one of foregoing embodiments, it further includes about 1wt%- about 35wt% (alternatively about 2wt%- about 30wt%, either about 3wt%- about 25wt% or about 5wt%- be about Total comonomer content 20wt%), the gross weight based on the prolylene polymer composition.
E19. the acrylic polymers of any one of foregoing embodiments, it further includes comonomer and 50% or bigger (alternatively 60% or bigger, 70% or bigger, 80% or bigger, 90% is either bigger or 95% or more CDBI greatly).
E20. the acrylic polymers of any one of foregoing embodiments, it is further comprising at least unit of 10% isotaxy five Group (the alternatively unit group of at least 20% isotaxy five, either the unit group of at least 30% isotaxy five or at least 40% The unit group of isotaxy five, or the unit group of at least 50% isotaxy five).
E21. the acrylic polymers of any one of foregoing embodiments, its further include be more than 5 (alternatively more than 10, Either more than 15 or more than 17, either more than 20 or more than 30, or more than 40) individual area defects/10000 propylene Unit, it is to pass through13C NMR measure.
E22. the acrylic polymers of any one of foregoing embodiments, it, which is further included, is less than 200 area defects (for choosing It is less than 175 with selecting or less than 150)/10000 propylene units.
E23. the acrylic polymers of any one of foregoing embodiments, wherein 1% Secant flexural modulus are at least 1300MPa (alternatively at least 1500MPa, either at least 1700MPa or at least 1800MPa, either at least 1900MPa or at least 2000MPa, either at least 2100MPa or at least 2200MPa), it is determined according to ASTM D790 (A, 1.0mm/min) 's.
E24. the acrylic polymers of any one of foregoing embodiments, it is further comprising at least 120 DEG C or bigger (for choosing It is either bigger or 140 DEG C or bigger to select 130 DEG C of ground, either 150 DEG C or bigger, either 160 DEG C or it is bigger) it is molten Point (Tm, DSC peak second melting).
E25. the acrylic polymers of any one of foregoing embodiments, its further include and be more than 1 (alternatively 1.1, or 1.2, either 1.3 or 1.4) to 20 (alternatively 15, either 10 or 5, or 4) as measured by GPC-DRI Mw/Mn。
E26. the acrylic polymers of any one of foregoing embodiments, it is further distributed comprising multimodal molecular weight, and whole Body Mw/Mn is greater than 1-20 and the Mw/Mn of at least one most probable value is greater than 1-5.
E27. the acrylic polymers of any one of foregoing embodiments, it further includes (selective from about 0.1dg/min Ground about 0.2dg/min, about about 0.5dg/min, about 1dg/min, about 15dg/min, 30dg/min, or about 45dg/min) it is high to about 300dg/min (alternatively about 75dg/min, about 100dg/min, about 200dg/min, Or about 300dg/min) melt flow rate (MFR) (MFR, ASTM1238,230 DEG C, 2.16kg).
E28. the acrylic polymers of any one of foregoing embodiments, it further includes 50000g/mol (alternatively 80000g/mol, 100000g/mol, 200000g/mol, 300000g/mol, or 330000g/mol) -1000000g/mol The Mw of (alternatively 800000g/mol, 600000g/mol, 550000g/mol, or 500000g/mol) (passes through GPC-DRI Measurement).
E29. [retain]
E30. [retain]
E31. the method for polypropylene, it includes：
(a) propylene monomer is contacted with catalyst system under polymerization conditions, the catalyst system includes single active center The average PS of catalyst precursor compounds, activator and carrier, the wherein carrier is greater than 30 μm of height to 200 μm, and SA is 400m2/ g is bigger, and PV is 0.5-2mL/g (alternatively 0.5-1.5mL/g), and average PD is 1-20nmIt is by BET nitrogen adsorption assays；With
(b) propylene polymer matrix is formed, it includes at least 50mol% propylene, and porosity is 15% or bigger, It is determined by mercury injection method.
E32. embodiment E31 method, the wherein carrier include the agglomerate of multiple primary granules.
E33. embodiment E32 method, the wherein primary granule have the particle mean size smaller than agglomerate, the primary The particle mean size of grain is 1nm-50 microns.
E34. embodiment E32 or embodiment E33 method, it further comprises agglomerate fragment in (b) Catalyst active center is dispersed in propylene polymer matrix by change.
E35. any one of embodiment E31-E34 method, the wherein carrier include metal oxide.
E36. any one of embodiment E31-E35 method, the wherein carrier include silica.
E37. any one of embodiment E31-E36 method, the wherein carrier are spray drying.
E38. the average PS of any one of embodiment E31-E37 method, the wherein carrier is greater than 30 μm (alternatively More than 40 μm, more than 50 μm, either more than 60 μm or more than 65 μm, either more than 70 μm or more than 75 μm, Huo Zhe great In 80 μm, either more than 85 μm or more than 90 μm, either more than 100 μm or more than 120 μm) it is high (selective to 200 μm Ground is less than 180 μm, either less than 160 μm or less than 150 μm, or less than 130 μm).
E39. any one of embodiment E31-E38 method, the wherein carrier include：
The SA that SA is less than the wherein carrier is less than 1400m2/ g is (alternatively less than 1200m2/ g, or less than 1100m2/ G, or less than 1000m2/ g, or less than 900m2/ g, or less than 850m2/ g, or less than 800m2/ g, or be less than 750m2/ g, or less than 700m2/ g, or less than 650m2/g；And/or more than 500m2/ g, or more than 600m2/ g, Huo Zhe great In 650m2/ g, or more than 700m2/g)；And/or
Average PD be more than 2nm (alternatively more than 3nm, either more than 4nm or more than 5nm, or more than 6nm, or Person is more than 7nm, or more than 8nm；And/or less than 20nm, either less than 15nm or less than 13nm, or less than 12nm, or Person is less than 10nm, either less than 8nm or less than 7nm, or less than 6nm).
E40. any one of embodiment E31-E39 method, the wherein SA are more than 650m2/ g and average pore diameter are less than
E41. any one of embodiment E31-E39 method, the wherein specific surface area are less than 650m2/ g or average Kong Zhi Footpath is more than
E42. any one of embodiment E31-E41 method, the wherein activator include aikyiaiurnirsoxan beta (alternatively MAO or Person MMAO).
E43. any one of embodiment E31-E42 method, the wherein catalyst system further include activator promotor, its It is selected from：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-octylaluminium, three hexyl aluminium and diethyl zinc (are alternatively selected from： Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three hexyl aluminium, tri-n-octylaluminium, dimethyl magnesium, magnesium ethide, dipropyl magnesium, Diisopropyl magnesium, dibutylmagnesium, diisobutyl magnesium, dihexyl magnesium, dioctyl magnesium, methyl-magnesium-chloride, ethylmagnesium chloride, propyl chloride Change magnesium, isopropylmagnesium chloride, butylmagnesium chloride, isobutyl group magnesium chloride, hexyl magnesium chloride, octylmagnesium chloride, methyl magnesium fluoride, second Base magnesium fluoride, propyl group magnesium fluoride, isopropyl magnesium fluoride, butyl magnesium fluoride, isobutyl group magnesium fluoride, hexyl magnesium fluoride, octyl group fluorination Magnesium, zinc methide, diethyl zinc, dipropyl zinc and dibutyl zinc) (alternatively it is selected from：Trimethyl aluminium, triethyl aluminum, three is different Butyl aluminium, tri-n-octylaluminium, three hexyl aluminium and diethyl zinc).
E44. under any one of embodiment E31-E43 method, wherein the single site catalysts precursor compound are Shown in formula：
(Cp)mRAnM4Qk
Wherein：
Each Cp is cyclopentadienyl moieties or taken with what one or more alkyl with 1-20 carbon atom substituted For cyclopentadienyl moieties；
RAIt is the structure bridge between two Cp parts；
M4It is the transition metal selected from the 4th or 5 races；
Q is alkyl of the hydrogen-based either with 1-20 carbon atom or the alkenyl with 2-20 carbon atom, or halogen；
M is 1,2 or 3, and if it is 2 or 3 to limit m, each Cp can be with identical or different；
N is 0 or 1, and if restriction m=1, n=0；With
K is so, i.e. so that k+m is equal to M4Oxidation state, and if limit k and be more than 1, each Q can with identical or It is different.
E45. under any one of embodiment E31-E43 method, wherein the single site catalysts precursor compound are Shown in formula：
RA(CpR”p)(CpR*q)M5Qr
Wherein：
Each Cp is cyclopentadienyl moieties or substituted cyclopentadienyl moieties；
Each R* and R " is the alkyl for having 1-20 carbon atom, and can be with identical or different；
P is 0,1,2,3 or 4；
Q is 1,2,3 or 4；
RA is the structure bridge between Cp parts, and it assigns metallocene compound solid hardness；
M5It is the 4th, 5 or 6 race's metal；
Q is the alkyl either halogen for having 1-20 carbon atom；
R is that s subtracts 2, and wherein s is M5Chemical valence；
Wherein (CpR*q) has two sides or false two sides symmetry；R*q is selected, to cause (CpR*q) to form fluorenyl, alkane The indenyl of base substitution, either four-, three-or dialkyl group substitution cyclopentadienyl group；(CpR " p) be included in remote location it One and only one in bulky group；
Wherein the bulky group is formula ARwv；With
Wherein A is selected from group-4 metal, oxygen or nitrogen, and Rw is methyl or phenyl, and v is that chemical valence A subtracts 1.
E46. under any one of embodiment E31-E43 method, wherein the single site catalysts precursor compound are Shown in formula：
Wherein：
M is the 4th, 5 or 6 race's metal；
T is bridged group；
Each X is independently anion leaving group；
Each R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12And R13It is independently halogen atom, hydrogen, alkyl, substitutes Alkyl, halocarbyl, substituted halocarbyl, silicyl is carbon-based, and substituted silicyl is carbon-based, and germyl is carbon-based, The carbon-based substituent of substituted germyl or-NR'2,-SR' ,-OR' ,-OSiR'3Or-PR'2Group, wherein R' are Halogen atom, C1-C10Alkyl or C6-C10One of aryl.
E47. embodiment E46 method, wherein R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12And R13In at least One is cyclopropyl substituent shown in following formula：
Each R' wherein in the cyclopropyl substituent is independently hydrogen, substituted alkyl, unsubstituted alkyl or halogen Element.
E48. embodiment E46 or embodiment E47 method, wherein：
M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten；
Each X is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10Alkyl, substituted or unsubstituted C1- C10Alkoxy, substituted or unsubstituted C6-C14Aryl, substituted or unsubstituted C6-C14Aryloxy group, substituted or unsubstituted C2- C10Alkenyl, substituted or unsubstituted C7-C40Aryl alkyl, substituted or unsubstituted C7-C40Alkylaryl and substitution are unsubstituted C7-C40Aryl alkenyl；Or optionally it is joined together to C4-C40Alkane diyl or conjugation C4-C40Diene ligand, its M is coordinated in the form of metal cyclopentene；Or conjugated diene is optionally represented, it is optionally with independently selected from alkyl, three hydrocarbon One or more groups of base silicyl and trihydrocarbylsilyl groups alkyl substitute, and described diene has at most 40 altogether Atom (does not include hydrogen), and forms pi complex with M；
Each R2, R4, R8And R10Independently selected from hydrogen, halogen, substituted or unsubstituted C1-C10Alkyl, substitution or unsubstituted C6-C14Aryl, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C7-C40Aryl alkyl, substitution or unsubstituted C7-C40Alkylaryl, substituted or unsubstituted C8-C40Aryl alkenyl and-NR'2,-SR' ,-OR' ,-SiR'3,- OSiR'3With-PR'2Group, wherein each R' is independently selected from halogen, substituted or unsubstituted C1-C10 alkyl and substitution or not Substituted C6-C14Aryl；
R3, R5, R6, R7, R9, R11, R12And R13Each it is selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10Alkyl, Substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C6-C14Aryl, substituted or unsubstituted C6-C14Aryloxy group, Substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C7-C40Aryl alkyl, substituted or unsubstituted C7-C40Alkyl virtue Base and C7-C40Substituted or unsubstituted aryl alkenyl；With
T is selected from：
—B(R14)-,-Al (R14)-,-Ge-,-Sn-,-O-,-S-,-SO-,-SO2- ,-N (R14)-,-CO-,-P (R14)-, and-P (O) (R14)—；
Wherein R14, R15And R16Each independently selected from hydrogen, halogen, C1-C20Alkyl, C6-C30Aryl, C1-C20Alkoxy, C2-C20Alkenyl, C7-C40Aryl alkyl, C8-C40Aryl alkenyl and C7-C40Alkylaryl, optionally R14And R15With being connected them Atom (one or more) form ring together；And M3Selected from carbon, silicon, germanium and tin；Or
T is shown in following formula：
Wherein R17, R18, R19, R20, R21, R22, R23And R24Each independently selected from hydrogen, halogen, hydroxyl, substitute or do not take The C in generation1-C10Alkyl, substituted or unsubstituted C1-C10Alkoxy, substituted or unsubstituted C6-C14Aryl, substitution or unsubstituted C6-C14Aryloxy group, substituted or unsubstituted C2-C10Alkenyl, substituted or unsubstituted C7-C40Alkylaryl, substitute or do not take The C in generation7-C40Alkylaryl and substituted or unsubstituted C8-C40Aryl alkenyl；Optionally two or more adjacent group R17, R18, R19, R20, R21, R22, R23, and R24, including R20And R21, one or more rings are formed together with connecting their atom； With
M2Represent one or more carbon atoms, or silicon, germanium or tin atom.
E49. any one of embodiment E31-E48 method, wherein contact of the propylene monomer with catalyst system be Carried out in liquid slurry phase.
E50. any one of embodiment E31-E48 method, wherein contact of the propylene monomer with catalyst system be Carried out in gas phase.
E51. any one of embodiment E31-E48 method, wherein contact of the propylene monomer with catalyst system be Carried out in solution.
E52. it is about 0.96MPa- that any one of embodiment E31-E51 method, the wherein polymerizing condition, which include pressure, About 7MPa.
E53. it is about -20 DEG C -150 that any one of embodiment E31-E52 method, the wherein polymerizing condition, which include temperature, ℃。
E54. any one of embodiment E31-E53 method, the wherein polymerizing condition are 15-720 points including the residence time Clock.
E55. any one of embodiment E31-E54 method, the wherein polymerizing condition include hydrogen being present.
E56. any one of embodiment E31-E54 method, the wherein polymerizing condition include being substantially absent from hydrogen.
E57. any one of embodiment E31-E56 method, the wherein polymerizing condition include ethene or C being present4-C20Altogether Polycondensation monomer.
E58. any one of embodiment E31-E56 method, wherein the propylene monomer in (a) there is no ethene and C4-C20Alhpa olefin, and the acrylic polymers formed are Noblens.
E59. any one of embodiment E31-E58 method, it further comprises that changing hydrogen or other chains in (a) turns Move the concentration of agent.
E60. any one of embodiment E31-E59 method, wherein the acrylic polymers formed in (b) includes multimodal point Son amount distribution.
E61. any one of embodiment E31-E60 method, the wherein polymerizing condition include further comprising from (b) Propylene polymer matrix contacted under polymerization conditions with one or more 'alpha '-olefin monomers, to form heterophasic copolymer, its wrap Filling phase containing the hole in filling substrate at least in part.
E62. any one of embodiment E31-E61 method, it further comprised the acrylic polymers at 1000 seconds-1Or Melt-processed under the bigger shear rate of person.
E63. any one of embodiment E31-E62 method, wherein the intermediate value of the propylene polymer matrix formed in (b) PD is less than 165 μm, its be determined by mercury injection method (alternatively more than 0.1 μm, either more than 1 μm or more than 2 μm, or Person be more than 5 μm, either more than 6 μm or more than 8 μm, either more than 10 μm or more than 12 μm, either more than 15 μm or More than 20 μm, and/or less than 160 μm, either less than 50 μm or less than 60 μm, either less than 70 μm or less than 80 μm, Either less than 90 μm or less than 100 μm, either less than 120 μm or less than 125 μm, either less than 140 μm or it is less than 150μm；Or from 8 μm of height to 150 μm).
E64. the PV of any one of embodiment E31-E63 method, the wherein carrier is 0.5-1.5mL/g.
E65. the average PS of any one of embodiment E31-E64 method, the wherein carrier is greater than 40 μm (alternatively More than 50 μm, either more than 60 μm or more than 65 μm, either more than 70 μm or more than 75 μm, or more than 80 μm, or Person is more than 85 μm, either more than 90 μm or more than 100 μm, or more than 120 μm；And/or at most 200 μm, or be less than 180 μm, either less than 160 μm or less than 150 μm, or less than 130 μm).
E66. the ratio SA of any one of embodiment E31-E65 method, the wherein carrier is less than 1400m2/ g is (alternatively Less than 1200m2/ g, or less than 1100m2/ g, or less than 1000m2/ g, or less than 900m2/ g, or less than 850m2/ g, Or less than 800m2/ g, or less than m2/ g, or less than 700m2/ g, or less than 650m2/g；And/or more than 600m2/ g, Or more than 650m2/ g, or more than 700m2/g)。
E67. it is (alternatively big that the average PD of any one of embodiment E31-E66 method, the wherein carrier is more than 2nm In 3nm, either more than 4nm or more than 5nm, either more than 6nm or more than 7nm, or more than 8nm；And/or it is less than 20nm, either less than 15nm or less than 13nm, either less than 12nm or less than 10nm, either less than 8nm or it is less than 7nm, or less than 6nm).
E68. any one of embodiment E31-E67 method, the wherein porosity be 20% or more it is big (alternatively 25% is either bigger or 30% or bigger, and either 35% or bigger, either 40% or bigger；At most 85%, or At most 80%, either at most 75% or at most 70%, either at most 60% or at most 50%).
E69. any one of embodiment E31-E68 method, wherein the acrylic polymers from (b) includes multimodal (for choosing Select bimodal) molecular weight distribution.
E70. any one of embodiment E31-E69 method, wherein the acrylic polymers from (b) is particle form.
E71. any one of embodiment E31-E70 method, wherein at least 90 volume % (alternatively at least 95 bodies Product %, either at least 98 volume % or at least 99 volume %) the acrylic polymers from (b) granularity more than about 120 μm (alternatively for from 150,200,300,400, or 500 μm of height to 10,5 or 1mm).
E72. any one of embodiment E31-E71 method, wherein the acrylic polymers from (b) includes multimodal (for choosing Select bimodal) size distribution.
E73. any one of embodiment E31-E72 method, wherein the ethylene copolymer that the acrylic polymers from (b) includes Thing content is from about 5wt% (alternatively about 8wt%, about 10wt%, either about 15wt% or about 20wt%, either about 30wt% or about 40wt%, or about 50wt%) it is high (alternatively big to about 25wt% About 30wt%, about 35wt%, either about 40wt% or about 50wt%, either about 60wt% or about 70wt%, either about 75wt% or about 80wt%, or about 85wt%), the gross weight based on the acrylic polymers Amount.
E74. any one of embodiment E31-E73 method, wherein total propylene that the acrylic polymers from (b) includes contains Amount is at least 75wt% (alternatively at least 80wt%, at least 85wt%, at least 90wt%, or at least 95wt%, Huo Zhezhi Few 100wt%), the weight based on the prolylene polymer composition.
E75. any one of embodiment E31-E74 method, wherein the comonomer that the acrylic polymers from (b) includes Total content is about 1wt%- about 35wt% (alternatively about 2wt%- about 30wt%, or about 3wt%- is about 25wt%, or about 5wt%- about 20wt%), the gross weight based on the prolylene polymer composition.
E76. any one of embodiment E31-E75 method, wherein the acrylic polymers from (b) includes comonomer, And CDBI be 50% either more it is big (alternatively 60% or bigger, 70% or bigger, 80% or bigger, 90% or Person is bigger, and either 95% or bigger).
E77. any one of embodiment E31-E76 method, wherein the acrylic polymers from (b) is complete comprising at least 10% With the vertical unit group of structure five (the alternatively unit group of at least 20% isotaxy five, or the unit group of at least 30% isotaxy five, Either the unit group of at least 40% isotaxy five or the unit group of at least 50% isotaxy five).
E78. any one of embodiment E31-E77 method, wherein the acrylic polymers from (b), which includes, is more than 5 (for choosing Select be more than 10, either more than 15 or more than 17, either more than 20 or more than 30, or more than 40) individual area defects/ 10000 propylene units, it is to pass through13C NMR measure.
E79. any one of embodiment E31-E78 method, wherein the acrylic polymers from (b), which includes, is less than 200 Area defects (alternatively less than 175 or less than 150 area defects)/10000 propylene units.
E80. any one of embodiment E31-E79 method, wherein the acrylic polymers from (b) is scratched comprising 1% secant Bent modulus be at least 1000MPa (alternatively at least 1300MPa, either at least 1500MPa or at least 1700MPa, or At least 1800MPa, either at least 1900MPa or at least 2000MPa, either at least 2100MPa or at least 2200MPa), It is determined according to ASTM D790 (A, 1.0mm/min).
E81. any one of embodiment E31-E80 method, wherein from (b) acrylic polymers include fusing point (Tm, DSC peaks second melting) be at least 120 DEG C either more it is big (alternatively 130 DEG C or bigger, either 140 DEG C or bigger, or 150 DEG C of person it is either bigger or 160 DEG C or it is bigger).
E82. any one of embodiment E31-E81 method, wherein the acrylic polymers from (b), which includes, passes through GPC- The Mw/Mn that DRI is determined be greater than 1 (alternatively 1.1, either 1.2 or 1.3, or 1.4) to 20 (alternatively 15, Either 10 or 5, or 4).
E83. any one of embodiment E31-E82 method, wherein the acrylic polymers from (b) includes multimodal molecular weight Distribution, and overall Mw/Mn is greater than 1-20, and the Mw/Mn of at least one most probable value is greater than 1-5.
E84. any one of embodiment E31-E83 method, wherein the acrylic polymers from (b) includes melt flows speed Rate (MFR, ASTM1238,230 DEG C, 2.16kg) be from about 0.1dg/min (alternatively about 0.2dg/min, about 0.5dg/min, about 1dg/min, about 15dg/min, about 30dg/min, or about 45dg/min) it is high to about 300dg/min (alternatively about 75dg/min, about 100dg/min, about 200dg/min, or about 300dg/ min)。
E85. any one of embodiment E31-E84 method, wherein the acrylic polymers from (b) (passes through comprising Mw GPC-DRI measure) be from 50000g/mol (alternatively 80000g/mol, 100000g/mol, 200000g/mol, 300000g/mol, or 330000g/mol) to 1000000g/mol (alternatively 800000g/mol, 600000g/mol, 550000g/mol, or 500000g/mol).
E86. the acrylic polymers of (b) is come from, it is by being prepared according to any one of embodiment E31-E85 method 's.
Experiment
It is all reaction be under nitrogen purge gas atmosphere, using standard glove box, high vacuum or Schlenk technologies, Carried out in CELSTIR reactors, unless otherwise directed.All solvents used are anhydrous, according to known program deoxidation With purification.All parent materials purify purchased from Aldrich and before use, or according to journey well known by persons skilled in the art It is prepared by sequence.Silica is obtained from Asahi Glass Co., Ltd.s or AGC Chemicals Americas, Inc. (D 150-60A, D 100-100A), PQ Corporation (PD 13054), and Davison Chemical Division of W.R.Grace and Company(GRACE948).MAO is obtained from as 30wt% solution of the MAO in toluene Albemarle (13.6wt% Al or 5.04mmol/g).The solvent of deuterate is obtained from Cambridge Isotope Laboratories (Andover, MA) andDried on molecular sieve.For all material, own1H NMR datas be Collected on Broker AVANCE III 400MHz spectrophotometers, the spectrophotometer runs Topspin in room temperature (RT)TM 3.0 softwares, use tetrachloroethanes-d2As solvent (5.98ppm chemical shift is used as into reference).
Gel permeation chromatography-DRI (GPC-DRI)：For this paper purpose, Mw, Mn and Mw/Mn are by using dress Have differential refraction rate detector (DRI) high-temperature gel permeation chromatography (Polymer Laboratories) measurement.Use Three Polymer Laboratories PLgel 10 μm of mixing-B posts.Nominal flow rate is 1.0mL/min, and nominal injection Volume is 300 μ L.Various transfer lines, post and differential refractometer (DRI detectors), which are contained in, to be held in 160 DEG C of baking oven. Solvent for experiment be by regarding 6g Yoshinox BHTs as the Aldrich SILVER REAGENTs 1,2 that antioxidant is dissolved in 4L, Prepared in 4- trichloro-benzenes (TCB).Then the TCB mixtures pass through 0.1 μm of Teflon filter and filtered.The TCB and then use On-line degassing device is de-gassed, subsequently into GPC instruments.Polymer solution is by the way that dry polymer is placed in into vial In, the TCB of desired amount is added, then the mixture is heated to simultaneously continuous oscillation at 160 DEG C about 2 hours to prepare.It is all Amount is gravimetric method measurement.Implantation concentration is 0.5-2.0mg/ml, and relatively low concentration is used for the sample of higher molecular weight. Before running each sample, the DRI detectors are purged.Then flow velocity in device increases to 1.0ml/min, and make the DRI Stablize 8 hours, be then injected into the first sample.Molecular weight is combined to determine by the way that universal calibration relation is corrected with post, should Post correction is carried out with a series of monodispersed polystyrene (PS) reference materials.Mw is with following in each elution volume Equation calculates.
Wherein the variable with subscript " X " represents test sample, and those with subscript " PS " represent PS.In this method In, aPS=0.67 and KPS=0.000175, KXObtained from open source literature.Specifically, the a/K=0.695/ for PE 0.000579, the a/K=0.705/0.0002288 for PP.
The concentration c each pointed out in chromatogram is the DRI signal IDRI by subtracting baseline, is counted using following equation Calculate：C=KDRIIDRI/ (dn/dc), wherein KDRI are the constants determined by correcting DRI, and (dn/dc)=0.109, It is the index increment for both PE and PP.Mass recovery be by integral area of the concentration chromatogram in elution volume and The ratio between plastic injection quality (its be equal to predetermined concentration be multiplied by injection loop volume) calculates.All molecular weight are using g/mol to be single Position report, unless otherwise directed.
Melt flow rate (MFR) (MFR)：MFR is according to ASTM D1238, condition L, is determined in 230 DEG C and 2.16kg load , unless otherwise directed.
Differential scanning calorimetry (DSC)：Peak crystallization temperature (Tc), peak melt temperature (Tm), heat of fusion (Hf) and glass It is by differential scanning calorimetry (DSC) to change transition temperature (Tg), is measured using DSCQ200 units.Sample is first at 25 DEG C Balance, then it is heated to 220 DEG C (once heating) using 10 DEG C/min of the rate of heat addition.The sample is maintained at 220 DEG C of 3min.The sample Product are then cooled to -100 DEG C (once cooling down) with constant 10 DEG C/min of cooldown rate.The sample -100 DEG C balance, then with 10 DEG C/min of constant heating rate is heated to 220 DEG C (reheatings).Crystalline exotherm peak (once cooling down) uses TA Gneral analysis Software is analyzed, and is determined corresponding to 10 DEG C/min cooldown rates.It is also general using TA to melt endothermic peak (reheating) Analysis software is analyzed, and determines the T corresponding to the 10 DEG C/min rates of heat additionm.Determined using the area under DSC curve Hf (in melting) or Hc(in crystallization) and Tg.
Secant flexural modulus：1% Secant flexural modulus (1%SFM) is to use the rod of ISO37- types 3, with crosshead speed What 1.0mm/min and support span 30.0mm was measured using Instron machines according to ASTM D790 (A, 1.0mm/min).
Capillary rheology：All capillary rheology tests on polymer are to use the rheometers of ARC 2, at 200 DEG C Carried out using 1mm die orifices and path length 30mm.Test condition is (to use capillary rheometer determining according to ASTM D3835 The standard method of test of polymeric material performance) reproduce, and shear viscosity data use Rabinowitsch correction factors Correction, to illustrate velocity gradient of the non-newtonian fluid at die orifice wall.
Mercury injection method：Using Autopore IV9500 series mercury porosimeters, porous iPP hole is determined using mercury injection method Rate and intermediate value PD, and unless otherwise directed, otherwise averagely Hg contact angles are 130.000 °, and Hg surface tension is 485.000dynes/cm, evacuation pressure are that 50 μm of Hg and Hg stuffing pressures are 3.65kPa (0.53psia), unless otherwise directed.
The calcining of starting silica：Starting silica is in CARBOLITE model VST12/600 tube furnaces, is made With EUROTHERM 3216P1 temperature controllers, calcined according to following program.The controller is with desired temperature curve Come what is programmed.Quartz ampoule is silica-filled with 100g, and open with control valve to make nitrogen flow through pipe, to cause two Silica fluidizes completely.The quartz ampoule is subsequently placed in inside the heating zone of stove.Silica is heated slowly to desired temperature Allow calcining completely with the temperature is maintained at least 8 hours and remove water or moisture.After the dehydration is completed, it is quartz ampoule is cold But environment temperature is arrived.The silica of calcining reclaims in silica trap, and is collected into the appearance of the glass in drying box In device.Quality control inspection is used as using diffusing reflection infrared Fourier transform spectroscopic methodology (DRIFTS).Table 1 is listed for following Embodiment some in different silica and their calcination condition.
Embodiment 1：The loads of MAO on silica：The MAO (sMAO) of load arrives RT for -20 DEG C in reaction initiation temperature Prepare, to reduce high SA, the risk of small PD silica fragmentation when being reacted with MAO；Either in height to 100 DEG C or more Prepared at high temperature, to promote higher MAO load capacity and/or stronger fixation to cause the MAO minimums leached from carrier Change.SMAO preparation conditions are listed in the table below in 2.
SMAO methods I：Prepare to cause sMAO fragmentations to minimize for (sMAO2, sMAO7), make for low temperature sMAO With following or similar program.Silica is used into 10X toluene slurrying in the reactor, pays attention to all slurry and solvent liquid The ratio between body be as relative to starting silica material (such as starting silica or silicon dioxide carried MAO and/or Catalyst) weight than providing.Reactor is cooled in refrigerator to -20 DEG C and/or is maintained at RT.Reactor with 500rpm is stirred.The 30wt%MAO of cold (- 20 DEG C) is slowly added in reactor temperature keeping below 40 DEG C, and then Reactor is stirred 3 hours with 350rpm in RT.Mixture is filtered by medium melt, by wet solid with 10X toluene and Then washed, and be dried under vacuum 3 hours with 10X hexanes.
SMAO methods II：For sMAO (sMAO3) partial pieceization and contrast non-fragmentation sMAO (CsMAO1, CsMAO4 for preparation), following or similar program is used.By silica slurrying in 4-5X toluene, -20 are cooled to DEG C, and solution of the 30wt% MAO in toluene is added with two equal portions.First equal portions add under agitation, and will be formed Slurry cooled down in refrigerator about 5 minutes, then add the second equal portions and temperature kept below into RT.Then the slurry is made to exist RT is stirred 2 hours, filtering, is filtered in 3X toluene again slurrying 15min and second.Then by the material second in 3X toluene Secondary slurrying again, 30min is stirred at 80 DEG C, filtering, the third time slurrying again in 3X toluene, 30min, mistake are stirred at 80 DEG C Filter, with 3X toluene rinses, rinsed, and be dried under vacuum overnight with 3X pentanes.
SMAO methods III：(fragmentation sMAO1 is prepared for high temperature sMAO；Non- fragmentation sMAO4, sMAO5, sMAO6, sMAO8；Contrast CsMAO2) for, use following or similar program.By silica in the reactor stirred with 500rpm In the slurrying in 6X toluene.30wt%MAO solution is slowly added to the reactor temperature is kept below 40 DEG C, then should Reactor stirs 30min with 350rpm in RT, and is then heated 3 hours at 100 DEG C.Mixture is filtered by medium melt, By wet solid 10X toluene, then washed, be dried under vacuum 3 hours with 10X hexanes.
CsMAO methods IV：For contrast CsMAO5, following or similar program is used.Silica is being stirred Mix in reactor the slurrying in 6X toluene and cooled down in refrigerator.By 30wt%MAO solution with 3 parts of additions, and in addition Between by SiO 2 slurry return refrigerator a few minutes.The slurry is stirred 2 hours in RT, filtering, in 4X toluene in RT again Slurrying 15min, and then filter again.By solid in 4X toluene in 80 DEG C of slurrying 30min, and then filtering again.Will be solid Body is in 4X toluene in 80 DEG C of slurrying 30min, and then last time filters again.Solid 2X toluene, is then washed with pentane Wash and be dried under vacuum 24 hours.
Embodiment 2：Catalyst loads.Metallocene catalyst precursors compound used in the following examples and comparative example (MCN) it is listed in Table 3 below with Ziegler-Natta catalyst (ZN).Table 4 gives catalyst preparation/loading condition and according to this hair The CATALYST EXAMPLE SC1-SC10 of bright load and comparative example CSC1 and CSC2 yield.
Finished catalyst method I (Scat1-Scat8, Scat10；Contrast CSC1)：Solid is added into reactor in RT SMAO and 5X toluene.The slurry is stirred with 350rpm.TIBA (pure) is slowly added into the sMAO with 0.34mmol/g sMAO to become silted up In slurry, and reactor is stirred into 15min.Then, MCN is added, and solution mixture is stirred into 1-2 hours in RT.Should Slurry is filtered by medium melt.Wet solid is washed twice with 10X toluene, washed once with 10X hexanes, and do under vacuo Dry 3 hours, so as to generate the catalyst of the solid supported of free-flowing (SCat or CSC).
Finished catalyst method II (Scat9, Scat11)：MCN with the MAO of 40 equivalents by mixing and stirring 1 in RT Hour carrys out pre-activate.Meanwhile sMAO slurrying and is cooled down into refrigerator 1min in 20mL toluene.The preactivated MCN is molten Liquid and then add in the sMAO slurry of cooling, and formed mixture stirred 1 hour, and every 10 minutes in refrigerator Cooling 1 minute.The slurry formed is heated into 40 DEG C to continue 2 hours and filter, at 60 DEG C 5min's in 20mL toluene Again slurrying in period, stir 30min and filter again.Toluene washing is repeated twice, by solid material 50mL pentanes Wash and be dried under vacuum acquisition pink/violet solid yesterday.
Embodiment 3：Prepare porous iPP (" first stage reactor " either " stage 1A and or 1B ").Porous iPP is root According to embodiment of the present invention (PiPP1-PiPP11) and according to comparative example (CiPP1-CiPP5), with following representativeness It is prepared by program or similar program.Load 2mL 0.091M TNOAL (AkzoNobel) into 35mL catalyst tubes at oneself Solution in alkane, and injected with nitrogen in the reactor.Then by the catalyst tube pressurized with hydrogen, it is then added into this Reactor.Then, 600mL propylene is added into the reactor by catalyst tube.By the reactor under stir speed (S.S.) 500rpm It is heated to 70 DEG C.Then, using load or comparative catalyst as dry powder load the second catalyst tube, and with 200mL third Alkene inserts the reactor together.The reactor is maintained at 70 DEG C 1 hour.Finally, the reactor is emptied and collected polymer. IPP aggregated datas are shown in table 5, and mercury injection method data are shown in table 6A, and capillary rheology data and polymer property It is shown in table 6B.
Inventive samples PiPP4 and comparative sample CiPP2 and CiPP3 increment intrusion (mL/ are illustrated in Fig. 4,5 and 6 G) to the representative diagram of aperture diameter (μm).Statistically, on the left of these increment intrusion figures shown in macropore represent particle it Between clearance space, and intrusion data report in illustrate.As seen from Figure 4, PiPP4 of the invention has relatively great amount of The hole of 6-100 μ ms, and median pore size diameter are 12.2 μm, as table 6A is reported.Conventional titanium dioxide is supported on using The iPP prepared by MCN catalyst on silicon carrier is compared, inventive samples PiPP1, PiPP2, PiPP3 and PiPP4 porosity More than 30% or more than 40%, and median pore size diameter is in suitable scope, such as 10-100 μm, and it is beneficial to relatively high Rubber load capacity.
From figure 5 it can be seen that have with the contrast CiPP2 for the metallocene preparation being supported on 948 silica relatively small number of Hole less than 100 μm, and median pore size diameter are 165 μm, and it is reported in Table 4.The median pore size diameter is more than 160 μm, has sent out Now it is too high for promoting high rubber load capacity.On the other hand, contrast CiPP3 that is visible in figure 6, being prepared with ZN There is visibly different form in the spectrum other end, there is a high proportion of hole for being less than 6 μ ms, and median pore size diameter is 5 μm, It is reported in Table 4.
From the capillary rheology data shown in table 6B, in the class that high-rate of shear is detected by capillary rheology Confirm that (that is, shear rate is 1000 seconds in the condition similar to commercial processing equipment like viscosity-1Or it is higher) as lower class plus Work.Therefore, capillary rheology confirm prepared with carrier of the present invention in existing commercial processing equipment it is of the invention porous IPP MCN performance benefits.
Compared with these embodiments confirm the similar iPP with being prepared using ZN catalyst systems, iPP of the invention can make With silicon dioxide carried MCN catalyst preparations, narrower molecular weight distribution is thus provided, it is narrower in the case of the copolymer Composition distribution, relatively low extractable, processability and with the single site catalysts such as MCN iPP prepared other are excellent Point.
Embodiment 4：It is polymerize by unimodal and bimodal iPP ICP.In this embodiment, it is pre- to be prepared for unimodal or bimodal iPP Polymers, it is then followed by adding comonomer to prepare ICP heterophasic copolymers.Table 7 is given for bimodal prepolymer, and based on list The aggregated data of peak and bimodal iPP IPC operation.
For bimodal iPP (operation 1,2,5)：Except running 1 stopped after iPP is prepared using following program, and Operation 2 and 5 polymerization time it is as shown in table 7 outside.In order to prepare iPP prepolymers, in drying box, it will contain and be urged shown in table 7 The sCat2 slurry of agent amount adds catalyst tube, then adds 1mL hexanes (N2Injection and molecular sieve purification).By 3mL syringes Catalyst tube is added, adds 1.0ml 5ml solution of the TNOAL in 100ml hexanes.By the catalyst tube and 3ml syringes Removed from drying box, and the catalyst tube is connected to 2L reactors, while the reactor is purged with nitrogen.By TNOAL The reactor is injected via the scavenger mouth of rubber septum seal, is then shut off the scavenger mouth valve.By propylene (1000ml) The reactor is introduced by the propylene pipeline of purification.Agitator is set to reach 500rpm.Mixture is set to be mixed 5 minutes in RT.Then Catalyst slurry in catalyst tube is poured in reactor with 250ml propylene.So that the polymerisation is run 5 minutes in RT.
For stage A1 iPP prepolymers：Temperature of reactor is raised and is maintained at the period as defined in 70 DEG C.For rank Section A2 iPP, at the end of the A1 stages, will have 0.207MPa (30psig) H2150mL high-pressure cylinders (bomb) be open into The reactor.It was observed that reactor pressure adds 0.220MPa (31.9psi) and temperature of reactor adds 3 DEG C.Adding H2After make the reaction operating provisions time.
For stage B ICP：Agitator is set in into 250rpm before A2 terminates in the period to run 1 minute.In A2 Between at the end of section, using reactor discharge line valve, reactor pressure is vented to 1.475MPa (214psig), while will be anti- Device temperature is answered to keep as close possible to 70 DEG C.The agitator increase is returned into 500rpm.Temperature of reactor is stable at 70 DEG C, and Reactor pressure reading is 1.481MPa (214.8psig).Ethylene gas is introduced by the reactor with 0.938MPa (136psi), Target reaches 2.41MPa (350psig) gross pressure.The reactor is maintained at the pressure 20 minutes.It is vented using reactor Stop valve, reactor Quick air-discharge is stopped polymerizeing.Reactor bottom is removed and collected polymer sample.It is being dried overnight Afterwards, sample is the ICP resins flowed freely.
Come from unimodal iPP ICP (operation 3-4,6-8)：IPP prepolymers are prepared as described generally above.By reactor It is heated to after 70 DEG C, with the H shown in table 72The 150mL high-pressure cylinders of pressure filling open into reactor.In H2Cause after addition Time A1 shown in reaction operation.1 minute before time A1, agitator is set to 250rpm.At the end of the A1 times, Using reactor discharge line valve, reactor pressure is vented to 1.475MPa (214psi), while temperature of reactor is kept As close possible to 70 DEG C.The agitator increase is returned into 500rpm.Temperature of reactor is stable at 70 DEG C, and reactor pressure is read Number is 1.481MPa (214.8psi).Ethylene gas is introduced by the reactor with 0.938MPa (136psig), target reaches 2.413MPa (350psi) gross pressure.The reactor is maintained at the pressure and continues shown B (ICP) phases-time.Use Discharge line valve, reactor Quick air-discharge is stopped polymerizeing.Sample is removed and collected to reactor bottom.Arranged using reactor Gas stop valve, reactor Quick air-discharge is stopped polymerizeing.Reactor bottom is removed and collected polymer sample.Dried After night, sample is the ICP resins flowed freely.
Embodiment 6：Come from the iPP of the controlled fragmentation of catalyst carrier.In this embodiment, MCN is compound loaded In on the sMAO in different temperature conditionss preparations, and carry out metal alkyl processing and come Study of Catalyst activity and PSD, hardness With the iPP and ICP other performances prepared with the catalyst system.Using catalyst system CSC3, SCat2, SCat11 and SCat1A, using embodiment 3 polymerization procedure the polymerizing condition listed by table 8 below come prepare respectively contrast and the present invention it is porous IPP polymer CiPP6, PiPP12, PiPP13 and PiPP13.
As shown in fig. 7, the median size of the CiPP6 particles produced using the MCN systems of conventional load has bell list Peak PSD, center is close to 700 μm.
As shown in figure 8, using generally non-fragmentation carrier, (it generally carries out 3 hours MAO in environment or lower temperature and born Be to maintain in load intact) PiPP12 that is produced generates relatively large iPP particles, its have it is considerably less (if Words) it is less than 500 μm of any particle, and to be more than about 600 μm of height to 1500 μm or bigger for most or all particles.
As shown in figure 9, use the carrier institute come from the partial piece of 80 DEG C of MAO load-reactions for carrying out 1 hour The PiPP13 of production generates bimodal PSD, its include center close to 200 μm little particle most probable value and with size from connecing It is high to 1000 μm or bigger larger particles to be bordering on 600 μm of increases.
As shown in Figure 10, produced using the fragmentation carrier come from 100 DEG C of MAO load-reactions for carrying out 3 hours PiPP14 generate such PSD, its mainly comprising (>Center 80wt%) is few close to 200 μm of little particle, and only Amount (<The bulky grain of 500 μm of -1000 μ m 10wt%).
Embodiment 7：Come from the iPP that the catalyst for carrying out and being handled without TIBA loads.In this embodiment, MAO In the case where carrying out and being handled without TIBA, using high temperature, (100 DEG C continue 3 hours, for high capacity amount (11.5mmol Al/g silica) obtain iPP polymerization activities) and low temperature (<30 DEG C continue 3 hours, for low-load amount (7mmol Al/g Silica) establish high porosity iPP resins) the two is supported on D150-60A silica, increased to study any activity By force.MAO and MCN load programs are as follows, and use catalyst system, and iPP is prepared using the program similar to embodiment 3-4 And ICP.
Carry out the high temperature load (iPP15) of TIBA processing：10g silica S1 and 5X toluene is added into reactor. While being stirred with 350rpm, 22.8g 30%MAO (11.5mmol Al/g silica) is slowly added in 15min In SiO 2 slurry, it is then set to stir 30min in RT, and then in oil bath be about heated to 100 DEG C in 35min. The temperature of the slurry is maintained at 100 DEG C 3 hours while stirring.Then remove oil bath and make reactor cold at ambient conditions But to 50 DEG C.Then the slurry is filtered and sampled filter liquor by thin melt and analyzed for NMR, which show in the absence of MAO, In the absence of TMA.The wet solid is washed and is dried under vacuum 90min with 4X hexanes, will so as to generate 18.0g sMAO It analyzes and found the solvent for still including about 7%.11.5mmol Al/g silica sMAO (" sMAO-11.5 ") is tested Show the absorptivity of other 5.07mmol Al/g silica.Then, by 3.1g sMAO-11.5 in 20mL bottles Slurrying in 8g toluene.The pure TIBA of about 0.17g (0.85mmol) are slowly added in the slurry under violent vibration.The slurry is right After be placed in 10min on shaking table, during this period observe gas release, this show sMAO 100 DEG C heat 3h while passed through Fragmentation is gone through, so as to expose the surface area of reservation and cause more reactive hydroxyls exposed to reaction.Then, by 30mg MCN3 (0.051mmol Zr) adds the slurry and vibrates the mixture 2 hours on shaking table in RT.By the dark-brown slurry Filtering, is washed with 10g toluene and 2x6g hexanes, is then dried 2 hours under vacuum, so as to generate 3.08g sCat+TIBA.Will The sCat is used to prepare the iPP15 shown in table 9.
The high temperature load (iPP16) handled without TIBA：11.0g sMAO-11.5 and 53g first is added into reactor Benzene, and stirred with 350rpm.Add 0.130g MCN3's (0.22mmol Zr) and 6.11g simultaneously into 20mL bottles MAO, for the addition of other 5mmol Al/g silica, based on above-mentioned sMAO absorptance analysis.Will be mixed in the bottle Compound fully vibrates, and then adds it in the slurry in reactor.Then the mixture is made to be stirred 2 hours in RT, Ran Houtong Meticulous melt filtering, is washed twice with 5X toluene and is washed twice with 4X hexanes, and is dried 60 hours in RT under vacuo, so as to Produce 11.3g sCat.The iPP16 shown in table 9 is prepared using the sCat.
Carry out the low temperature load (ICP1) of TIBA processing：In glove box, 5.0g silica S2 and 10X toluene are added In the reactor, and it is placed in 30min in -20 DEG C of refrigerators.Then, 30%MAO (the 7.0mmol Al/g bis- 7.0g precooled Silica) it is slowly added into 20min with the SiO 2 slurry of 600rpm stirrings.Stir speed (S.S.) be reduced to 300rpm and The reactor is maintained at RT3 hours.Stop the agitator, and the slurry is settled 5min, then filtered by thick melt. Wet cake is washed twice with 10X toluene.The wet cake is added reactor together with 7X toluene and stirred with 300rpm.Then will 0.501g TIBA add the slurry, and after 15min is stirred, 0.139g MCN3 is added into the reactor.1h is stirred in RT Afterwards, the slurry is filtered by thick melt and is washed twice with 8X toluene and washed twice with 8X hexanes.By wet cake in vacuum Lower dry 1h, so as to generate 7.04g.The sCat is used to prepare the ICP1 shown in table 9.
The low temperature handled without TIBA loads (ICP1)：Similar program has been used, but without addition TIBA, and yield It is 7.07g.The sCat is used to prepare the ICP2 shown in table 9.
As shown in table 9, TIBA processing adds catalyst activity, and this, which is considered as being attributed to the fact that, eliminates possible hydroxyl, It may expose in MAO loads and/or carrier Fragmentation.Table 10 lists polymer features and hardness data. These data further demonstrate provides the obvious of iPP and/or ICP hardness according to the catalyst of embodiment disclosed herein Improving, it is characterized by 1% Secant flexural modulus hardness, is greater than about 1950MPa, more than about 2000MPa, More than about 2100MPa, more than about 2200MPa.
Figure 11 is ICP1 GPC-4D chromatograms, is that about 18-20wt% and EP rubber is inhaled which show ethylene absorption rate Yield is 37wt%.Calculated by yield data, total EP rubber absorptivity is 44wt%.Therefore, 37-44wt%EP rubber absorptivity It can be realized according to embodiment of the present invention, which represent given birth to relative to using ZN catalyst systems known in the art The vast improvement of the impact copolymer (it usually requires post-reactor and adds plastic body to produce ICP) of production.
For wherein allowing the purpose in all area under one's jurisdictions of such practice, All Files as described herein is by quoting simultaneously Enter, including any priority document, related application and/or test program, as long as they with not contradicting herein.Such as from foregoing one As it is obvious in property description and specific embodiment, although the form of the present invention has been shown and described, do not departing from In the case of the spirit and scope of the present invention, various changes can be carried out.Therefore, it is not intended to thus limit the present invention.Equally, art It is synonymous that language "comprising", which is considered as with term " comprising ",.Equally no matter when carried before the group of composition, key element or key element During conjunction "comprising", it should be understood that it is also contemplated that the composition, one or more key elements record before with connection Word " substantially by ... form ", " by ... form ", the identical of " be selected from by ... the group formed " or "Yes" form or The group of person's key element, vice versa.
Table 1：The performance and calcining heat of silica
Tc- calcining heats；PS- particle mean sizes (come from manufacturer)；SA-BET surface areas (come from manufacturer)；PV- Pore volume (comes from manufacturer)；PD- bore dias (come from manufacturer)
The MAO preparation conditions that table 2. loads
aMAO ratios are provided with total mmol Al/g silica；bMAO adds temperature T1；cMAO reactions after MAO additions Temperature T2；dThe MAO time under reaction temperature T2.* by assuming that the molecular weight of the MAO on carrier=59g/mol is added based on MAO Material evaluation.
Table 3：Catalyst

Claims (25)

1. acrylic polymers, it is included：
At least 50mol% propylene；
1% Secant flexural modulus is at least 1000MPa, and it is determined according to ASTM D790 (A, 1.0mm/min)；
More than 5 and it is less than 200 area defects/10000 propylene units, it is to pass through13C NMR measure；With
If there is comonomer, then it is 50% or bigger to form Distribution Breadth Index (CDBI)；
Matrix, its include porosity be 15% or bigger and median pore size diameter between more than 6 and less than 160 μm, it is logical Cross mercury injection method measure.
2. the acrylic polymers of claim 1, the wherein porosity are 30% or bigger.
3. the acrylic polymers of claim 1, it is distributed comprising multimodal molecular weight.
4. the acrylic polymers of claim 1, the wherein polymer are particle form, wherein at least 95 volume %, which have, to be more than greatly About 120 μm of granularity.
5. the acrylic polymers of claim 1, it includes multimodal size distribution.
6. the acrylic polymers of claim 1, it is further comprising the active catalyst system being dispersed in the matrix, the catalysis Agent system includes single site catalysts precursor compound, for the activator of precursor compound, and carrier, the ratio of the carrier Surface area is 400m2/ g is bigger, and pore volume is 0.5-2mL/g and average pore diameter is
7. the acrylic polymers of claim 1, it includes heterophasic copolymer, and the heterophasic copolymer includes and fills base at least in part The filling phase in the hole in matter.
8. the acrylic polymers of claim 1, it is further included：
Total propylene content is at least 75wt%；
If there is comonomer, then total comonomer content is that about 3wt% height arrives about 25wt%；
If there is comonomer, then CDBI is at least 60%；
Matrix pores rate is at least 35%；
Matrix median pore size diameter is more than 8 μm and less than 150 μm, and it is determined by mercury injection method；
At least 50% unit group of isotaxy five；
More than 10 area defects/10000 propylene units, it is to pass through13C NMR measure；
1% Secant flexural modulus is at least 1800MPa；
Fusing point (Tm, DSC peak second melting) is at least 145 DEG C；
It is high to 5 that 1 is greater than by the GPC-DRI Mw/Mn measured；
Multimodal molecular weight is distributed, and overall Mw/Mn is greater than 1-20 and at least one most probable value with the Mw/ more than 1-5 Mn；
At least 95 volume % have the granularity for being more than 150 μm of height to 10mm；
Melt flow rate (MFR) (MFR, ASTM1238,230 DEG C, 2.16kg), which is that about 0.1dg/min is high, arrives about 300dg/min；
Mw (being measured by GPC-DRI) is 50000-1000000g/mol；Or
It is combined.
9. the method for polypropylene, it includes：
(a) propylene monomer is contacted with catalyst system under polymerization conditions, the catalyst system includes single-site catalyzed The particle mean size of agent precursor compound, activator and carrier, the wherein carrier is 30 microns of height to 200 microns, and surface area is 400m2/ g is bigger, and pore volume is 0.5-2mL/g and average pore diameter is 1-20nm (10-200 angstrom), and it is by BET nitrogen Gas determining adsorption；With
(b) propylene polymer matrix is formed, it includes at least 50mol% propylene, and porosity is 15% or bigger, and it is Determined by mercury injection method.
10. the method for claim 9, the wherein carrier include the agglomerate of multiple primary granules.
11. the method for claim 10, it further comprises, by the agglomerate fragmentation, catalyst active center being dispersed in In the propylene polymer matrix.
12. the method for claim 9, the wherein carrier include the silica of spray drying, the silica of the spray drying Particle mean size with more than 50 μm, less than 1000m2/ g specific surface area or its combination.
13. the method for claim 9, the wherein specific surface area are more than 650m2/ g and average pore diameter are less than
14. the method for claim 9, the wherein specific surface area are less than 650m2/ g or average pore diameter are more than
15. the method for claim 9, the wherein activator include aikyiaiurnirsoxan beta.
16. the method for claim 9, the wherein catalyst system further include activator promotor, it is selected from：Trimethyl aluminium, three Aluminium ethide, triisobutyl aluminium, tri-n-octylaluminium, three hexyl aluminium and diethyl zinc.
17. the method for claim 9, wherein contact of the propylene monomer with catalyst system is carried out in slurry.
It is about 0.96MPa (140psi)-about 7MPa that 18. the method for claim 9, the wherein polymerizing condition, which include pressure, (1kpsi), temperature are about -20 DEG C to 150 DEG C, and the residence time is 15-720 minutes, are existed or in the absence of hydrogen, and exist or Ethene or C is not present in person4-C20Comonomer.
19. the method for claim 9, wherein the propylene monomer in (a) there is no ethene and C4-C20Alhpa olefin, and institute's shape Into acrylic polymers be Noblen.
20. the method for claim 9, it further comprises changing hydrogen or the concentration of other chain-transferring agents in (a), and wherein (b) acrylic polymers formed in is distributed comprising multimodal molecular weight.
21. the method for claim 9, it further comprises the propylene polymer matrix from (b) and one or more α-alkene Hydrocarbon monomer contacts under polymerization conditions, and to form heterophasic copolymer, it includes the filling in the hole in filling substrate at least in part Phase.
22. the method for claim 9, it further comprised the acrylic polymers at 1000 seconds-1Or bigger shear rate Lower melt-processed.
23. the method for claim 9, wherein the single site catalysts precursor compound is shown in following formula：
(Cp)mRAnM4Qk
Wherein：
Each Cp is cyclopentadienyl moieties or the substitution ring substituted with one or more alkyl with 1-20 carbon atom Pentadienyl part；
RAIt is the structure bridge between two Cp parts；
M4It is the transition metal selected from the 4th or 5 races；
Q is alkyl of the hydrogen-based either with 1-20 carbon atom or the alkenyl with 2-20 carbon atom, or halogen；
M is 1,2 or 3, and if it is 2 or 3 to limit m, each Cp can be with identical or different；
N is 0 or 1, and if restriction m=1, n=0；With
K is so, i.e. so that k+m is equal to M4Oxidation state, and if limit k be more than 1, each Q can be with identical or different.
24. the method for claim 9, wherein the single site catalysts precursor compound is shown in following formula：
RA(CpR”p)(CpR*q)M5Qr
Wherein：
Each Cp is cyclopentadienyl moieties or substituted cyclopentadienyl moieties；
Each R* and R " is the alkyl for having 1-20 carbon atom, and can be with identical or different；
P is 0,1,2,3 or 4；
Q is 1,2,3 or 4；
RAIt is the structure bridge between Cp parts, it assigns metallocene compound solid hardness；
M5It is the 4th, 5 or 6 race's metal；
Q is the alkyl or halogen for having 1-20 carbon atom；
R is that s subtracts 2, and wherein s is M5Chemical valence；
Wherein (CpR*q) there is two sides or false two sides symmetry；Select R*q, to cause (CpR*q) form fluorenyl, alkyl substitution Indenyl, or four-, three-or dialkyl group substitution cyclopentadienyl group；(CpR "p) it is included in one of remote location and only Bulky group in one of only；
Wherein the bulky group is formula ARw v；With
Wherein A is selected from group-4 metal, oxygen or nitrogen, and RwIt is methyl or phenyl, and v is that A chemical valence subtracts 1.
25. the method for claim 9, wherein the single site catalysts precursor compound is shown in following formula：
Wherein：
M is the 4th, 5 or 6 race's metal；
T is bridged group；
Each X is independently anion leaving group；
Each R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12And R13It is independently halogen atom, hydrogen, alkyl, substituted hydrocarbon Base, halocarbyl, substituted halocarbyl, silicyl is carbon-based, and substituted silicyl is carbon-based, and germyl is carbon-based, substitution The carbon-based substituent of germyl or-NR'2,-SR' ,-OR' ,-OSiR'3Or-PR'2Group, wherein R' are halogen atoms, C1-C10Alkyl or C6-C10One of aryl.
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