CN106608933A - Catalyst component for olefin polymerization, preparation method and application thereof - Google Patents
Catalyst component for olefin polymerization, preparation method and application thereof Download PDFInfo
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- CN106608933A CN106608933A CN201510707980.3A CN201510707980A CN106608933A CN 106608933 A CN106608933 A CN 106608933A CN 201510707980 A CN201510707980 A CN 201510707980A CN 106608933 A CN106608933 A CN 106608933A
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Abstract
The invention relates to a preparation method of a catalyst component for olefin polymerization, a catalyst component obtained by the preparation method, and a catalyst system for olefin polymerization. In addition, the invention also relates to a polymerization method of polyolefin for pipe polymerization. The catalyst component and catalyst system obtained by the preparation method provided by the invention have the characteristics of good particle morphology, high polymerization activity, insensitive hydrogen regulation, and no use of phthalate compounds, a polymer obtained by applying the catalyst component and catalyst system to corresponding olefin polymerization has wide molecular weight distribution.
Description
Technical field
The present invention relates to a kind of preparation method of the catalytic component for olefinic polymerization, the use prepared by the method
Catalytic component and its application in olefinic polymerization.
Background technology
At present, it is using magnesium, titanium and electron donor as the catalytic component of basis, i.e., well known in the art
Ziegler-Natta (Z-N) catalyst, can be used for CH2=CHR olefinic polyreactions, particularly have
The polymerization of higher yields and higher stereospecificity can be obtained in the alpha-olefine polymerizing of 3 carbon or more carbon atoms
Thing.One of its preparation method is first magnesium chloride to be prepared into into homogeneous solution, then is contained by crystallizing to separate out and load
The active component of titanium.In solution modeling system, the only presence of precipitation additive is possible to obtain granularity
Uniform solidss, precipitation additive is typically using class chemical combination such as organic acid anhydride, organic acid, ketone, ether, esters
Thing.
CN85100997A discloses titanium-containing catalyst component, be by magnesium halide be dissolved in organic epoxy compound thing and
Organic phosphorus compound forms homogeneous solution, the solution and titanium tetrahalide or derivatives thereof and mixes, in precipitation additive
As in the presence of organic acid anhydride, solidss are separated out；This solids is processed with multi-carboxylate so as to be attached to solid
On body thing, then processed with titanium tetrahalide and inert diluent and obtained.When the catalyst is used for propylene polymerization,
Catalyst activity is higher, and the isotacticity of resulting polymers is higher, and apparent density is big.But the preparation of the catalyst
Technics comparing is complicated, and raw materials used species is various, and reaction process is longer.Meanwhile, this method prepares catalysis
The yield and catalyst performance of agent all needs further raising.
CN1042156A discloses a kind of using the catalyst system for being eutectoid out method preparation, in the catalyst system
Ingredient of solid catalyst containing Ti be in decane solvent, solid magnesium dichloride to be dissolved in into organic alcohol compound
After as in 2-Ethylhexyl Alcohol, added organic acid anhydride dissolving, precipitation is separated out under titanium tetrahalide effect, then through four
The process such as halogenated titanium obtains main catalyst component.The catalyst is used for propylene polymerization, and catalyst activity is higher,
Morphology is preferable.But catalyst titanium tetrachloride amount used in building-up process is larger, polymer
Isotacticity is lower slightly, and the yield and catalyst performance of catalyst all need further raising.
CN1436766A discloses a kind of polyhydric alcohol ester type compound, and the compound is suitable for olefinic polymerization
The preparation of catalyst.All disclose in CN1436796A, CN1453298A with this special polyol ester
The polyolefin catalyst active component that class compound is obtained for internal electron donor, the catalyst has higher activity
With preferable stereoselectivity.But when the method prepares catalyst, because polyol ester is formed in catalyst granules
Catalyst surface is carried on afterwards, and load may not be uniform, meanwhile, in order to obtain preferable catalyst performance, two
Than larger, data of this point from given in patent have also embodied the usage amount of first alcohol ester.
CN1763108A discloses a kind of catalytic component and preparation method for olefinic polymerization, solid containing Ti
Catalytic component is in solvent naphtha, solid magnesium dichloride to be dissolved in into organic alcohol compound such as 2-Ethylhexyl Alcohol
In, after adding organic acid anhydride and titanate esters dissolving, precipitation is separated out under titanium tetrahalide effect, then through four halogen
Change the process such as titanium and obtain main catalyst component.The catalyst be used for propylene polymerization, morphology compared with
It is good.But catalyst titanium tetrachloride amount used in building-up process is larger, and catalyst activity is lower slightly, catalyst
Yield and polymerization all need further raising.
Disclose in CN102276765B and be prepared for granule using the precipitation additive system containing glycol ester compounds
Form is good, and polymerization activity is high and the strong catalyst solid constituent of capacity of orientation.In above-mentioned catalyst solid group
There are a certain amount of glycol ester compounds in point.The content of diol-lipid compound in catalyst>6 weight %.
The polymer prepared when this catalyst solid constituent is used for into olefinic polymerization has the wider spy of molecular weight distribution
Point.However, such catalyst solid constituent is still suffered from terms of more wide molecular weight distribution polyolefin is obtained
It is not enough.
It is well known that homopolymerization or combined polymerization polyolefin pipe material are the very low polyolefin products of a class melting means, this is just
The Z-N catalyst that requirement is used in process of production can not be too sensitive to molecular weight regulator hydrogen, otherwise can make
The melting means process of product produces difficult；In addition, hydrogen has necessarily to the activity of Z-N catalyst under finite concentration
Facilitation, the Z-N catalyst too sensitive to hydrogen is used to prepare when eutectic refers to product because using hydrogen amount relatively low,
The polymerization activity of catalyst is also low.Molecular weight distribution (MWD) affects the mechanical performance of polymer and processing
Performance.High molecular weight moieties determine to a great extent the long term mechanical strength of polymer, and low molecular weight fraction
Its extrusion performance is determined to a great extent.In the industry generally, it is considered that the wide polyolefin products of molecular weight distribution for
It is favourable as tube material.The also polyolefin products of some specific uses, such as high melt strength, propylene,
It also is intended to wide molecular weight distribution.Sum it up, in the production and preparation of some special polyolefin material,
It is desirable to the Z-N catalyst for using not only molecular distribution width, and hydrogen adjusts insensitive；Certainly, this catalysis
Agent should also have high activity and good capacity of orientation.
But, there is problems with when tubing polyolefin is prepared in above-mentioned existing catalyst：
1) molecular weight distribution is not wide enough, so as to have influence on the processing characteristics and mechanical property of product；
2) catalyst is more sensitive to the hydrogen as molecular weight regulator, is unfavorable for that eutectic refers to polyolefinic system
It is standby.
In addition, in view of the hot and cold water of pipe-type polyolefin products conveying not only possible directly connects with human body
Touch, it is also possible to directly drink, and the presence of phthalic acid ester (one kind of plasticiser) can shadow in polyolefin
The development to male fecundity is rung, it is exceeded that various countries work out corresponding regulation restriction phthalic acid ester content in succession
Plastic use (scope).Therefore the phthalic acid used in polyolefin catalyst preparation process is avoided
Ester is pursued in the industry.
As can be seen here, it is to prepare tubing polyolefin, it is desirable to provide particle shape is good, polymerization activity is high,
Hydrogen adjusts insensitive, and does not use the catalytic component and catalyst system of phthalate compound, should
Catalytic component and catalyst system are used for the molecular weight distribution width of corresponding olefinic polymerization resulting polymers.
The content of the invention
First purpose of the present invention is to overcome the existing method for preparing the catalytic component for olefinic polymerization,
Resulting catalytic component when being polymerized for catalyst system, prepared polyolefinic molecular weight
Narrowly distributing, so as to be not suitable for tube material, and using the defect of phthalate compound, there is provided
A kind of preparation method of new catalytic component for olefinic polymerization.
Second object of the present invention is to provide the catalysis for olefinic polymerization prepared using above-mentioned preparation method
Agent component.
Third object of the present invention is to provide a kind of catalyst system for olefinic polymerization.
Fourth object of the present invention is to provide a kind of olefine polymerizing process.
The present inventor has found in the research and development for the olefin polymerization catalysis of tube material are prepared, in Z-N
In polyolefin catalyst, compound as internal electron donor and the titanium as polymerization activity center are adsorbed to
, there is competitive Adsorption relation to a certain extent in the crystalline surface of active magnesium chloride.In other words, internal electron donor
The quality and quantity of the titanium as active center is influenced whether in the adsorbance and state of chlorination magnesium surface.Separately
Outward, as the total amount of titanium in active center, not the higher the better, desired for tubing use as the present invention
Catalytic component prepared by polyolefin, it is desirable to which Ti content controls the ideal range in 2.5-3.5 weight %.If titanium
Too high levels, catalyst is more easy to occur temperature fluctuation etc. when continuous polymerization is applied to unstable uncontrollable existing
As；Also, Ti content is too high, the active center of the low capacity of orientation in catalyst is increased, and can reduce final
The stereoregularity of polyolefin products, so as to reduce properties of product.Further, based on cyano group succinic acid esters
The high preparation cost of compound considers, it is necessary to improve its service efficiency.Therefore, especially with containing cyanogen
The catalytic component of base succinic acid ester type compound and glycol ester compounds, while controlling titanium atom in catalyst
Content has the olefin polymer as tube material of wide molecular weight distribution for preparing, and has important impact.
Furthermore, it is contemplated that the direction of the restriction of regulation and technology development, does not use phthalate compound,
And adjust the preparation of the catalyst.Thus, inventor provides the present invention.
Provided by the present invention for the preparation method of the catalytic component of olefinic polymerization, comprise the following steps：
1) magnesium halide and alcohol compound are carried out into the first haptoreaction in the presence of varsol, is formed molten
Liquid, is preferably formed as homogeneous solution；
2) in the presence of precipitation additive, by step 1) obtained by solution and Part I titanium compound carry out the
Two haptoreactions, obtain the mixture containing solid precipitation；
3) by step 2) obtained by mixture and Part I internal electron donor carry out the 3rd haptoreaction, obtain
Suspension；
4) by step 3) suspension that obtains carries out solid-liquid separation, the solid constituent for obtaining and Part II titanizing
Compound, Part II internal electron donor carry out the 4th haptoreaction, then carry out solid-liquid separation (such as by filtering
Or centrifugation etc.), obtain solid product；
5) by step 4) solid product that obtains carries out the 5th haptoreaction with Part III titanium compound, obtains
The catalytic component.
The preferred implementation of preparation in accordance with the present invention, the precipitation additive includes precipitation additive a, its
Described in precipitation additive a be formula (I) shown in diol-lipid compound,
In formula (I), R1-R2May be the same or different, each respectively substituted or unsubstituted C1-C20Straight chain alkane
Base, substituted or unsubstituted C3-C20Branched alkyl, substituted or unsubstituted C3-C20Cycloalkyl, replacement or not
Substituted C6-C20Aryl, substituted or unsubstituted C7-C20Alkaryl, substituted or unsubstituted C7-C20Aralkyl
Base, substituted or unsubstituted C2-C10Alkylene or substituted or unsubstituted C10-C20Fused ring aryl；R3-R8
May be the same or different, each respectively hydrogen, halogen, substituted or unsubstituted C1-C20Straight chained alkyl, replacement or
Unsubstituted C3-C20Branched alkyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C6-C20
Aryl, substituted or unsubstituted C7-C20Alkaryl, substituted or unsubstituted C7-C20Aralkyl, replacement or not
Substituted C2-C10Alkylene or substituted or unsubstituted C10-C20Fused ring aryl；Or R3-R6In at least
One and R7-R8At least one of cyclization.
The preferred implementation of preparation in accordance with the present invention, the precipitation additive includes precipitation additive b, its
Described in precipitation additive b be formula Ti (OR9)nX4-nShown titanate ester compound, wherein, R9For C1-C10
Straight chained alkyl, C3-C10Branched alkyl or C3-C10Cycloalkyl, X is halogen, preferred fluorine, chlorine, bromine or iodine,
1≤n≤4, and n is integer.
The preferred implementation of preparation in accordance with the present invention, the precipitation additive includes above-mentioned precipitation additive a
With above-mentioned precipitation additive b.
The preferred implementation of preparation in accordance with the present invention, the Part I internal electron donor and described
One or both of which includes the cyano group succinic acid esters chemical combination shown in formula (II) in two part internal electron donors
Thing,
In Formula II, R1＇ and R2＇ can be identical or differs, and is each independently selected from hydrogen, C1-C14Straight chain alkane
Base, C3-C14Branched alkyl, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Virtue
Alkyl；R3＇ and R4＇ can be identical or differs, and is each independently selected from C1-C10Straight chained alkyl, C3-C10
Alkyl group, C3-C10Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl and C7-C20Aralkyl.
Preferably, R1＇ and R2＇ is each independently selected from hydrogen, C1-C8Straight chained alkyl and C3-C8Branched alkyl.
Preferably, R3＇ and R4＇ is each independently selected from C1-C6Straight chained alkyl and C3-C6Branched alkyl.
The preferred implementation of method produced according to the present invention, step 2) used in precipitation additive a with
The mol ratio of the total internal electron donor for being used in the method is (0.05-0.5):1, preferably
(0.1-0.4):1, more preferably (0.15-0.35):1.
The preferred implementation of method produced according to the present invention, the Part I internal electron donor and described
The mol ratio of two part internal electron donors is (0.1-10):1, preferably (0.2-5):1, more preferably
(0.2-1):1。
The preferred implementation of method produced according to the present invention, the precipitation additive include the precipitation additive a and
The precipitation additive b, and the mol ratio of the precipitation additive a and precipitation additive b is 1:(0.01-5),
Preferably 1:(0.5-3), more preferably 1:(0.5-1.5).
The preferred implementation of method produced according to the present invention, the titanium compound in terms of titanium elements, the halogenation
Magnesium in terms of magnesium elements, alcohol compound, in the method total titanium compound used in the method, institute
Total internal electron donor and the mol ratio of magnesium halide is (2-4):(12-160):(0.01-3):1,
Preferably (2.5-3.5):(20-140):(0.02-0.3):1.
The preferred implementation of method produced according to the present invention, step 1) used by magnesium halide and step 2) institute
The mol ratio of total precipitation additive is 1:(0.025-0.9), preferably 1:(0.03-0.3).
In order to processability it is excellent be suitable to prepare tubing polyolefin catalyst solid constituent, need strict control
Diol-lipid compound processed content in the catalyst.Content is too low, then the activity of catalyst can be subject to certain journey
The impact of degree.But if the precipitation additive diol-lipid compounds content remained in catalyst is higher, corresponding two
The amount of ester compounds is also required to higher.However, the capacity of internal electron donor is limited in catalyst.Gu
This, it is necessary to diol-lipid compound residual in catalyst solid constituent of the control as precipitation additive
Amount.Therefore, it is necessary to strictly control the mol ratio of the precipitation additive a and the total amount of the internal electron donor.Root
According to the present invention, the precipitation additive a exists with the mol ratio of the total amount of the internal electron donor for control
(0.05-0.5):1, preferably (0.1-0.4):1, more preferably (0.15-0.35):1.
According to the present invention, in the preparation method, the alcohol compound, titanium compound, internal electron donor
With the consumption of the magnesium halide, can be carried out with the composition of polyolefinic catalytic component according to expected tubing
Properly select.Under preferable case, in terms of titanium elements, the magnesium halide is with magnesium elements for the titanium compound
Meter, the alcohol compound, the total amount of titanium compound, the total amount of internal electron donor are rubbed with the magnesium halide
Your ratio can be (2-4):(12-160):(0.01-3)：1；Preferably (2.5-3.5):(20-140):
(0.02-0.3):1。
In the method that the present invention is provided, titanium compound can be added several times, such as step 2) middle addition first
Divide titanium compound, step 4) middle addition Part II titanium compound, step 5) middle addition Part III titanizing
Compound etc..The method can also as needed be further added by the step of adding titanium compound, until meeting preparation side
Method needs the total amount of the titanium compound for providing.In addition the addition of Part I titanium compound can meet first
Part titanium compound：The mol ratio of the magnesium halide (being counted with magnesium elements) is as 3-40:1, preferably 5-35:1；
As long as the amount of the other parts titanium compound of addition can with the addition total amount for making final titanium compound meet it is aforementioned with
Mol ratio between the magnesium halide.Substep adds titanium compound to better control over titanium active component
Overall control and well distributed, the service efficiency of raising internal electron donor in catalytic component, is conducive to
Tubing polyolefin is prepared with broader molecular weight distribution and high chain regularity.
According to the present invention, 1 the step of the preparation method) in, the first catalytic purpose be in order to
Make the magnesium halide, alcohol compound that magnesium halide and the adduct of alcohol are formed in the presence of varsol (can claim again
For magnesium halide alcohol adduct) homogeneous solution.The present invention is to carrying out the first haptoreaction to form the bar of homogeneous solution
Part can determine without specific restriction according to the concrete halogenated magnesium compound for using.Under preferable case,
Forming the first haptoreaction of homogeneous solution can be carried out under the conditions of alcohol is closed, the first catalytic bar
Part generally can include：First catalytic temperature is 30-150 DEG C, preferably 60-140 DEG C；First contact
The time of reaction is 0.5-10 hours, preferably 0.5-6 hours.
According to the present invention, the magnesium halide can for magnesium dihalide, the complex of the water of magnesium dihalide or alcohol,
The one of the derivant that one or two halogen atom in magnesium dihalide molecular formula is replaced by alkyl or halocarbon epoxide
Plant or various.In the present invention, the halogen can be at least one in fluorine, chlorine, bromine and iodine, preferably
Chlorine and/or bromine.The instantiation of the magnesium halide can be magnesium dichloride, dibrominated magnesium, chlorination phenoxy group
One or more in magnesium, chlorination isopropoxy magnesium, chlorination butoxy, preferably anhydrous magnesium dichloride.
According to the present invention, the alcohol compound can be at least in fatty alcohol, alicyclic ring alcohol and aromatic alcohol
Kind.Wherein fatty alcohol is preferably C1-C10Straight chain or C3-C10Branched fatty alcohol；Alicyclic ring alcohol is preferably
C3-C12Alicyclic ring alcohol；Aromatic alcohol is preferably C6-C20Aryl alcohol or C7-C20Alkylaryl alcohol.The alcohol
The specific example of class compound can be in ethanol, propanol, butanol, 2-Ethylhexyl Alcohol, benzyl alcohol and phenethanol
At least one, preferably 2-Ethylhexyl Alcohol.
According to the present invention, 1 the step of the preparation method) in, the varsol for using can be ability
There is no chemically interactive varsol in conventional various in domain, specific real with the magnesium halide alcohol adduct
Example can for alkane, cycloalkane, one or more of aromatic hydrocarbon, preferably decane, benzene, toluene, diformazan
One or more in benzene, more preferably toluene.
According to the step of the present invention, the preparation method 2) concrete operations in be not particularly limited, can refer to
Prior art is carried out, for example step 2) in Part I titanium compound can individually with step 1) obtained by
Homogeneous solution is reacted in the presence of precipitation additive, it is also possible to which Part I titanium compound and inertia is dilute
Release and reacted in the presence of precipitation additive with the homogeneous solution after agent is mixed.Under preferable case,
With homogeneous solution the depositing in precipitation additive after Part I titanium compound is mixed with inert diluent
The second haptoreaction is carried out under.Usually, preparation method according to the present invention, the inert diluents
Agent can be at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene, preferred first
Benzene.Part I titanium compound (being counted with titanium elements) can be as 1-20 with the mol ratio of the inert diluent:1,
Preferably 2-8:1.
According to the present invention, step 2) in the described second catalytic condition can include：In precipitation additive
In the presence of, by step 1) obtained by homogeneous solution contact 3-5 at a temperature of -40 DEG C to 0 DEG C with titanium compound
Hour, then heat to 50-150 DEG C；Preferably, in the presence of precipitation additive, by step 1) obtained by
Homogeneous solution contacts 3.5-4.5 hours with titanium compound at a temperature of -30 DEG C to -20 DEG C, then heats to
90-130℃.Step 2) in, can be first lazy with described by the titanium compound at a temperature of -40 DEG C to 0 DEG C
Property diluent mixture and the homogeneous solution mixing, be subsequently adding precipitation additive solution contact 3-5 hours,
50-150 DEG C is then heated to, the mixture containing solid precipitation is obtained；Or be first added to precipitation additive solution
In the homogeneous solution, then at a temperature of -40 DEG C to 0 DEG C, then with the titanium compound and the inert diluents
50-150 DEG C is warming up to after the mixture contact 3-5 hours of agent, the mixture containing solid precipitation is obtained；It is preferred that first
Precipitation additive solution is added in the homogeneous solution, then at a temperature of -40 DEG C to 0 DEG C, with the titanizing
Compound is contacted after 3-5 hours with the mixture of the inert diluent and is warming up to 50-150 DEG C, obtains heavy containing solid
The mixture in shallow lake；More preferably first precipitation additive solution is added in the homogeneous solution, then at -30 DEG C
To at a temperature of -20 DEG C, contact after 3.5-4.5 hours with the titanium compound with the mixture of the inert diluent
90-130 DEG C is warming up to, the mixture containing solid precipitation is obtained.
According to the present invention, step 2) in, the magnesium halide (in terms of magnesium elements) and the precipitation additive total amount
Mol ratio be 1：(0.025-0.9), preferably 1：(0.03-0.3).
, according to the invention it is preferred in the case of, in step 2) in, the magnesium halide in terms of magnesium elements, the halogen
It is 1 to change magnesium with the mol ratio of the precipitation additive a:(0.005-0.3), preferably 1:(0.01-0.05)；It is described to help analysis
The mol ratio for going out agent a and precipitation additive b can be 1:(0.01-5), preferably 1:(0.5-3), more preferably 1:
(0.5-1.5)。
According to the present invention, the titanium compound that in multiple steps substep is added can be commonly used in the art
Various titanium compounds, under preferable case, the titanium compound can be three halogenated titaniums and/or formula
Ti(OR10)mX4-mShown titanium compound, in the formula, R10Can be alkyl, preferably C1-C10Alkane
Base, X can be halogen, such as Cl, Br or I, and 0≤m≤3, m is integer.Preferably, the titanium compound
For titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, the halogenated titanium of alkoxyl three, dialkoxy dihalide titanium, three
One or more in alkoxy titanium, preferably titanium tetrachloride.
, according to the invention it is preferred in the case of, the precipitation additive a can be 2- ethyls -1,3-PD hexichol first
Acid esters, 2- propyl group -1,3- propylene glycol dibenzoates, the dipropylene of 2- isopropyl -2- isopentyl -1,3
Ester, 1,3 butylene glycol mesitylenic acid ester, 2- methyl isophthalic acids, the m-chlorobenzoic acid ester of 3- butanediols two, 2,3- dimethyl
- 1,3 butylene glycol dibenzoate, the pivalate of 1,3- pentanediols two, 2,4-PD dibenzoate, 2- methyl
- 1,3- pentanediol benzoic acid cinnamate, 2,2- dimethyl -1,3- glycol dibenzoates, 2,4- heptandiols two
Benzoate, 3,5- heptandiol dibenzoates, 4- ethyls -3,5- heptandiols dibenzoate and 2- methyl -3,5-
At least one in heptandiol dibenzoate；Preferably 3,5- heptandiols dibenzoate, 4- ethyls -3,5- heptan
At least one in bisbenzoate and 2,4-PD dibenzoate.
, according to the invention it is preferred in the case of, the precipitation additive b is formula Ti (OR9)nX4-nShown metatitanic acid
Ester type compound, wherein, R9For C1-C10Alkyl or C3-C10Cycloalkyl, X is halogen, 1≤n≤
4, n is integer；Preferably, R9Carbon number be preferably 2-6.
It is highly preferred that the precipitation additive b is tetramethoxy titanate ester, butyl titanate, tetraethyl titanate and metatitanic acid
At least one in four isopropyl esters；More preferably butyl titanate.
According to the present invention, in step 3) in, it is wider and regular for the molecular weight distribution of tube material in order to prepare
Property higher olefin polymer, Part I internal electron donor can be two ester type compounds shown in formula (II).
Dihydroxylic alcohols ester type compound, phthalic acid ester of other internal electron donors known in the industry as shown in formula (I)
Class, malonic acid esters, 1,3- diether compounds, 1,3-propanedicarboxylic acid esters, pivalate or carbonats compound
Because the molecular weight distribution for preparing is narrow, internal electron donor of the present invention is not suitable for.
According to the present invention, 3 the step of the preparation method) in, the 3rd catalytic condition includes：
The temperature of reaction is 20-120 DEG C, preferably 70-110 DEG C；The time of reaction be 0.5-6 hours, preferably 1-4
Hour.
The preferred implementation of method produced according to the present invention, electronics in electron and Part II in Part I
Body is identical or different, is each independently selected from：
2- cyano group -2,3- diisopropyl dimethyl succinates, 2- cyano group -2,3- diisopropyl diethyl succinates,
2- cyano group -2,3- dimethyl succinic acid diethylesters, 2- cyano group -2,3- diethyl succinic acid diethylesters, 2- cyano group -2,3-
Diη-propyl diethyl succinate, 2- cyano group -2,3- di-n-butyl diethyl succinates, 2- cyano group -2,3- bis- positive penta
Base diethyl succinate, 2- cyano group -2,3- diisoamyl diethyl succinates, 2- cyano group -2,3- di-n-hexyls fourth two
Diethyl phthalate, 2- cyano group -2, the isohesyl diethyl succinates of 3- bis-, 2- cyano group -2,3- diisopropyls succinic acid two is just
Propyl ester, 2- cyano group -2,3- diisopropyl diisopropyl ester amber acids, 2- cyano group -2,3- diisopropyls succinic acid two are just
Butyl ester, 2- cyano group -2,3- diisopropyl succinic acid diisobutyl esters, 2- cyano group -2,3- diisopropyl succinic acid -1-
Methyl ester -4- ethyl ester (R4=methyl, R3=ethyl), 2- cyano group -2,3- diisopropyl succinic acid -1- ethyl ester -4- first
Ester (R4=ethyl, R3=methyl), 2- cyano group -2,3- diisopropyl succinic acid -1- N-butyl -4- ethyl ester (R4=
Normal-butyl, R3=ethyl), 2- cyano group -2,3- diisopropyl succinic acid -1- ethyl ester -4- N-butyl (R4=ethyl,
R3=normal-butyl), 2- cyano group -2,3- diisobutyl dimethyl succinates, 2- cyano group -2,3- diisobutyls fourth two
Diethyl phthalate, 2- cyano group -2,3- diisobutyl succinic acid di-n-propyl esters, 2- cyano group -2,3- diisobutyl succinic acid
Diisopropyl ester, 2- cyano group -2,3- diisobutyl succinic acid di-n-butyls, 2- cyano group -2,3- diisobutyl succinic acid
Diisobutyl ester, 2- cyano group -2,3- diisobutyl succinic acid -1- methyl ester -4- ethyl ester (R4=methyl, R3=ethyl),
2- cyano group -2,3- diisobutyl succinic acid -1- ethyl ester -4- methyl ester (R4=ethyl, R3=methyl), 2- cyano group -2,3-
Diisobutyl succinic acid -1- N-butyl -4- ethyl ester (R4=normal-butyl, R3=ethyl), -2,3- two is different for 2- cyano group
Butyl succinic acid -1- ethyl ester -4- N-butyl (R4=ethyl, R3=normal-butyl), 2- cyano group -2,3- di-sec-butyls
Dimethyl succinate, 2- cyano group -2,3- di-sec-butyl diethyl succinates, 2- cyano group -2,3- di-sec-butyls fourth two
Sour di-n-propyl ester, 2- cyano group -2,3- di-sec-butyl diisopropyl ester amber acids, 2- cyano group -2,3- di-sec-butyls fourth two
Sour di-n-butyl, 2- cyano group -2,3- di-sec-butyl succinic acid diisobutyl esters, 2- cyano group -2,3- di-sec-butyls fourth two
Acid -1- methyl ester -4- ethyl ester (R4=methyl, R3=ethyl), 2- cyano group -2,3- di-sec-butyl succinic acid -1- ethyl esters
- 4- methyl ester (R4=ethyl, R3=methyl), 2- cyano group -2,3- di-sec-butyl succinic acid -1- N-butyl -4- ethyl esters
(R4=normal-butyl, R3=ethyl), 2- cyano group -2,3- di-sec-butyl succinic acid -1- ethyl ester -4- N-butyl (R4=
Ethyl, R3=normal-butyl), 2- cyano group -2,3- bicyclopentyl dimethyl succinates, 2- cyano group -2,3- bicyclo- penta
Base diethyl succinate, 2- cyano group -2,3- bicyclopentyl succinic acid di-n-propyl esters, 2- cyano group -2,3- bicyclopentyls
Diisopropyl ester amber acid, 2- cyano group -2,3- bicyclopentyl succinic acid di-n-butyls, 2- cyano group -2,3- bicyclopentyls
Succinic acid diisobutyl ester, 2- cyano group -2,3- bicyclopentyl succinic acid -1- methyl ester -4- ethyl ester (R4=methyl, R3=
Ethyl), 2- cyano group -2,3- bicyclopentyl succinic acid -1- ethyl ester -4- methyl ester (R4=ethyl, R3=methyl),
2- cyano group -2,3- bicyclopentyl succinic acid -1- N-butyl -4- ethyl ester (R4=normal-butyl, R3=ethyl), 2- cyanogen
Base -2,3- bicyclopentyl succinic acid -1- ethyl ester -4- N-butyl (R4=ethyl, R3=normal-butyl), 2- cyano group -2,3-
Dicyclohexyl dimethyl succinate, 2- cyano group -2,3- dicyclohexyl-succinates, 2- cyano group -2,3- bicyclo-
Hexyl succinic acid di-n-propyl ester, 2- cyano group -2,3- dicyclohexyl diisopropyl ester amber acids, 2- cyano group -2,3- bicyclo-
Hexyl succinic acid di-n-butyl, 2- cyano group -2,3- dicyclohexyl succinic acid diisobutyl esters, 2- cyano group -2,3- bicyclo-
Hexyl succinic acid -1- methyl ester -4- ethyl ester (R4=methyl, R3=ethyl), 2- cyano group -2,3- dicyclohexyls fourth two
Acid -1- ethyl ester -4- methyl ester (R4=ethyl, R3=methyl), the positive fourths of 2- cyano group -2,3- dicyclohexyl succinic acid -1-
Ester -4- ethyl ester (R4=normal-butyl, R3=ethyl), 2- cyano group -2,3- dicyclohexyl succinic acid -1- ethyl esters -4- just
Butyl ester (R4=ethyl, R3=normal-butyl)；
2- cyano group -2- methyl -3- ethyl succinic acid diethylesters, 2- cyano group -2- methyl -3- n-pro-pyl diethyl succinates,
2- cyano group -2- methyl -3- isopropyl diethyl succinates, 2- cyano group -2- methyl -3- normal-butyl diethyl succinates, 2-
Cyano group -2- methyl -3- isobutyl group diethyl succinates, 2- cyano group -2- methyl -3- n-pentyl diethyl succinates, 2-
Cyano group -2- methyl -3- isopentyl diethyl succinates, 2- cyano group -2- methyl -3- cyclopenta diethyl succinates, 2-
Cyano group -2- methyl -3- n-hexyl diethyl succinates, 2- cyano group -2- methyl -3- isohesyl diethyl succinates；
2- cyano group -2- ethyl -3- diethyl methylsuccinates, 2- cyano group -2- ethyl -3- n-pro-pyl diethyl succinates,
2- cyano group -2- ethyl -3- isopropyl diethyl succinates, 2- cyano group -2- ethyl -3- normal-butyl diethyl succinates, 2-
Cyano group -2- ethyl -3- isobutyl group diethyl succinates, 2- cyano group -2- ethyl -3- n-pentyl diethyl succinates, 2-
Cyano group -2- ethyl -3- isopentyl diethyl succinates, 2- cyano group -2- ethyl -3- cyclopenta diethyl succinates, 2-
Cyano group -2- ethyl -3- n-hexyl diethyl succinates, 2- cyano group -2- ethyl -3- isohesyl diethyl succinates；
2- cyano group -2- n-pro-pyl -3- diethyl methylsuccinates, 2- cyano group -2- n-pro-pyl -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- n-pro-pyl -3- isopropyl diethyl succinates, 2- cyano group -2- n-pro-pyl -3- normal-butyls succinic acid two
Ethyl ester, 2- cyano group -2- n-pro-pyl -3- isobutyl group diethyl succinates, 2- cyano group -2- n-pro-pyl -3- n-pentyl succinic acid
Diethylester, 2- cyano group -2- n-pro-pyl -3- isopentyl diethyl succinates, 2- cyano group -2- n-pro-pyl -3- cyclopenta fourth two
Diethyl phthalate, 2- cyano group -2- n-pro-pyl -3- n-hexyl diethyl succinates, 2- cyano group -2- n-pro-pyl -3- isohesyl fourths
Diethyl adipate；
2- cyano group -2- isopropyl -3- diethyl methylsuccinates, 2- cyano group -2- isopropyl -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- isopropyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- isopropyl -3- normal-butyls succinic acid two
Ethyl ester, 2- cyano group -2- isopropyl -3- isobutyl group diethyl succinates, 2- cyano group -2- isopropyl -3- n-pentyl succinic acid
Diethylester, 2- cyano group -2- isopropyl -3- isopentyl diethyl succinates, 2- cyano group -2- isopropyl -3- cyclopenta fourth two
Diethyl phthalate, 2- cyano group -2- isopropyl -3- n-hexyl diethyl succinates, 2- cyano group -2- isopropyl -3- isohesyl fourths
Diethyl adipate；
2- cyano group -2- normal-butyl -3- diethyl methylsuccinates, 2- cyano group -2- normal-butyl -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- normal-butyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- normal-butyl -3- isopropyls succinic acid two
Ethyl ester, 2- cyano group -2- normal-butyl -3- isobutyl group diethyl succinates, 2- cyano group -2- normal-butyl -3- n-pentyl succinic acid
Diethylester, 2- cyano group -2- normal-butyl -3- isopentyl diethyl succinates, 2- cyano group -2- normal-butyl -3- cyclopenta fourth two
Diethyl phthalate, 2- cyano group -2- normal-butyl -3- n-hexyl diethyl succinates, 2- cyano group -2- normal-butyl -3- isohesyl fourths
Diethyl adipate；
2- cyano group -2- isobutyl group -3- diethyl methylsuccinates, 2- cyano group -2- isobutyl group -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- isobutyl group -3- n-pro-pyl diethyl succinates, 2- cyano group -2- isobutyl group -3- isopropyls succinic acid two
Ethyl ester, 2- cyano group -2- isobutyl group -3- normal-butyl diethyl succinates, 2- cyano group -2- isobutyl group -3- n-pentyl succinic acid
Diethylester, 2- cyano group -2- isobutyl group -3- isopentyl diethyl succinates, 2- cyano group -2- isobutyl group -3- cyclopenta fourth two
Diethyl phthalate, 2- cyano group -2- isobutyl group -3- n-hexyl diethyl succinates, 2- cyano group -2- isobutyl group -3- isohesyl fourths
Diethyl adipate；
2- cyano group -2- n-pentyl -3- diethyl methylsuccinates, 2- cyano group -2- n-pentyl -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- n-pentyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- n-pentyl -3- isopropyls succinic acid two
Ethyl ester, 2- cyano group -2- n-pentyl -3- normal-butyl diethyl succinates, 2- cyano group -2- n-pentyl -3- isobutyl group succinic acid
Diethylester, 2- cyano group -2- n-pentyl -3- isopentyl diethyl succinates, 2- cyano group -2- n-pentyl -3- cyclopenta fourth two
Diethyl phthalate, 2- cyano group -2- n-pentyl -3- n-hexyl diethyl succinates, 2- cyano group -2- n-pentyl -3- isohesyl fourths
Diethyl adipate；
2- cyano group -2- isopentyl -3- diethyl methylsuccinates, 2- cyano group -2- isopentyl -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- isopentyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- isopentyl -3- isopropyls succinic acid two
Ethyl ester, 2- cyano group -2- isopentyl -3- normal-butyl diethyl succinates, 2- cyano group -2- isopentyl -3- isobutyl group succinic acid
Diethylester, 2- cyano group -2- isopentyl -3- n-pentyl diethyl succinates, 2- cyano group -2- isopentyl -3- cyclopenta fourth two
Diethyl phthalate, 2- cyano group -2- isopentyl -3- n-hexyl diethyl succinates, 2- cyano group -2- isopentyl -3- isohesyl fourths
Diethyl adipate；
2- cyano group -2- cyclopenta -3- diethyl methylsuccinates, 2- cyano group -2- cyclopenta -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- cyclopenta -3- n-pro-pyl diethyl succinates, 2- cyano group -2- cyclopenta -3- isopropyls succinic acid two
Ethyl ester, 2- cyano group -2- cyclopenta -3- normal-butyl diethyl succinates, 2- cyano group -2- cyclopenta -3- isobutyl group succinic acid
Diethylester, 2- cyano group -2- cyclopenta -3- n-pentyl diethyl succinates, 2- cyano group -2- cyclopenta -3- isopentyl fourth two
Diethyl phthalate, 2- cyano group -2- cyclopenta -3- n-hexyl diethyl succinates, 2- cyano group -2- cyclopenta -3- isohesyl fourths
Diethyl adipate；
2- cyano group -2- n-hexyl -3- diethyl methylsuccinates, 2- cyano group -2- n-hexyl -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- n-hexyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- n-hexyl -3- isopropyls succinic acid two
Ethyl ester, 2- cyano group -2- n-hexyl -3- normal-butyl diethyl succinates, 2- cyano group -2- n-hexyl -3- isobutyl group succinic acid
Diethylester, 2- cyano group -2- n-hexyl -3- n-pentyl diethyl succinates, 2- cyano group -2- n-hexyl -3- isopentyl fourth two
Diethyl phthalate, 2- cyano group -2- n-hexyl -3- cyclopenta diethyl succinates, 2- cyano group -2- n-hexyl -3- isohesyl fourths
Diethyl adipate；And
2- cyano group -2- isohesyl -3- diethyl methylsuccinates, 2- cyano group -2- isohesyl -3- ethyl succinic acid diethyls
Ester, 2- cyano group -2- isohesyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- isohesyl -3- isopropyls succinic acid two
Ethyl ester, 2- cyano group -2- isohesyl -3- normal-butyl diethyl succinates, 2- cyano group -2- isohesyl -3- isobutyl group succinic acid
Diethylester, 2- cyano group -2- isohesyl -3- n-pentyl diethyl succinates, 2- cyano group -2- isohesyl -3- isopentyl fourth two
Diethyl phthalate, 2- cyano group -2- isohesyl -3- cyclopenta diethyl succinates, 2- cyano group -2- isohesyl -3- n-hexyl fourths
At least one in diethyl adipate；
The preferred embodiment of method produced according to the present invention, in Part I in electron and Part II
Electron is identical or different, is each independently selected from：
2- cyano group -2,3- diethyl succinic acid diethylesters, 2- cyano group -2,3- diη-propyl diethyl succinates, 2- cyano group
- 2,3- diisopropyl diethyl succinate, 2- cyano group -2,3- di-n-butyl diethyl succinates, 2- cyano group -2,3- bis- is different
Butyl diethyl succinate, 2- cyano group -2, the n-pentyl diethyl succinates of 3- bis-, 2- cyano group -2,3- diisoamyl fourths
Diethyl adipate, 2- cyano group -2,3- bicyclopentyl diethyl succinates, 2- cyano group -2,3- di-n-hexyls succinic acid two
Ethyl ester, 2- cyano group -2, the isohesyl diethyl succinates of 3- bis-；2- cyano group -2,3- diisopropyl succinic acid di-n-propyl esters,
2- cyano group -2,3- diisopropyl diisopropyl ester amber acids, 2- cyano group -2,3- diisopropyl succinic acid di-n-butyls,
2- cyano group -2,3- diisopropyls-succinic acid diisobutyl ester, 2- cyano group -2,3- diisopropyl diethyl succinates,
2- cyano group -2- normal-butyl -3- isopropyl diethyl succinates, 2- cyano group -2- isobutyl group -3- isopropyls succinic acid two
Ethyl ester, 2- cyano group -2- n-pentyl -3- isopropyl diethyl succinates, 2- cyano group -2- isopentyl -3- isopropyl fourths
At least one in diethyl adipate and 2- cyano group -2- cyclopenta -3- isopropyl diethyl succinates；More preferably
Selected from 2- cyano group -2,3- diη-propyl diethyl succinates, 2- cyano group -2,3- diisopropyl diethyl succinates, 2-
Cyano group -2,3- di-n-butyl diethyl succinates, 2- cyano group -2,3- diisobutyl diethyl succinates, 2- cyano group -2,3-
Two n-pentyl diethyl succinates, 2- cyano group -2,3- diisoamyl diethyl succinates, 2- cyano group -2,3- bicyclo- penta
Base diethyl succinate, 2- cyano group -2- normal-butyl -3- isopropyl diethyl succinates, 2- cyano group -2- isobutyl group -3-
Isopropyl diethyl succinate, 2- cyano group -2- n-pentyl -3- isopropyl diethyl succinates, 2- cyano group -2- are different
In amyl group -3- isopropyls diethyl succinate and 2- cyano group -2- cyclopenta -3- isopropyl diethyl succinates
It is at least one.
In the present invention, Part I internal electron donor can only be in step 2) in solid precipitation separate out after add, it is excellent
It is selected in step 3) middle addition.This is primarily due to, in step 1) or step 2) solid precipitation separate out before plus
Enter, on the one hand influence whether step 2) in solid precipitation precipitation effect, that is, have influence on catalytic component
Grain form, and eventually affect the combination property of catalyst；On the other hand, research shows to be analysed in solid precipitation
Internal electron donor is added to also affect the service efficiency of internal electron donor before going out, specifically, even if adding
Substantial amounts of two ester type compound also is difficult to obtain two more esters chemical combination in final catalyst solid constituent
Thing, so as to have influence on the performance for finally preparing resin so as to be unsuitable for the use of the preparation of tube material.
According to the present invention, 4 the step of the preparation method) in, Part II internal electron donor is added again.
Part II internal electron donor can be above-mentioned Part I internal electron donor, and specifically chosen compound can be with
It is identical or different.By internal electron donor substep with special ratios in step 3) and (4) addition, and consumption can be with
By above-mentioned restriction.
If relative in step 3) in add all of internal electron donor, using in step 3) and step 4)
In be separately added into the preparation method of internal electron donor, the comprehensive of catalyst can be improved in the following aspects
Energy：1st, the internal electron donor for being carried on the magnesium halide can be made more homogeneous, so that being prepared into
To the decay of activity of catalyst make moderate progress.Specifically, the polymerization of 2 hours of the catalyst for preparing is lived
Property can increase with the ratio of the polymerization activity of 1 hour, show that the decay of activity of catalyst is slack-off.This is high-performance
The target that catalyst is pursued；2nd, the service efficiency of internal electron donor is improved, i.e., is given using less interior of total amount
Electron to cause catalyst solid component in internal electron donor content it is identical；3rd, effectively reduce in catalyst
Titanium elements content, so as to reduce unstable active center and low capacity of orientation active center, reduce urging
Agent temperature of reactor fluctuation risk in polymerization process, and the polymer isotactic index for avoiding generating is inclined
Low problem.
In the present invention, step 4) and 5) in the type of service of titanium compound be not particularly limited, such as step 4)
Or the titanium compound in (5) individually can be used directly, it is also possible to by titanium compound elder generation and inert diluent
Mixing, then carries out with the solid constituent again the 4th haptoreaction, or carries out institute with the solid product
State the 5th haptoreaction.The titanium compound and inert diluent are as it was noted above, will not be described here.
In the present invention, step 4) with 5) in the described 4th can be with identical, bag with the 5th haptoreaction condition
Include：Reaction temperature is 50-150 DEG C, preferably 80-120 DEG C；Response time is 1-6 hours, preferably
2.5-4.5 hour.
What the present invention was provided prepares the preparation method of the polyolefinic catalytic component of tubing can also include, complete
Into step 5) after, the liquid in the product that the 5th haptoreaction is obtained is filtered out, obtain solid reaction product
Thing, repeats the 5th haptoreaction 1-3 time；Through washing, it is dried, obtains the catalysis of the titaniferous of solid
Agent component, to provide the catalytic component of solid as the catalytic component for olefinic polymerization.
The present invention step 4) and 5) in, the Part II titanium compound of addition, Part III titanium compound
Amount, as long as meet make titanium compound total amount meet it is aforementioned with the magnesium halide (in terms of magnesium elements) mole
Than for example can with the mol ratio of magnesium halide with Part II titanium compound or Part III titanium compound
Think (3-40):1, preferably (5-35):1.
A preferred embodiment of the invention, the catalyst of the preparation olefinic polymerization that the present invention is provided is consolidated
The method of body component can be carried out in accordance with the following steps：
(1) under varsol, by anhydrous magnesium chloride and alcohol compound at 30-150 DEG C (preferably
60-140 DEG C) the first haptoreaction 0.5-10 hour (preferably 0.5-6 hours) is carried out, obtain uniform alcohol
Polymer solution, wherein, anhydrous magnesium chloride is 1 with the mol ratio of alcohol compound:(2-4) (preferably 1:
(2.5-3.5))；
(2) by diol-lipid compound (precipitation additive a) and formula Ti (OR9)nX4-nShown titanate ester
(precipitation additive b) is added in above-mentioned alcohol adduct solution compound, anhydrous magnesium chloride and diol-lipid compound
Mol ratio be 1:(0.005-0.3) (preferably 1:(0.01-0.05)), precipitation additive a and precipitation additive b
Addition mol ratio be 1:(0.01-5) (preferably 1:(0.5-3), more preferably 1:(0.5-1.5))；
By the above-mentioned alcohol adduct solution added with precipitation additive, -40 DEG C to 0 DEG C of Part I titanium compound is added to
It is anti-under -40 DEG C to 0 DEG C (preferably -30 DEG C to -20 DEG C) by stirring in the mixture of inert diluent
Should, and 50-150 DEG C (preferably 90-130 DEG C) is warming up in 3-5 hours (preferably 3.5-4.5 hours),
Solid precipitation is separated out in temperature-rise period, the second haptoreaction is completed, the mixture containing solid precipitation is obtained；Its
In, Part I titanium compound is (3-40) with the mol ratio of anhydrous magnesium chloride:1, preferably (5-35):1；
(3) Part I internal electron donor is added in the mixture obtained in above-mentioned (2), is in temperature
The 3rd haptoreaction 0.5-6 hour (preferably 1-4 hours) is carried out under 20-120 DEG C (preferably 70-110 DEG C),
Float is obtained, wherein, diol-lipid compound is with the mol ratio of the total amount of the internal electron donor for adding
0.05:1 to less than 0.5:1 (preferably 0.1-0.4:1, more preferably 0.15-0.35:1)；In the Part I of addition
Electron donor and subsequent step 4) in add Part II internal electron donor between mol ratio be 0.1-10:1
(preferably 0.2-5：1, more preferably 0.2-1：1)；
(4) float obtained in above-mentioned (3) is carried out into solid-liquid separation and filters out liquid, obtain solid constituent,
And will add in solid constituent in mixture of the Part II titanium compound with inert diluent, Part II
Electron donor, carries out the 4th haptoreaction 1-6 hour (preferably under 50-150 DEG C (preferably 80-120 DEG C)
For 2.5-4.5 hours), after reaction terminates, liquid is filtered out, obtain solid product；Wherein, Part II titanium
Compound is (3-40) with the mol ratio of anhydrous magnesium chloride:1, preferably (5-35):1；
(5) solid product that will be obtained in above-mentioned (4), with Part III titanium compound and inert diluent
Mixture (preferably 80-120 DEG C) at 50-150 DEG C carries out the 5th haptoreaction 1-6 hour (preferably 2.5-4.5
Hour), product is obtained, wherein, Part III titanium compound is (3-40) with the mol ratio of anhydrous magnesium chloride:1,
Preferably (5-35):1；
(6) product for obtaining above-mentioned (5), filters out liquid, obtains solid reaction product, and this is consolidated
Precursor reactant product repeats the 5th haptoreaction 1-3 with the mixture of titanium compound and inert diluent
It is secondary, through washing, it is dried, obtain the catalytic component of the titaniferous of solid；Wherein, the titanium compound with
The mol ratio of anhydrous magnesium chloride can be (3-40):1, preferably (5-35):1.
In a kind of preferred implementation of the present invention, particularly preferred precipitation additive a is 3,5- heptandiol dibenzoic acids
Ester, internal electron donor be 2- cyano group -2,3- diisopropyl diethyl succinates；The precipitation additive a with it is described
The mol ratio of total internal electron donor is (0.05-0.5):1, preferably (0.1-0.4):1, more preferably
(0.15-0.35):1.Step 3) in, the Part I internal electron donor and Part II internal electron donor
Mol ratio be (0.1-10):1, preferably (0.2-5):1, more preferably (0.2-1):1.In the application, can
Especially to use specific precipitation additive a, internal electron donor, and substep adds internal electron donor and titanizing to close
Thing, and specific consumption is limited, so as to preferably solve technical problems to be solved in this application.
In the present invention, internal electron donor is made by using the cyano group succinic acid ester type compound of formula (II), and strictly
Control the amount ratio of cyano group succinic acid ester type compound and the diol-lipid compound of the formula (I) as precipitation additive a
And in specific proportions substep add internal electron donor, so as to be prepared for high comprehensive performance, be suitable to prepare
The polyolefinic catalyst solid constituent of tube material.The granule of the catalyst solid constituent can be good with form, poly-
Close the polyolefin molecular weight distribution that activity is high, capacity of orientation is good, obtain wider.
Present invention also offers a kind of catalytic component for olefinic polymerization, it can be by present invention offer
Preparation method obtain.
According to the catalytic component that the present invention is provided, based on the gross weight of the catalytic component, contain
The titanium of 1-3.5 weight %, the precipitation additive a of 1-3.5 weight %, the internal electron donor of 6-15 weight %, and
Precipitation additive a is 0.05 with the mol ratio of internal electron donor:1-0.5:1；It is highly preferred that containing 1.8-3.2 weights
The titanium of amount %, the precipitation additive a of 1.5-3 weight %, the internal electron donor of 7-11 weight %, and precipitation additive
A is (0.1-0.3) with the mol ratio of internal electron donor:1.
In the catalytic component that the present invention is provided, it is preferable that the gross weight based on the catalytic component, contain
There are the titanium of 1-3.5 weight %, the glycol ester compounds of 1-3.5 weight %, two esters chemical combination of 6-15 weight %
Thing, and the mol ratio of glycol ester compounds and the ester type compound of 1,3- bis- is 0.05:1 to less than 0.5:1；More preferably
Ground, based on the gross weight of the catalytic component, the titanium containing 1.8-3.2 weight %, the two of 1.5-3 weight %
Alcohol ester compounds, two ester type compounds of 7-11 weight %, and glycol ester compounds rub with two ester type compounds
You are than being (0.1-0.3):1.
Present invention also offers the above-mentioned catalytic component for olefinic polymerization is preparing urging for olefinic polymerization
Application in agent system.
Therefore, present invention also offers a kind of use polyolefinic catalyst for olefinic polymerization in particular for preparing
System, the catalyst system and catalyzing contains：(1) catalytic component of the present invention；(2) alkyl aluminum compound；
And the external donor compound that (3) are optional.
According to the present invention, the olefinic polymerization refers to formula CH2The polyreaction of the alkene that=CHR is represented, its
Middle R is hydrogen or C1-C6Alkyl (preferred hydrogen or methyl).
According to the present invention, the consumption of the alkyl aluminum compound can be the conventional amount used of this area.It is preferred that feelings
Under condition, the alkyl aluminum compound in terms of aluminum, the catalytic component in terms of titanium, the alkyl aluminum compound
It is (5-5000) with the mol ratio of the catalytic component:1；Preferably, the alkyl aluminum compound with it is described
The mol ratio of catalytic component is 20-1000:1.It is highly preferred that the alkyl aluminum compound and the catalyst
The mol ratio of component is 50-500:1.
In the present invention, preparing tubing with polyolefinic catalyst system, the alkyl aluminum compound can be with
The alkyl aluminum of the various promoters that can act as Ziegler-natta catalyst commonly used for field of olefin polymerisation
Compound.In the case of preferred, the alkyl aluminum compound can be the compound shown in formula (III),
AlR'n'X'3-n'(III),
In formula (III), R' is hydrogen, C1-C20Alkyl or C6-C20Aryl, X' is halogen, and n' is 1-3's
Integer.Preferably, the specific example of the alkyl aluminum compound for example can be trimethyl aluminium, triethyl group
Aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, a chlorine diethyl
At least one in aluminum, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminum and ethyl aluminum dichloride.
According to the present invention, tubing is being prepared with polyolefinic catalyst system, the external electron donor chemical combination
The species and content of thing are not particularly limited.The alkyl aluminum compound and institute under preferable case, in terms of aluminum
The mol ratio for stating external donor compound is 0.1-500:1, preferably 1-300:1, more preferably 3-100:1.
According to the present invention, the external donor compound can be field of olefin polymerisation commonly use it is various can
The external donor compound of the promoter as Ziegler-natta catalyst.It is described under preferable case
External donor compound can be the organo-silicon compound shown in formula (IV),
R1”m”R2”n”Si(OR3”)4-m”-n”(IV),
In formula (IV), R1 " and R2 " can be identical or different, each respectively halogen, hydrogen atom, C1-C20
Alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl in one kind；R3 " is
C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl in one kind；
M " and n " is respectively the integer of 0-3, and m "+n "<4.As the specific example of the external donor compound
Trimethylmethoxysilane, trimethylethoxysilane, trimethylbenzene epoxide triethyl group methoxyl group can be enumerated
Silane, triethyl-ethoxy-silicane alkane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, ethyl
Isopropyl dimethoxysilane, propyl iso-propyl dimethoxysilane, diisopropyl dimethoxy silane, two
Isobutyl group dimethoxysilane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane,
Tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tert-butyl group dimethylamine epoxide silicon
Alkane, ter /-butylisopropyl dimethoxysilane, tert-butyl group butyldimethoxysilane, tert-butyl group isobutyl group two
Methoxy silane, the tert-butyl group (sec-butyl) dimethoxysilane, t-butyl amyl dimethoxysilane, the tert-butyl group
Nonyl dimethoxysilane, tert-butyl group hexyl dimethoxysilane, tert-butyl group heptyl dimethoxysilane, uncle
Butyl octyl dimethoxysilane, tert-butyl group decyl dimethyl TMOS, methyl tertbutyl dimethoxy silicon
Alkane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl-ethyl dimethoxysilane, Cyclohexylpropyl dimethoxy
Base silane, cyclohexyl isobutyl group dimethoxysilane, Dicyclohexyldimethoxysilane, the cyclohexyl tert-butyl group
Dimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, cyclopenta
Propyldimethoxy-silane, cyclopenta t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, ring
Pentylcyclohexyl dimethoxysilane, double (2- methylcyclopentyls) dimethoxysilanes, diphenyl dimethoxy silicon
Alkane, diphenyl diethoxy silane, phenyl triethoxysilane, MTMS, the second of methyl three
TMOS, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, isopropyl
Base trimethoxy silane, butyl trimethoxy silane, butyl triethoxysilane, isobutyl trimethoxy silicon
Alkane, tert-butyl trimethoxy silane, sec-butyl trimethoxy silane, amyltrimethoxysilane, isopentyl
Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, diphenyl dimethoxy
Silane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-pro-pyl
Trimethoxy silane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, four fourth oxygen
Base silane, 2- ethyl piperidine base -2- t-butyldimethoxysilanes, (the fluoro- 2- propyl group of 1,1,1- tri-) -2- ethyl piperidines
At least one in base dimethoxysilane and (the fluoro- 2- propyl group of 1,1,1- tri-)-methyl dimethoxysilane.More preferably
Ground, the external donor compound can be dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy
Silane, second, isobutyl dimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, methyl tertbutyl dimethoxy
At least one in base silane and tetramethoxy-silicane.
Present invention also offers a kind of tubing uses polyolefinic polymerization, the method to include：In olefinic polymerization
Under the conditions of, contact the catalyst system that one or more alkene is provided with the present invention, in the alkene extremely
Few one kind is by formula CH2The alkene that=CHR is represented, wherein R are hydrogen or C1-C6Alkyl.The present invention is carried
For the polyolefinic polymerization of tubing can be used for the homopolymerization of alkene, it is also possible to for by various alkene
Carry out combined polymerization.The alkene can with instantiation include：Ethylene, propylene, 1- n-butenes, 1- positive penta
At least one in alkene, 1- n-hexylenes, the positive octenes of 1- and 4-methyl-1-pentene.Preferably, the alkene can be with
For at least one in ethylene, propylene, 1- n-butenes, 4-methyl-1-pentene and 1- n-hexylenes.It is highly preferred that
The alkene is propylene.
According to the present invention, the catalyst solid component is applied in tubing polyolefin is prepared, and prepares tubing
With the component of polyolefinic catalyst system, the i.e. catalyst solid constituent of present invention offer, as co-catalysis
The organo-aluminum compound of agent and as external donor compound can contact olefinic monomer before first be connect
Touch, it is in the field of business to be referred to as " pre-contact " or " pre- complexation "；Can also three components be added separately to alkene
Carry out polyreaction in hydrocarbon monomer again, i.e., do not implement " pre-contact ".According to the olefinic polymerization that the present invention is provided
Method, the method that each component in preferred alkenes polymerisation catalyst system adopts " pre-contact "." pre-terminated
Touch " time be 0.1-30min, preferred 1-10 minutes；The temperature of " pre-contact " is -20 DEG C to 80 DEG C, excellent
Select 10-50 DEG C.
The catalyst system is first carried out into a certain degree of polymerization in the presence of a small amount of olefinic monomer and obtains pre-
Polymerization catalyst, then pre-polymerized catalyst is further contacted with olefinic monomer carry out reaction and obtain olefinic polymerization
Thing.This technology is in the field of business to be referred to as " prepolymerization " technique, contributes to polymerization catalyst activity and polymer
Raising of bulk density etc..According to the olefine polymerizing process that the present invention is provided, " prepolymerization " work can be adopted
Skill, it is also possible to do not adopt " prepolymerization " technique, it is preferred to use " prepolymerization " technique." prepolymerization "
Multiplying power is 5-1000gPP/gCat, preferred 10-500gPP/gCat when olefinic monomer is propylene；" pre-polymerization
The temperature of conjunction " is -20 DEG C to 80 DEG C, preferred 10-50 DEG C.
Of the invention to prepare the polyolefinic polymerization of tubing, the polymerizing condition can be this area
Normal condition.The consumption of catalyst can be the consumption of the various catalyst of prior art.
Specific embodiment
Describe the present invention in detail with reference to embodiments, but be not intended to limit the present invention.
In following examples, the method for testing being related to is as follows：
1st, the yield (%) of catalytic component=(gained catalyst quality/magnesium chloride quality used) × 100%；
2nd, the Ti content in catalytic component：Using 721 spectrophotometric determinations；
3rd, the particle size distribution of the solid of catalytic component：Using the laser particle size analyzer of Malvern 2000, according to
Normal hexane dispersant laser diffractometry is measured；
4th, in catalytic component precipitation additive a compounds contents (diol ester) and internal electron donor content (two
Ester content)：Waters 600E liquid chromatograph is measured；
5th, melt index (MI)：Determined according to GB/T3682-2000；
6th, acrylic polymers isotacticity index (II)：Determined using heptane extraction process：The polymer-like that 2g is dried
Product, are placed in extractor after being extracted 6 hours with boiling heptane, by residue drying to the polymer obtained by constant weight
Weight (g) is isotacticity with the ratio of 2 (g)；
7th, molecular weight distribution MWD (MWD=Mw/Mn)：Using PL-GPC220, with three
Chlorobenzene is solvent, and (standard specimen is determined at 150 DEG C：Polystyrene, flow velocity：1.0ml/min, pillar：
3xPlgel 10um MlxED-B 300x7.5nm)。
8th, activity is calculated：Catalyst activity=(the polyolefin quality of preparation)/(catalyst solid component quality) g/g
9th, sedimentating density measuring：Polymer powders obtained by preparation are freely fallen in funnel from 10cm height
To in 100mL containers, polymer powders weight is Mg to body in weighing container, then polymer bulk density is
M/100g/cm3。
Preparation example 1
The preparation of 2- cyano group -2,3- diisopropyl diethyl succinates：In 1000mL round-bottomed flasks, 48.1g is added
Sodium tert-butoxide and 300mLDMF.Temperature rising reflux.Stirring is while Deca 81.5g cyano group ethyl isovalerate.Heat up
Flow back 2 hours to 80 DEG C.The mixed solution of Deca 99.6g bromo ethyl isovalerate and 100mLDMF.After
It is continuous to be warming up to 100 DEG C and react 20 hours.Stopped reaction, cooling is filtered.Cake Wash.Filtrate rotation is steamed
Send out and remove solvent.Add saturated ammonium chloride solution washing, point liquid.Organic faciess are dried, and filter, and are spin-dried for solvent.
Obtain crude product.Rectification under vacuum obtains product 94.2g, (8mbar, 123-127 DEG C).1H-NMR(CDCl3/TMS,
300MHz)(δppm):0.99-1.04 (m, 8H), 1.08-1.38 (m, 10H), 2.12-2.16 (m, 1H),
2.28-2.37 (m, 1H), 2.97-3.02 (m, 1H), 4.14-4.30 (m, 4H).
Preparation example 2
It is prepared by 2- cyano group -2- n-pentyl -3- isopropyls diethyl succinate：It is using the method for preparation example 1, cyano group is different
Ethyl valerate is changed to cyano group enanthic ether and prepares 2- cyano group -2- n-pentyl -3- isopropyl diethyl succinates,
Rectification under vacuum obtains product 53.7g (8mbar, 145-148 DEG C).1H NMR(CDCl3/TMS,300MHz)δ
(ppm):0.85-0.91(t,3H),0.97-1.10(m,6H),1.21-1.37(t,6H,m,4H),1.56-1.64(m,
2H),1.73-1.82(t,2H),2.15-2.22(m,1H),2.81-2.83(d,1H),4.14-4.30(m,4H)。
Embodiment 1-3 is used to illustrate catalyst component for olefin polymerization, olefin polymerization catalysis and the alkene of the present invention
Polymerized hydrocarbon method.
Embodiment 1
(1) preparation of catalytic component A1
(1) in the reactor that High Purity Nitrogen repeats displacement, sequentially add 3.150mol's (300.0g)
Anhydrous magnesium chloride, the toluene of 19.68mol (2.1L), the 2-Ethylhexyl Alcohol of 8.4mol (1.1L), in stirring
Rotating speed 450rpm, temperature are under conditions of 115 DEG C, to react 3.0 hours, and the alcohol adduct for obtaining stable and uniform is molten
Liquid；
(2) in above-mentioned alcohol adduct solution add 3,5- heptandiols dibenzoate 124mmol (42ml) and
Butyl titanate 132mmol (45ml), stirs 60 minutes, is cooled to room temperature, obtains homogeneous solution；Will
Above-mentioned homogeneous solution is added to Jing nitrogen and is sufficiently displaced from and equipped with four chlorinations of -20 DEG C of 60mol (6.6L)
In the reactor of the toluene of titanium and 11.4mol (1.2L), them are made to be fully contacted at -20 DEG C by stirring,
Jing after 5 hours, 100 DEG C are warming up to, solid precipitation is separated out in temperature-rise period, obtain mixed containing solid precipitation
Compound；
(3) 2- cyano group -2,3- diisopropyls diethyl succinate 123.5mmol (35g) is added into above-mentioned containing
Have in the mixture of solid precipitation and react 1 hour, after reaction terminates, filter out liquid；
(4) then by the toluene of the solid constituent being filtrated to get in (3) and 40.8mol (4.32L), 26.2
The titanium tetrachloride of mol (2.88L) and the 2- cyano group -2,3- diisopropyl succinic acid of 247.0mmol (70g)
Diethylester is contacted 1.5 hours at 100 DEG C, after reaction terminates, filters out liquid；
(5) and then by the toluene and 26.2 of the solid product being filtrated to get in (4) and 40.8mol (4.32L)
The titanium tetrachloride of mol (2.88L) haptoreaction 0.5 hour at 110 DEG C；
(6) product that (5) reaction is obtained is filtered, by the solid reaction product being filtrated to get 40.8mol (4.32
L) toluene and 26.2mol (2.88L) titanium tetrachlorides carry out haptoreaction once at 110 DEG C；Obtain final
The solidss for arriving are washed 5 times with 55.14mol (7.2L) hexane, are then dried, and are obtained for olefinic polymerization
Catalytic component A1.
For the Ti content of the catalytic component A1 of olefinic polymerization, the content of precipitation additive a, internal electron donor
Content and as shown in table 1 for the result of the particle size distribution of the catalytic component A1 of olefinic polymerization.
(2) olefinic polyreaction
Polymerization examination in (1) 1 hour：In 5 liters of autoclaves, Jing after gas-phase propene is sufficiently displaced from, in room
The hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of the triethyl aluminum of the lower addition 5ml of temperature, the ring of lml
The hexane solution (concentration of CHMMS is 0.1mmol/ml) of hexyl methyl dimethoxysilane (CHMMS),
The anhydrous hexane of 10ml and the catalytic component A1 of 10mg.Autoclave is closed, the hydrogen of 0.18mol is introduced
With the liquid propene of 2.4L；Under agitation, temperature is risen to into 70 DEG C in 10 minutes.It is anti-in 70 DEG C of polymerizations
Answer 60 minutes, reaction stops stirring after terminating, remove unpolymerized propylene monomer, collected polymer, at 70 DEG C
Lower vacuum drying 1 hour, calculating catalyst activity of weighing.
Polymerization examination in (2) 2 hours：Examine with polymerization in above-mentioned 1 hour, be simply reduced to catalyst charge amount
8mg, hydrogen usage is reduced to 0.02mol, while polymerization reaction time increased to 2 hours by 1 hour.
Caltalyst containing catalytic component A1 ties up to the performance ginseng of the polymerization activity in propylene polymerization and polymer
Number is shown in Table 2.
Comparative example 1
(1) preparation of catalytic component D1
(1) in the reactor that High Purity Nitrogen repeats displacement, the anhydrous chlorine of 3.150mol (300.0g) is sequentially added
Change magnesium, 19.68mol (2.1L) toluene, 8.4mol (1.1L) 2-Ethylhexyl Alcohol, speed of agitator 450rpm,
Temperature obtains the alcohol adduct solution of stable and uniform under conditions of 110 DEG C, to react 3.0 hours；
(2) 3,5- heptandiols dibenzoate 124mmol (42ml) is added in above-mentioned alcohol adduct solution,
Butyl titanate 132mmol (45ml), stirs 60 minutes, is cooled to room temperature, obtains homogeneous solution；Will
Above-mentioned homogeneous solution is added to Jing nitrogen and is sufficiently displaced from and equipped with -20 DEG C of 60mol (6.6L) titanium tetrachloride
And in the reactor of 11.4mol (1.2L) toluene, them is fully contacted at -20 DEG C by stirring, Jing 5
After hour, 110 DEG C are warming up to, solid precipitation is separated out in temperature-rise period, obtain the mixing containing solid precipitation
Thing；
(3) 2- cyano group -2,3- diisopropyls diethyl succinate 425.0mmol (120.4g) is added above-mentioned
React 1 hour in mixture containing solid precipitation, after reaction terminates, filter out liquid；
(4) and then by the toluene and 26.2 of the solid constituent being filtrated to get in (3) and 40.8mol (4.32L)
The titanium tetrachloride of mol (2.88L) is contacted 1 hour at 110 DEG C, is filtered；
(5) and then again by the solid product being filtrated to get in (4) and 40.8mol (4.32L) toluene and 26.2
Mol (2.88L) titanium tetrachlorides are contacted 0.5 hour at 110 DEG C；
(6) product that (5) reaction is obtained is filtered, by the solid reaction product 55.14mol being filtrated to get
(7.2L) hexane is washed 5 times, is then dried, and obtains the catalytic component D1 for olefinic polymerization.
For the Ti content of the catalytic component D1 of olefinic polymerization, the content of precipitation additive a, internal electron donor
Content and as shown in table 1 for the result of the particle size distribution of the catalytic component D1 of olefinic polymerization.
(2) olefinic polyreaction：
According to the method in (two) in embodiment 1, except for the difference that, substitute A1 with D1 and be polymerized.
Caltalyst containing catalytic component D1 ties up to the performance ginseng of the polymerization activity in propylene polymerization and polymer
Number is shown in Table 2.
Embodiment 2
(1) preparation of catalytic component A2
(1) in the reactor that High Purity Nitrogen repeats displacement, sequentially add 3.150mol's (300.0g)
Anhydrous magnesium chloride, the toluene of 19.68mol (2.1L), the 2-Ethylhexyl Alcohol of 8.4mol (1.1L), in stirring
Rotating speed 450rpm, temperature are under conditions of 115 DEG C, to react 3.0 hours, and the alcohol adduct for obtaining stable and uniform is molten
Liquid；
(2) in above-mentioned alcohol adduct solution add 3,5- heptandiols dibenzoate 124mmol (42ml) and
Butyl titanate 132mmol (45ml), stirs 60 minutes, is cooled to room temperature, obtains homogeneous solution；Will
Above-mentioned homogeneous solution is added to Jing nitrogen and is sufficiently displaced from and equipped with four chlorinations of -20 DEG C of 60mol (6.6L)
In the reactor of the toluene of titanium and 11.4mol (1.2L), them are made to be fully contacted at -20 DEG C by stirring,
Jing after 5 hours, 110 DEG C are warming up to, solid precipitation is separated out in temperature-rise period, obtain mixed containing solid precipitation
Compound；
(3) by 2- cyano group -2- n-pentyl -3- isopropyl diethyl succinate 112.4mmol (35.0g) additions
State in the mixture containing solid precipitation and react 1 hour, after reaction terminates, filter out liquid；
(4) then by the toluene of the solid constituent being filtrated to get in (3) and 40.8mol (4.32L), 26.2
The titanium tetrachloride of mol (2.88L), and the 2- cyano group -2- n-pentyl -3- isopropyls of 224.8mmol (70.0g)
Base diethyl succinate is contacted 1.5 hours at 100 DEG C, after reaction terminates, filters out liquid；
(5) and then by the toluene and 26.2 of the solid product being filtrated to get in (4) and 40.8mol (4.32L)
The titanium tetrachloride of mol (2.88L) is contacted 0.5 hour at 110 DEG C；
(6) product that (5) reaction is obtained is filtered, by the solid reaction product being filtrated to get 40.8mol (4.32
L) toluene and 26.2mol (2.88L) titanium tetrachlorides carry out haptoreaction once at 110 DEG C；Obtain final
The solidss for arriving are washed 5 times with 55.14mol (7.2L) hexane, are then dried, and are obtained for olefinic polymerization
Catalytic component A2.
For the Ti content of the catalytic component A2 of olefinic polymerization, the content of precipitation additive a, internal electron donor
Content and as shown in table 1 for the result of the particle size distribution of the catalytic component A2 of olefinic polymerization.
(2) olefinic polyreaction
According to the method in (two) in embodiment 1, except for the difference that, substitute A1 with A2 and be polymerized.
Caltalyst containing catalytic component A2 ties up to the performance ginseng of the polymerization activity in propylene polymerization and polymer
Number is shown in Table 2.
Embodiment 3
(1) preparation of catalytic component A3
(1) in the reactor that High Purity Nitrogen repeats displacement, sequentially add 3.150mol's (300.0g)
Anhydrous magnesium chloride, the toluene of 19.68mol (2.1L), the 2-Ethylhexyl Alcohol of 8.4mol (1.1L), in stirring
Rotating speed 450rpm, temperature are under conditions of 115 DEG C, to react 3.0 hours, and the alcohol adduct for obtaining stable and uniform is molten
Liquid；
(2) in above-mentioned alcohol adduct solution add 3,5- heptandiols dibenzoate 124mmol (42ml) and
Butyl titanate 132mmol (45ml), stirs 60 minutes, is cooled to room temperature, obtains homogeneous solution；Will
Above-mentioned homogeneous solution is added to Jing nitrogen and is sufficiently displaced from and equipped with four chlorinations of -20 DEG C of 60mol (6.6L)
In the reactor of the toluene of titanium and 11.4mol (1.2L), them are made to be fully contacted at -20 DEG C by stirring,
Jing after 5 hours, 100 DEG C are warming up to, solid precipitation is separated out in temperature-rise period, obtain mixed containing solid precipitation
Compound；
(3) 2- cyano group -2,3- diisopropyls diethyl succinate 123.5mmol (35g) is added into above-mentioned containing
Have in the mixture of solid precipitation and react 1 hour, after reaction terminates, filter out liquid；
(4) then by the toluene of the solid constituent being filtrated to get in (3) and 40.8mol (4.32L), 26.2
The titanium tetrachloride of mol (2.88L), and 2, the 3- diisopropyl -2- cyano group fourths of 300.0mmol (85g)
Diethyl adipate is contacted 1.5 hours at 100 DEG C, after reaction terminates, filters out liquid；
(5) and then by the toluene and 26.2 of the solid product being filtrated to get in (4) and 40.8mol (4.32L)
The titanium tetrachloride of mol (2.88L) haptoreaction 0.5 hour at 110 DEG C；
(6) product that (5) reaction is obtained is filtered, by the solid reaction product being filtrated to get 40.8mol (4.32
L) toluene and 26.2mol (2.88L) titanium tetrachlorides carry out haptoreaction once at 110 DEG C；Obtain final
The solidss for arriving are washed 5 times with 55.14mol (7.2L) hexane, are then dried, and are obtained for olefinic polymerization
Catalytic component A3.
For the Ti content of the catalytic component A3 of olefinic polymerization, the content of precipitation additive a, internal electron donor
Content and as shown in table 1 for the result of the particle size distribution of the catalytic component A3 of olefinic polymerization.
(2) olefinic polyreaction
According to the method in (two) in embodiment 1, except for the difference that, substitute A1 with A3 and be polymerized.
Caltalyst containing catalytic component A3 ties up to the polymerization activity in propylene polymerization and the performance parameter of polymer is shown
In table 2.
Embodiment 4
As described in Example 1, except for the difference that, the cyclohexyl methyl of 1ml is added without in (1) of (two)
The hexane solution of dimethoxysilane (CHMMS).
The performance parameter of polymerization activity and polymer is shown in Table 2.
Comparative example 2
(1) preparation of catalytic component D2
According to the method for () in comparative example 1, except for the difference that, " the O-phthalic of 95g is used in step (3)
Sour diisobutyl ester " replacement " the 2- cyano group -2,3- diisopropyl diethyl succinates of 120.4g ".
Obtain catalytic component D2.
The particle size distribution of the Ti content, the content of precipitation additive a and catalytic component D2 of catalytic component D2
Result it is as shown in table 1.
The content of diisobutyl phthalate is 8.8 weight % in D2.
(2) olefinic polyreaction
According to the method in (two) in embodiment 1, except for the difference that, substitute A1 with D2 and be polymerized.
Caltalyst containing catalytic component D2 ties up to the polymerization activity in propylene polymerization and the performance parameter of polymer is shown
In table 2.
Comparative example 3
(1) preparation of catalytic component D3
(1) in the reactor that High Purity Nitrogen repeats displacement, sequentially add 3.150mol's (300.0g)
Anhydrous magnesium chloride, the toluene of 19.68mol (2.1L), the 2-Ethylhexyl Alcohol of 8.4mol (1.1L), in stirring
Rotating speed 450rpm, temperature are under conditions of 110 DEG C, to react 3.0 hours, and the alcohol adduct for obtaining stable and uniform is molten
Liquid；
(2) in above-mentioned alcohol adduct solution add 3,5- heptandiols dibenzoate 124mmol (42ml),
2- cyano group -2,3- diisopropyls diethyl succinate 148.2mmol (42g), butyl titanate 132mmol (45
Ml), stir 60 minutes, be cooled to room temperature, obtain homogeneous solution；Above-mentioned homogeneous solution is added to into Jing nitrogen
Gas is sufficiently displaced from, the toluene of the titanium tetrachloride equipped with -20 DEG C of 60mol (6.6L) and 11.4mol (1.2L)
Reactor in, by stirring them is fully contacted at -20 DEG C, Jing after 5 hours, be warming up to 110 DEG C,
Solid precipitation is separated out in temperature-rise period, the mixture containing solid precipitation is obtained；
(3) dibutyl phthalate 336mmol (90.0ml) is added above-mentioned mixed containing solid precipitation
After reacting 1 hour in compound, liquid is filtered out；
(4) and then by the toluene and 26.2 of the solid constituent being filtrated to get in (3) and 40.8mol (4.32L)
The titanium tetrachloride of mol (2.88L) is contacted 1 hour at 110 DEG C, after reaction terminates, filters out liquid；
(5) and then by the toluene and 26.2 of the solid product being filtrated to get in (4) and 40.8mol (4.32L)
The titanium tetrachloride of mol (2.88L) haptoreaction 0.5 hour at 110 DEG C；
(6) product that (5) reaction is obtained is filtered, by the solid reaction product 55.14mol being filtrated to get
(7.2L) hexane is washed 5 times, is then dried, and obtains catalytic component D3.
The Ti content of catalytic component D3, the content of precipitation additive a, internal electron donor content and catalyst
The result of the particle size distribution of component D3 is as shown in table 1.
(2) olefinic polyreaction
According to the method in (two) in embodiment 1, except for the difference that, substitute A1 with D3 and be polymerized.
Caltalyst containing catalytic component D3 ties up to the performance of the polymerization activity in propylene polymerization and polymer
Parameter is shown in Table 2.
Comparative example 4
(1) preparation of catalytic component D4
According to the method for () in comparative example 1, except for the difference that, " 2- cyano group -2 of 90.0g, 3- are used in (3)
Diisopropyl diethyl succinate " replacement " 2- cyano group -2,3- diisopropyl succinic acid the diethyls of 120.4g
Ester ".
Obtain catalytic component D4.
The Ti content of catalytic component D4, the content of precipitation additive a, internal electron donor content and catalyst
The result of the particle size distribution of component D4 is as shown in table 1.
(2) olefinic polyreaction
According to the method in (two) in embodiment 1, except for the difference that, substitute A1 with D4 and be polymerized.
Caltalyst containing catalytic component D4 ties up to the performance ginseng of the polymerization activity in propylene polymerization and polymer
Number is shown in Table 2.
Table 1
Note：D (10) is represented：The cumulative particle sizes distribution number of one sample reaches particle diameter corresponding when 10%.Its physical significance is grain
Footpath accounts for 10% less than its granule；
D (50) is represented：The cumulative particle sizes percentile of one sample reaches particle diameter corresponding when 50%.Its physical significance is grain
Footpath accounts for 50% more than its granule, also accounts for 50%, D50 less than its granule and is also meso-position radius or median particle diameter.D50 is commonly used to table
Show the particle mean size of powder body；
D (90) is represented：The cumulative particle sizes distribution number of one sample reaches particle diameter corresponding when 90%.Its physical significance is that particle diameter is little
90% is accounted in its granule；
Span is represented：(D90-D10)/D50, for representing particle diameter distribution.
Table 2
Note：Damped expoential is the ratio of the polymerization activity of 2 hours and the polymerization activity of 1 hour.
From the data of table 1, table 2 catalytic component obtained by the present invention is can be seen that in composition, granulated
The aspects such as state, polymerization have more preferably performance.With comparative example 1 (adding internal electron donor without substep) phase
Than：1st, the service efficiency of ester compounds is higher in the present invention, i.e., using the diester total amount of 105g just using catalysis
Two ester contents in agent have reached 13.4 weight % (embodiment 1), and used in comparative example 1 120.4g two
Diester reserves in the final catalyst of ester also only reach 8.9 weight %；2nd, in catalyst solid constituent of the present invention
Total Ti content is lower, is conducive to raising (the higher expression catalyst of polymer isotactic index of catalyst capacity of orientation
Capacity of orientation is higher) and catalyst decay of activity speed reduce, while also reducing olefinic polymerization production process
In the risk that occurs of the unstable situation such as temperature fluctuation.It is (interior to electricity without two ester type compounds with comparative example 2
Daughter) and comparative example 3 (two ester type compounds are added before solid precipitation is separated out, it is class in catalytic component
Compound content is low) to compare, when prepared catalytic component is used for olefinic polymerization in embodiment, hydrogen is adjusted more unwise
Sense (it is equally lower with melt flow rate during hydrogen amount, it is brighter when 0.18mol is polymerized with hydrogen amount
It is aobvious), and prepared molecular weight distribution width, the raising of these parameters is conducive to special material for tube
Preparation.In addition, when the content of the diester compound in catalytic component is relatively low (comparative example 4), catalysis
The hydrogen response of agent, the molecular weight of polymer, and catalyst activity damped expoential, are unfavorable for tubing
The production of PP Pipe Compound.
Claims (13)
1. a kind of preparation method of the catalytic component for olefinic polymerization, comprises the following steps：
1) magnesium halide and alcohol compound are carried out into the first haptoreaction in the presence of varsol, is formed molten
Liquid；
2) in the presence of precipitation additive, by step 1) obtained by solution and Part I titanium compound carry out the
Two haptoreactions, obtain the mixture containing solid precipitation；
3) by step 2) obtained by mixture and Part I internal electron donor carry out the 3rd haptoreaction, obtain
Suspension；
4) by step 3) suspension that obtains carries out solid-liquid separation, the solid constituent for obtaining and Part II titanizing
Compound, Part II internal electron donor carry out the 4th haptoreaction, then carry out solid-liquid separation, obtain solid product；
5) by step 4) solid product that obtains carries out the 5th haptoreaction with Part III titanium compound, obtains
The catalytic component.
2. preparation method according to claim 1, it is characterised in that the precipitation additive includes helping analysis
Go out agent a and/or precipitation additive b, the precipitation additive a is the diol-lipid compound shown in formula (I),
In formula (I), R1-R2It is identical or different, respectively substituted or unsubstituted C1-C20Straight chained alkyl, take
Generation or unsubstituted C3-C20Branched alkyl, substituted or unsubstituted C3-C20It is cycloalkyl, substituted or unsubstituted
C6-C20Aryl, substituted or unsubstituted C7-C20Alkaryl, substituted or unsubstituted C7-C20Aralkyl, take
Generation or unsubstituted C2-C10Alkylene or substituted or unsubstituted C10-C20Fused ring aryl；R3-R8It is identical or
Difference, each respectively hydrogen, halogen, substituted or unsubstituted C1-C20It is straight chained alkyl, substituted or unsubstituted
C3-C20Branched alkyl, substituted or unsubstituted C3-C20Cycloalkyl, substituted or unsubstituted C6-C20Aryl,
Substituted or unsubstituted C7-C20Alkaryl, substituted or unsubstituted C7-C20It is aralkyl, substituted or unsubstituted
C2-C10Alkylene or substituted or unsubstituted C10-C20Fused ring aryl；Or R3-R6At least one of with
R7-R8At least one of cyclization；
The precipitation additive b is formula Ti (OR9)nX4-nShown titanate ester compound, wherein, R9For
C1-C10Straight chained alkyl, C3-C10Branched alkyl or C3-C10Cycloalkyl, X is halogen, 1≤n≤4, and
N is integer.
3. preparation method according to claim 1 and 2, it is characterised in that give in the Part I
One or both of which includes the cyano group shown in formula (II) in electron and the Part II internal electron donor
Succinic acid ester type compound,
In Formula II, R1＇ and R2＇ is identical or differs, and is each independently selected from hydrogen, C1-C14Straight chained alkyl,
C3-C14Branched alkyl, C3-C10Cycloalkyl, C6-C10Aryl, C7-C10Alkaryl and C7-C10Aralkyl
Base；R3＇ and R4＇ is identical or differs, and is each independently selected from C1-C10Straight chained alkyl, C3-C10Branched alkane
Base, C3-C10Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl and C7-C20Aralkyl.
4. the preparation method according to any one of claim 2-3, it is characterised in that step 2) in institute
The precipitation additive a for using is with the mol ratio of the total internal electron donor used in the preparation method
(0.05-0.5):1, preferably (0.1-0.4):1, more preferably (0.15-0.35):1.
5. the preparation method according to any one of claim 1-4, it is characterised in that described first
The mol ratio for dividing internal electron donor and the Part II internal electron donor is (0.1-10):1, preferably
(0.2-5):1, more preferably (0.2-1):1.
6. the preparation method according to any one of claim 2-5, it is characterised in that the precipitation additive
Including the precipitation additive a and precipitation additive b, and the precipitation additive a and the precipitation additive
The mol ratio of b is 1:(0.01-5), preferably 1:(0.5-3), more preferably 1:(0.5-1.5).
7. the preparation method according to any one of claim 1-6, it is characterised in that the titanium compound
In terms of titanium elements, the magnesium halide in terms of magnesium elements, alcohol compound, total titanium used in the method
The mol ratio of compound, total internal electron donor used in the method and magnesium halide is (2-4):
(12-160):(0.01-3):1, preferably (2.5-3.5):(20-140):(0.02-0.3):1.
8. the preparation method according to any one of claim 1-7, it is characterised in that step 1) it is used
Magnesium halide and step 2) mol ratio of total precipitation additive that used is 1:(0.025-0.9), preferably
1:(0.03-0.3)。
9. the preparation method according to any one of claim 2-8, it is characterised in that precipitation additive a is selected
It is different from 2- ethyl -1,3- propylene glycol dibenzoates, 2- propyl group -1,3- propylene glycol dibenzoates, 2- isopropyl -2-
The propylene glycol dibenzoate of amyl group -1,3,1,3 butylene glycol mesitylenic acid ester, 2- methyl isophthalic acids, between 3- butanediols two
Chlorobenzoic acid ester, 2,3- dimethyl -1,3 butylene glycol dibenzoate, the pivalate of 1,3- pentanediols two, 2,4- penta
Bisbenzoate, 2- methyl isophthalic acids, 3- pentanediol benzoic acid cinnamate, 2,2- dimethyl -1,3- pentanediol hexichol
Formic acid esters, 2,4- heptandiol dibenzoates, 3,5- heptandiol dibenzoates, 4- ethyl -3,5- heptandiol hexichol
At least one in formic acid esters and 2- methyl -3,5- heptandiol dibenzoates；Preferably 3,5- heptandiols hexichol first
At least one in acid esters, 4- ethyls -3,5- heptandiols dibenzoate and 2,4-PD dibenzoate；
Precipitation additive b is in tetramethoxy titanate ester, butyl titanate, tetraethyl titanate and tetraisopropyl titanate
It is at least one；Preferably butyl titanate.
10. the preparation method according to any one of claim 1-9, it is characterised in that in Part I
Electron is identical or different in electron and Part II, is respectively selected from 2- cyano group -2,3- diisopropyl succinic acid
Dimethyl ester, 2- cyano group -2,3- diisopropyl diethyl succinates, 2- cyano group -2,3- dimethyl succinic acid diethylesters,
2- cyano group -2,3- diethyl succinic acid diethylesters, 2- cyano group -2,3- diη-propyl diethyl succinates, 2- cyano group -2,3-
Di-n-butyl diethyl succinate, the n-pentyl diethyl succinates of 2- cyano group -2,3- two, 2- cyano group -2,3- diisoamyls
Base diethyl succinate, 2- cyano group -2,3- di-n-hexyl diethyl succinates, the isohesyl fourths two of 2- cyano group -2,3- two
Diethyl phthalate, 2- cyano group -2,3- diisopropyl succinic acid di-n-propyl esters, 2- cyano group -2,3- diisopropyl succinic acid
Diisopropyl ester, 2- cyano group -2,3- diisopropyl succinic acid di-n-butyls, 2- cyano group -2,3- diisopropyl succinic acid
Diisobutyl ester, 2- cyano group -2,3- diisopropyl succinic acid -1- methyl ester -4- ethyl esters, 2- cyano group -2,3- diisopropyls
Succinic acid -1- ethyl ester -4- methyl ester, 2- cyano group -2,3- diisopropyl succinic acid -1- N-butyl -4- ethyl esters, 2- cyano group
- 2,3- diisopropyl succinic acid -1- ethyl ester -4- N-butyls, 2- cyano group -2,3- diisobutyl dimethyl succinates,
2- cyano group -2,3- diisobutyl diethyl succinates, 2- cyano group -2,3- diisobutyl succinic acid di-n-propyl esters, 2-
Cyano group -2,3- diisobutyl diisopropyl ester amber acids, 2- cyano group -2,3- diisobutyl succinic acid di-n-butyls, 2-
Cyano group -2,3- diisobutyl succinic acid diisobutyl esters, 2- cyano group -2,3- diisobutyl succinic acid -1- methyl ester -4- second
Ester, 2- cyano group -2,3- diisobutyl succinic acid -1- ethyl ester -4- methyl ester, 2- cyano group -2,3- diisobutyl succinic acid -1-
N-butyl -4- ethyl esters, 2- cyano group -2,3- diisobutyl succinic acid -1- ethyl ester -4- N-butyls, 2- cyano group -2,3- two
Sec-butyl dimethyl succinate, 2- cyano group -2,3- di-sec-butyl diethyl succinates, 2- cyano group -2,3- di-secondary fourths
Base succinic acid di-n-propyl ester, 2- cyano group -2,3- di-sec-butyl diisopropyl ester amber acids, 2- cyano group -2,3- di-secondary fourths
Base succinic acid di-n-butyl, 2- cyano group -2,3- di-sec-butyl succinic acid diisobutyl esters, 2- cyano group -2,3- di-secondary fourths
Base succinic acid -1- methyl ester -4- ethyl esters, 2- cyano group -2,3- di-sec-butyl succinic acid -1- ethyl ester -4- methyl ester, 2- cyano group
- 2,3- di-sec-butyl succinic acid -1- N-butyl -4- ethyl esters, 2- cyano group -2,3- di-sec-butyl succinic acid -1- ethyl ester -4-
N-butyl, 2- cyano group -2,3- bicyclopentyl dimethyl succinates, 2- cyano group -2,3- bicyclopentyl succinic acid diethyls
Ester, 2- cyano group -2,3- bicyclopentyl succinic acid di-n-propyl esters, 2- cyano group -2,3- bicyclopentyl succinic acid diisopropyls
Ester, 2- cyano group -2,3- bicyclopentyl succinic acid di-n-butyls, the isobutyl of 2- cyano group -2,3- bicyclopentyls succinic acid two
Ester, 2- cyano group -2,3- bicyclopentyl succinic acid -1- methyl ester -4- ethyl esters, 2- cyano group -2,3- bicyclopentyl succinic acid -1-
Ethyl ester -4- methyl ester, 2- cyano group -2,3- bicyclopentyl succinic acid -1- N-butyl -4- ethyl esters, 2- cyano group -2,3- bicyclo-
Amyl group succinic acid -1- ethyl ester -4- N-butyls, 2- cyano group -2,3- dicyclohexyl dimethyl succinates, 2- cyano group -2,3-
Dicyclohexyl-succinate, 2- cyano group -2,3- dicyclohexyl succinic acid di-n-propyl esters, 2- cyano group -2,3-
Dicyclohexyl diisopropyl ester amber acid, 2- cyano group -2,3- dicyclohexyl succinic acid di-n-butyls, 2- cyano group -2,3-
Dicyclohexyl succinic acid diisobutyl ester, 2- cyano group -2,3- dicyclohexyl succinic acid -1- methyl ester -4- ethyl esters, 2- cyanogen
Base -2,3- dicyclohexyl succinic acid -1- ethyl ester -4- methyl ester, 2- cyano group -2,3- dicyclohexyl succinic acid -1- N-butyls
- 4- ethyl esters, 2- cyano group -2,3- dicyclohexyl succinic acid -1- ethyl ester -4- N-butyls, 2- cyano group -2- methyl -3- ethyls
Diethyl succinate, 2- cyano group -2- methyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- methyl -3- isopropyl fourths
Diethyl adipate, 2- cyano group -2- methyl -3- normal-butyl diethyl succinates, 2- cyano group -2- methyl -3- isobutyl groups fourth two
Diethyl phthalate, 2- cyano group -2- methyl -3- n-pentyl diethyl succinates, 2- cyano group -2- methyl -3- isopentyl succinic acid
Diethylester, 2- cyano group -2- methyl -3- cyclopenta diethyl succinates, 2- cyano group -2- methyl -3- n-hexyls succinic acid two
Ethyl ester, 2- cyano group -2- methyl -3- isohesyl diethyl succinates, 2- cyano group -2- ethyl -3- diethyl methylsuccinates,
2- cyano group -2- ethyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- ethyl -3- isopropyl diethyl succinates, 2-
Cyano group -2- ethyl -3- normal-butyl diethyl succinates, 2- cyano group -2- ethyl -3- isobutyl group diethyl succinates, 2-
Cyano group -2- ethyl -3- n-pentyl diethyl succinates, 2- cyano group -2- ethyl -3- isopentyl diethyl succinates, 2-
Cyano group -2- ethyl -3- cyclopenta diethyl succinates, 2- cyano group -2- ethyl -3- n-hexyl diethyl succinates, 2-
Cyano group -2- ethyl -3- isohesyl diethyl succinates, 2- cyano group -2- n-pro-pyl -3- diethyl methylsuccinates, 2-
Cyano group -2- n-pro-pyl -3- ethyl succinic acid diethylesters, 2- cyano group -2- n-pro-pyl -3- isopropyl diethyl succinates,
2- cyano group -2- n-pro-pyl -3- normal-butyl diethyl succinates, 2- cyano group -2- n-pro-pyl -3- isobutyl group succinic acid diethyls
Ester, 2- cyano group -2- n-pro-pyl -3- n-pentyl diethyl succinates, 2- cyano group -2- n-pro-pyl -3- isopentyl succinic acid two
Ethyl ester, 2- cyano group -2- n-pro-pyl -3- cyclopenta diethyl succinates, 2- cyano group -2- n-pro-pyl -3- n-hexyl succinic acid
Diethylester, 2- cyano group -2- n-pro-pyl -3- isohesyl diethyl succinates, 2- cyano group -2- isopropyl -3- dimethyl succinic acids
Diethylester, 2- cyano group -2- isopropyl -3- ethyl succinic acid diethylesters, 2- cyano group -2- isopropyl -3- n-pro-pyl succinic acid
Diethylester, 2- cyano group -2- isopropyl -3- normal-butyl diethyl succinates, 2- cyano group -2- isopropyl -3- isobutyl groups fourth two
Diethyl phthalate, 2- cyano group -2- isopropyl -3- n-pentyl diethyl succinates, 2- cyano group -2- isopropyl -3- isopentyl fourths
Diethyl adipate, 2- cyano group -2- isopropyl -3- cyclopenta diethyl succinates, 2- cyano group -2- isopropyl -3- n-hexyls
Diethyl succinate, 2- cyano group -2- isopropyl -3- isohesyl diethyl succinates, 2- cyano group -2- normal-butyl -3- methyl
Diethyl succinate, 2- cyano group -2- normal-butyl -3- ethyl succinic acid diethylesters, 2- cyano group -2- normal-butyl -3- n-pro-pyls
Diethyl succinate, 2- cyano group -2- normal-butyl -3- isopropyl diethyl succinates, 2- cyano group -2- normal-butyl -3- isobutyls
Base diethyl succinate, 2- cyano group -2- normal-butyl -3- n-pentyl diethyl succinates, 2- cyano group -2- normal-butyl -3-
Isopentyl diethyl succinate, 2- cyano group -2- normal-butyl -3- cyclopenta diethyl succinates, 2- cyano group -2- normal-butyls
- 3- n-hexyl diethyl succinates, 2- cyano group -2- normal-butyl -3- isohesyl diethyl succinates, 2- cyano group -2- isobutyls
Base -3- diethyl methylsuccinates, 2- cyano group -2- isobutyl group -3- ethyl succinic acid diethylesters, 2- cyano group -2- isobutyl groups
- 3- n-pro-pyl diethyl succinates, 2- cyano group -2- isobutyl group -3- isopropyl diethyl succinates, 2- cyano group -2- isobutyls
Base -3- normal-butyl diethyl succinates, 2- cyano group -2- isobutyl group -3- n-pentyl diethyl succinates, 2- cyano group -2-
Isobutyl group -3- isopentyl diethyl succinates, 2- cyano group -2- isobutyl group -3- cyclopenta diethyl succinates, 2- cyano group
- 2- isobutyl group -3- n-hexyl diethyl succinates, 2- cyano group -2- isobutyl group -3- isohesyl diethyl succinates, 2-
Cyano group -2- n-pentyl -3- diethyl methylsuccinates, 2- cyano group -2- n-pentyl -3- ethyl succinic acid diethylesters, 2-
Cyano group -2- n-pentyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- n-pentyl -3- isopropyl diethyl succinates,
2- cyano group -2- n-pentyl -3- normal-butyl diethyl succinates, 2- cyano group -2- n-pentyl -3- isobutyl group succinic acid diethyls
Ester, 2- cyano group -2- n-pentyl -3- isopentyl diethyl succinates, 2- cyano group -2- n-pentyl -3- cyclopenta succinic acid two
Ethyl ester, 2- cyano group -2- n-pentyl -3- n-hexyl diethyl succinates, 2- cyano group -2- n-pentyl -3- isohesyl succinic acid
Diethylester, 2- cyano group -2- isopentyl -3- diethyl methylsuccinates, 2- cyano group -2- isopentyl -3- ethyl succinic acids two
Ethyl ester, 2- cyano group -2- isopentyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- isopentyl -3- isopropyl succinic acid
Diethylester, 2- cyano group -2- isopentyl -3- normal-butyl diethyl succinates, 2- cyano group -2- isopentyl -3- isobutyl groups fourth two
Diethyl phthalate, 2- cyano group -2- isopentyl -3- n-pentyl diethyl succinates, 2- cyano group -2- isopentyl -3- cyclopenta fourths
Diethyl adipate, 2- cyano group -2- isopentyl -3- n-hexyl diethyl succinates, 2- cyano group -2- isopentyl -3- isohesyls
Diethyl succinate, 2- cyano group -2- cyclopenta -3- diethyl methylsuccinates, 2- cyano group -2- cyclopenta -3- ethyl fourths
Diethyl adipate, 2- cyano group -2- cyclopenta -3- n-pro-pyl diethyl succinates, 2- cyano group -2- cyclopenta -3- isopropyls
Diethyl succinate, 2- cyano group -2- cyclopenta -3- normal-butyl diethyl succinates, 2- cyano group -2- cyclopenta -3- isobutyls
Base diethyl succinate, 2- cyano group -2- cyclopenta -3- n-pentyl diethyl succinates, 2- cyano group -2- cyclopenta -3-
Isopentyl diethyl succinate, 2- cyano group -2- cyclopenta -3- n-hexyl diethyl succinates, 2- cyano group -2- cyclopenta
- 3- isohesyl diethyl succinates, 2- cyano group -2- n-hexyl -3- diethyl methylsuccinates, 2- cyano group -2- n-hexyls
- 3- ethyl succinic acid diethylesters, 2- cyano group -2- n-hexyl -3- n-pro-pyl diethyl succinates, 2- cyano group -2- n-hexyls
- 3- isopropyl diethyl succinates, 2- cyano group -2- n-hexyl -3- normal-butyl diethyl succinates, 2- cyano group -2- just oneself
Base -3- isobutyl group diethyl succinates, 2- cyano group -2- n-hexyl -3- n-pentyl diethyl succinates, 2- cyano group -2-
N-hexyl -3- isopentyl diethyl succinates, 2- cyano group -2- n-hexyl -3- cyclopenta diethyl succinates, 2- cyano group
- 2- n-hexyl -3- isohesyl diethyl succinates, 2- cyano group -2- isohesyl -3- diethyl methylsuccinates, 2- cyano group
- 2- isohesyl -3- ethyl succinic acid diethylesters, 2- cyano group -2- isohesyl -3- n-pro-pyl diethyl succinates, 2- cyano group
- 2- isohesyl -3- isopropyl diethyl succinates, 2- cyano group -2- isohesyl -3- normal-butyl diethyl succinates, 2-
Cyano group -2- isohesyl -3- isobutyl group diethyl succinates, 2- cyano group -2- isohesyl -3- n-pentyl diethyl succinates,
2- cyano group -2- isohesyl -3- isopentyl diethyl succinates, 2- cyano group -2- isohesyl -3- cyclopenta diethyl succinates
With at least one in 2- cyano group -2- isohesyl -3- n-hexyl diethyl succinates；
It is preferably selected from 2- cyano group -2,3- diethyl succinic acid diethylesters, 2- cyano group -2,3- diη-propyl succinic acid diethyls
Ester, 2- cyano group -2,3- diisopropyl diethyl succinates, 2- cyano group -2,3- di-n-butyl diethyl succinates, 2-
Cyano group -2,3- diisobutyl diethyl succinates, the n-pentyl diethyl succinates of 2- cyano group -2,3- two, 2- cyano group -2,3-
Diisoamyl diethyl succinate, 2- cyano group -2,3- bicyclopentyl diethyl succinates, 2- cyano group -2,3- two just oneself
Base diethyl succinate, the isohesyl diethyl succinates of 2- cyano group -2,3- two；2- cyano group -2,3- diisopropyls fourth two
Sour di-n-propyl ester, 2- cyano group -2,3- diisopropyl diisopropyl ester amber acids, 2- cyano group -2,3- diisopropyls fourth two
Sour di-n-butyl, 2- cyano group -2,3- diisopropyls-succinic acid diisobutyl ester, 2- cyano group -2,3- diisopropyl fourths
Diethyl adipate, 2- cyano group -2- normal-butyl -3- isopropyl diethyl succinates, 2- cyano group -2- isobutyl group -3- are different
Propyl succinimide diethyl phthalate, 2- cyano group -2- n-pentyl -3- isopropyl diethyl succinates, 2- cyano group -2- isoamyls
In base -3- isopropyls diethyl succinate and 2- cyano group -2- cyclopenta -3- isopropyl diethyl succinates extremely
Few one kind；
It is more preferably selected from 2- cyano group -2,3- diη-propyl diethyl succinates, 2- cyano group -2,3- diisopropyl succinic acid
Diethylester, 2- cyano group -2,3- di-n-butyl diethyl succinates, 2- cyano group -2,3- diisobutyl diethyl succinates,
The n-pentyl diethyl succinates of 2- cyano group -2,3- two, 2- cyano group -2,3- diisoamyl diethyl succinates, 2- cyano group
- 2,3- bicyclopentyl diethyl succinates, 2- cyano group -2- normal-butyl -3- isopropyl diethyl succinates, 2- cyano group
- 2- isobutyl group -3- isopropyl diethyl succinates, 2- cyano group -2- n-pentyl -3- isopropyl diethyl succinates,
2- cyano group -2- isopentyl -3- isopropyls diethyl succinate and 2- cyano group -2- cyclopenta -3- isopropyl succinic acid
At least one in diethylester.
The catalysis for olefinic polymerization that 11. preparation methoies according to any one of claim 2-10 are obtained
Agent component, it is characterised in that the gross weight based on the catalytic component, the titanium containing 1-3.5 weight %,
The precipitation additive a of 1-3.5 weight %, the internal electron donor of 6-15 weight %, and precipitation additive a are with interior to electricity
The mol ratio of daughter is 0.05：1 to less than 0.5:1；It is highly preferred that the titanium containing 1.8-3.2 weight %,
The precipitation additive a of 1.5-3 weight %, the internal electron donor of 7-11 weight %, and precipitation additive a are with interior to electricity
The mol ratio of daughter is 0.1-0.3:1.
A kind of 12. catalyst systems for olefinic polymerization, including：
A catalytic component or claim 11 that) preparation method any one of claim 1-10 is obtained
Described catalytic component；
B) alkyl aluminum compound；And
C) optional external donor compound.
A kind of 13. olefine polymerizing process, the method includes：Under olefin polymerization conditions, one or more alkene is made
Hydrocarbon is contacted with the catalyst system described in claim 12, and at least one in the alkene is by formula
CH2The alkene that=CHR is represented, wherein R are hydrogen or C1-C6Alkyl.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109111538A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111535A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| WO2019223683A1 (en) | 2018-05-21 | 2019-11-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, and catalyst including same |
| CN110511302A (en) * | 2018-05-21 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for olefinic polymerization |
| CN110511301A (en) * | 2018-05-21 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for olefinic polymerization |
| RU2779192C2 (en) * | 2018-05-21 | 2022-09-05 | Чайна Петролеум Энд Кемикал Корпорейшн | Catalytic component for olefin polymerization, its production method, and catalyst including it |
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| CN104558285A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst |
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| CN104558285A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst |
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| CN109111538A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111535A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111538B (en) * | 2017-06-23 | 2021-02-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN109111535B (en) * | 2017-06-23 | 2021-03-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| WO2019223683A1 (en) | 2018-05-21 | 2019-11-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, and catalyst including same |
| CN110511302A (en) * | 2018-05-21 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for olefinic polymerization |
| CN110511301A (en) * | 2018-05-21 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for olefinic polymerization |
| CN110511301B (en) * | 2018-05-21 | 2020-10-20 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| US20210205787A1 (en) * | 2018-05-21 | 2021-07-08 | China Petroleum & Chemical Corporation | Catalyst component for olefin polymerization, preparation method thereof, and catalyst including same |
| EP3798241A4 (en) * | 2018-05-21 | 2022-06-22 | China Petroleum & Chemical Corporation | Catalyst component for olefin polymerization, preparation method thereof, and catalyst including same |
| RU2779192C2 (en) * | 2018-05-21 | 2022-09-05 | Чайна Петролеум Энд Кемикал Корпорейшн | Catalytic component for olefin polymerization, its production method, and catalyst including it |
| US12121880B2 (en) * | 2018-05-21 | 2024-10-22 | China Petroleum & Chemical Corporation | Catalyst component for olefin polymerization, preparation method thereof, and catalyst including same |
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