JP2005023323A - ETHYLENE-alpha-OLEFIN COPOLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new ethylene-α-olefin copolymer having excellent physical properties such as mechanical strengths, low-temperature heat sealability, thermal and chemical stabilities and electrical properties. <P>SOLUTION: The copolymer has the following (A) to (D) and ≤0.4 eV electrical activation energy and is a copolymer of ethylene with a 3-20C α-olefin: (A) 0.86-0.96 g/cm<SP>3</SP>density; (B) 0.01-200 g/10min melt flow rate (MFR); (C) 1.5-4.5 molecular weight distribution (Mw/Mn); and (D) 1.08-2.00 composition distribution parameter Cb. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel ethylene / α-olefin copolymer having excellent physical properties such as mechanical strength, low-temperature heat sealability, moldability, and thermal, chemical stability, and electrical properties. More specifically, while having a relatively wide composition distribution, it has a low content of low molecular weight components and amorphous components, and has excellent thermal, chemical stability, and electrical characteristics, particularly in polymers. Halogen-free ethylene-α-olefin copolymers are suitable for food packaging, such as packaging films and containers, and are excellent in electrical properties and used in various molded products such as electric wires and cables. An ethylene / α-olefin copolymer is provided.

  Conventionally, linear low-density polyethylene (referred to as LLDPE), which is an ethylene / α-olefin copolymer produced with a Ziegler-type catalyst, is stronger and tougher than high-pressure radical method low-density polyethylene (referred to as HPLDPE). However, it is used for various applications such as a film, a sheet, a hollow molded body, an injection molded body, and the like. However, in order to reduce the weight of the molded product, further higher strength is required. In recent years, high-strength ethylene / α-olefin copolymers having a very narrow molecular weight distribution and composition distribution have been developed by metallocene catalysts. However, ethylene / α-olefin copolymers based on these metallocene catalysts have several drawbacks. For example, the composition distribution is very narrow, so the viscosity and strength changes with temperature are very rapid. The application range such as the temperature and the extrusion conditions is narrow and the molding processability is difficult. In addition, the molded product has disadvantages such as poor heat resistance and hot tack. The hot tack property is a property indicating the relationship between the adhesive strength of the joining portion immediately after heat sealing and the temperature, and it is determined that the wider the temperature range than a certain strength, the better.

  As a method for improving such drawbacks, attempts have been made to mix polyethylene resins with a plurality of Ziegler type catalysts (for example, JP-A-3-207736 and JP-A-3-207737). However, this method simultaneously increases the molecular weight distribution, so that improvement in strength cannot be expected, and there is a concern that various properties may be deteriorated due to the low melting point component and the low molecular weight component.

  On the other hand, as a method for improving the molding processability of the polymer by the metallocene catalyst, an attempt has been made to improve the melting characteristics of the resin while keeping the composition distribution narrow by using a metallocene catalyst having a plurality of ligands ( For example, it is difficult for JP-A-6-206939) to adjust the composition distribution while keeping the molecular weight distribution narrow.

  An object of the present invention is to provide a novel ethylene / α-olefin copolymer having excellent physical properties such as mechanical strength, low-temperature heat sealability, molding processability, and thermal, chemical stability, and electrical properties. It is in.

  As a result of diligent investigations along the above-mentioned purpose, the present inventors have a relatively wide composition distribution despite a narrow molecular weight distribution, and have a low content of low molecular weight components and amorphous components, and are thermally By obtaining a novel ethylene / α-olefin copolymer having excellent chemical stability and electrical characteristics, the above-mentioned object has been achieved.

Claim 1 of the present invention includes (A) density 0.86 to 0.96 g / cm ³ , (B) melt flow rate (MFR) 0.01 to 200 g / 10 min, (C) molecular weight distribution (Mw / Mn ) 1.5 to 4.5, (D) ethylene having a composition distribution parameter Cb of 1.08 to 2.00 and an electrical activation energy of 0.4 eV or less, and α having 3 to 20 carbon atoms -Copolymers with olefins.

Claim 2 of the present invention includes (A) a density of 0.86 to 0.96 g / cm ³ , (B) a melt flow rate (MFR) of 0.01 to 200 g / 10 minutes, and (C) a molecular weight distribution (Mw / Mn). ) 1.5 to 4.5, (D) composition distribution parameter Cb is 1.08 to 2.00, (E) the amount X (wt%) and density d of orthodichlorobenzene (ODCB) soluble component at 25 ° C. MFR satisfies the following relationship (A) or (B) (A) When the values of density d and MFR are d-0.008 x log MFR ≥ 0.93
X <2.0
(B) Density d and MFR values are d−0.008 × log MFR <0.93
X <9.8 × 10 ³ × (0.9300−d + 0.008 × log MFR) ² +2.0
It is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms that satisfies the above (A) to (E) and has an electrical activation energy of 0.4 eV or less.

Claim 3 of the present invention includes (A) a density of 0.86 to 0.96 g / cm ³ , (B) a melt flow rate (MFR) of 0.01 to 200 g / 10 minutes, and (C) a molecular weight distribution (Mw / Mn). ) 1.5 to 4.5, (D) composition distribution parameter Cb is 1.08 to 2.00, (E) the amount X (wt%) and density d of orthodichlorobenzene (ODCB) soluble component at 25 ° C. MFR satisfies the following relationship (A) or (B) (A) When the values of density d and MFR are d−0.008 × logMFR ≧ 0.93
X <2.0
(B) Density d and MFR values are d−0.008 × log MFR <0.93
X <9.8 × 10 ³ × (0.9300−d + 0.008 × log MFR) ² +2.0
Multiple peaks in the elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF)
It is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms that satisfies the above (A) to (F) and has an electrical activation energy of 0.4 eV or less.

Claim 4 of the present invention is obtained by polymerizing or copolymerizing olefins in the presence of a catalyst obtained by contacting at least the following components (1) to (4) with each other: 3 is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.
(1) Compound represented by general formula Me ¹ R ¹ pR ² q (OR ³ ) X ¹ _4-pqr
(In the formula, R ^1, R ³ is independently a hydrocarbon group or a trialkylsilyl group having 1 to 24 carbon atoms, R ² is 2,4-pentanedionato ligand or a derivative thereof (CH3COCHCOCH3) and its derivatives, X ¹ represents a halogen atom, Me ¹ represents Zr, Ti, or Hf, and p, q, and r are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4)
(2) Compound represented by the general formula: Me ² R ⁴ m (OR ⁵ ) nX ² _zmn
(In the formula, Me ² is a group I-III element in the periodic table, R ⁴ and R ⁵ are individually hydrocarbon groups having 1 to 24 carbon atoms, X ² is a hydrogen atom or a halogen atom (when X ² is a hydrogen atom) Me ² is the periodic table group III element) is, z represents the valence of Me ^2, m, n is 0 ≦ m ≦ z, 0 ≦ n ≦ z, 0 ≦ m + n ≦ z)
(3) Organocyclic compound having two or more double bonds that are conjugated (4) Modified organoaluminum compound and / or boron compound containing Al—O—Al bond

The ethylene / α-olefin copolymer of the present invention has a relatively wide composition distribution despite its narrow molecular weight distribution, and is suitable for molding processability, mechanical properties, optical properties and electrical properties, low-temperature heat seal properties, etc. It is excellent and suitable for films and various molded products. In particular, it is suitable as various molded films such as T-die molding, blown film molding, etc., and film molded bodies such as laminate raw materials.
In addition, the ethylene / α-olefin copolymer of the present invention containing no chlorine is a hollow molded body such as a container for mayonnaise, a tubular container for wasabi, a thin container for interior such as corrugated cardboard, a container for liquid detergent, etc. It is suitably used in the field of food packaging such as caps and container lids. In the electrical field, it is used for applications such as coating of electric wires, cables, insulation layers, steel pipes, or injection molded articles such as ski shoes. Used.
Furthermore, the ethylene / α-olefin copolymer of the present invention can be used as various multilayer films, laminated sheet runts, and laminated films by dry lamination, coextrusion, and extrusion lamination. In addition, it is particularly suitable for medical use because it is extremely thermally and chemically stable.

The present invention will be further described below.
The ethylene / α-olefin copolymer of the present invention is a copolymer of ethylene and one or more selected from C 3-20 α-olefins. The α-olefin having 3 to 20 carbon atoms is preferably one having 3 to 12, specifically, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and the like. Further, the content of these α-olefins is generally selected in the range of usually 30 mol% or less, preferably 3 to 20 mol%.

The (A) density of the ethylene / α-olefin copolymer of the present invention is 0.86 to 0.96 g / cm ³ , preferably 0.88 to 0.945 g / cm ³ , more preferably 0.89 to 0. Selected in the range of 940 g / cm ³ .

  The (B) MFR of the ethylene / α-olefin copolymer of the present invention is in the range of 0.01 to 200 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes, more preferably 0.1 to 50 g / 10 minutes. It is in.

(C) Mw / Mn of the ethylene / α-olefin copolymer of the present invention is 1.5 to 4.5, preferably 1.6 to 4.0, more preferably 1.8 to 3.5. It is in the range.
The calculation method of (C) molecular weight distribution Mw / Mn (C) of the ethylene / α-olefin copolymer of the present invention was determined by gel permeation chromatography (GPC) and weight average molecular weight (Mw) and number average molecular weight (Mn). ) To obtain this ratio Mw / Mn.

  The (D) composition distribution parameter Cb of the ethylene / α-olefin copolymer of the present invention is 1.08 to 2.00, preferably 1.10 to 1.80, more preferably 1.12 to 1. It is in the range of 70. If it is less than 1.08, the hot tack property is inferior, and if it is 2.00 or more, the transparency may be lowered and a polymer gel may be formed in the molded product.

The method for measuring the (D) composition distribution parameter Cb of the ethylene / α-olefin copolymer of the present invention is as follows.
A heat-resistant stabilizer is added to the sample, and dissolved in ODCB (orthodichlorobenzene) by heating at 135 ° C. so that the sample concentration becomes 0.2% by weight. This heated solution is transferred to a column packed with diatomaceous earth (Celite 545), and after filling, cooled to 25 ° C. at 0.1 ° C./min, and the sample is deposited on the celite surface. Next, a solution in which the sample is dissolved is collected at each temperature while ODCB is allowed to flow through the column at a constant flow rate and the column temperature is raised stepwise to 120 ° C. in steps of 5 ° C. After cooling this solution, the sample is reprecipitated with methanol, filtered and dried to obtain samples at each elution temperature. The weight fraction and the degree of branching (number of branches per 1000 carbon atoms) of the sorted sample are measured. The degree of branching is determined by 13C-NMR.

  For each fraction collected at 30 ° C. to 90 ° C. by such a method, the degree of branching is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, the correlation is approximated to a straight line by the method of least squares, and a calibration curve is created. This approximate correlation coefficient is sufficiently large. The value obtained from this calibration curve is taken as the degree of branching of each fraction. For the fraction collected at an elution temperature of 95 ° C. or higher, the linear relationship is not necessarily established between the elution temperature and the degree of branching, so this correction is not performed.

  Next, the weight fraction wi of each fraction is divided by the amount of change in the degree of branching bi (bi-bi-1) per elution temperature of 5 ° C. to obtain the relative concentration ci, and the relative concentration is plotted against the degree of branching. Obtain a composition distribution curve. The composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation (Equation 1).

  Here, cj and bj are the relative density and the branching degree of the jth section, respectively. The composition distribution parameter Cb is 1.0 when the composition of the sample is uniform, and increases as the composition distribution increases.

Many methods have been proposed for describing the composition distribution of the ethylene / α-olefin copolymer. For example, in JP-A-60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (logarithmic normal distribution) with respect to the number of branches of each fractionated sample obtained by solvent fractionation of the sample, The ratio of the weight average branching degree (Cw) and the number average branching degree (Cn) is obtained. This approximate calculation decreases in accuracy when the number of sample branches and the cumulative weight fraction deviate from the logarithmic normal distribution, and the correlation coefficient R ² is considerably low when measurement is performed on commercially available LLDPE, and the accuracy of the value is not sufficient. The definition and measurement method of Cw / Cn and Cb of the present invention are different.

In the ethylene / α-olefin copolymer of the present invention, (E) the amount X of ODCB soluble component at 25 ° C. is the ratio of the high branching component and the low molecular weight component contained in the ethylene / α-olefin copolymer. This indicates an index of heat resistance and stickiness of the surface of the molded product. The amount of ODCB solubles is affected by the α-olefin content and average molecular weight of the entire copolymer, that is, density and MFR.
Therefore, the amount X (% by weight) of the ODCB soluble component is less than 2% by weight, preferably 1 when the relationship between the density d and MFR satisfies (a) d−0.008 × log MFR ≧ 0.93. Less than wt%, more preferably less than 0.5 wt%.

When the relationship between d and MFR satisfies (b) d−0.008 × log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 × log MFR) ² +2.0 X <7.4 × 10 ³ × (0.9300−d + 0.008 × log MFR) ² +1.0, more preferably X <5.6 × 10 ³ × (0.9300− d + 0.008 × log MFR) ² +0.5.
The fact that the density, MFR and ODCB soluble content satisfy the above relationship indicates that the α-olefin contained in the entire copolymer is not ubiquitous.
In general, the amount of soluble ODCB is more in the ethylene / α-olefin copolymer of the conventional Ziegler type catalyst than in the ethylene / α-olefin copolymer of the present invention. It is a distinction.

The ODCB soluble content X at 25 ° C. is measured by the following method.
That is, 0.5 g of the sample is added to 20 ml of ODCB and heated at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. The solution is allowed to stand at 25 ° C. overnight and then filtered through a Teflon filter to collect the filtrate. The filtrate, which is the sample solution, is measured for the absorption peak intensity in the vicinity of the wave number of 2925 cm ⁻¹ of the asymmetric stretching vibration of methylene using an infrared spectrometer, and the concentration of the sample in the filtrate is calculated using a calibration curve prepared in advance. From this value, the ODCB soluble content at 25 ° C. is determined.

  The ethylene / α-olefin copolymer of the present invention preferably has a plurality of peaks in the elution temperature-elution amount curve determined by (F) continuous temperature rising elution fractionation method (TREF), and more preferably It is particularly preferred that the peak exists between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.

  FIG. 1 shows a TREF elution temperature-elution amount curve of the ethylene / α-olefin copolymer of the present invention, and FIG. 2 shows a TREF elution temperature-elution of the ethylene / α-olefin copolymer with a commercially available metallocene catalyst. A quantity curve is shown. As is clear from this figure, the ethylene / α-olefin copolymer of the present invention is clearly distinguished from the ethylene / α-olefin copolymer produced by a metallocene catalyst on the market today.

The TREF measurement method according to the present invention is as follows.
A heat-resistant stabilizer is added to the sample, and dissolved in ODCB by heating at 135 ° C. to a sample concentration of 0.05% by weight. After 5 ml of this heated solution is injected into a column filled with glass beads, it is cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, while flowing ODCB through this column at a constant flow rate, the column temperature is raised at a constant rate of 50 ° C./hr, and samples that can be dissolved in the solution are sequentially eluted at each temperature. At this time, the concentration of the sample in the solvent is continuously detected by an infrared detector with respect to the absorption of a methylene asymmetric stretching vibration with a wave number of 2925 cm ⁻¹ . From this concentration, an elution temperature-elution amount curve can be obtained.
TREF analysis is a very small amount of sample, and since it is possible to continuously analyze changes in elution rate with respect to temperature changes, relatively fine peaks that cannot be detected by a fractionation method can be detected.

The electrical activation energy of the ethylene / α-olefin copolymer of the present invention is 0.4 eV or less, preferably 0.3 eV or less, more preferably 0.25 eV or less. If it exceeds 0.4 eV, it indicates that the amount or mobility of charge carriers such as ions or electrons greatly increases with increasing temperature, and the thermal and chemical stability decreases.
This value is very small compared to the conventional polyethylene material, and the ethylene / α-olefin copolymer of the present invention is special in that the amount and mobility of the charge carrier contained in the copolymer are less affected by temperature. It is considered to have a structure.

  The activation energy is one of the constants included in the Arrhenius equation that represents the temperature change of the rate constant in the process of transport phenomenon, and the transition state and the original system in the process of moving from the original system or transition state to the generating system. It corresponds to the energy difference between the state and the energy. In particular, the electrical activation energy is used in the Arrhenius equation indicating the temperature dependence of the current. Here, a small activation energy indicates that the temperature dependence of the current is small.

The electrical activation energy according to the present invention can be obtained from the following equation (Arrhenius equation).
I ｅｘ exp ^{(-U / kT)}
(I: current, U: activation energy, k: Boltzmann constant, T: absolute temperature)
It can obtain | require by substituting the electric current value in room temperature (20 degreeC) and 90 degreeC to the said Formula.

Since the ethylene / α-olefin copolymer of the present invention has an electrical activation energy of 0.4 eV or less, the electrical characteristics are remarkably improved. For example, the volume resistivity at 20 ° C. is 10 ¹⁶ Ωcm or more, preferably 10 ¹⁷ Ωcm or more, and more preferably 10 ¹⁸ Ωcm. A high volume resistance value and a small activation energy indicate that the content of charge carriers such as ions or electrons is small or that the mobility thereof is small.

  The production of the specific ethylene / α-olefin copolymer of the present invention satisfies the properties (A) to (D), (A) to (E) or (A) to (F), and It is desirable to polymerize with a catalyst comprising at least (1) to (4).

That is, (1): General formula ^{Me 1 R 1 p R 2 q} (OR 3) r X 1 compound represented by the 4-pqr (wherein Me ¹ represents a Zr, Ti or Hf, R ¹ and R ³ Is a hydrocarbon group or trialkylsilyl group having 1 to 24 carbon atoms, R ² is a 2,4-pentandionato ligand or a derivative thereof, X ¹ is a halogen atom, p, q and r are each 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4) (2): General formula: Me ² R ⁴ m (OR ⁵ ) n X ² zmn (wherein Me ² is a group I-III element of the periodic table, R ⁴ and R ⁵ are each independently a carbon hydrogen group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom ( However, if X ² is a hydrogen atom Me ² is limited to the case of periodic table group III element) indicates, z represents the valence of Me ^2, And n are integers satisfying the ranges of 0 ≦ m ≦ z, 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z), (3): an organic cyclic compound having a conjugated double bond, and (4) : A catalyst obtained by bringing a modified organoaluminum compound containing an Al—O—Al bond and / or a boron compound into contact with each other.

Wherein Me ¹ of the general formula ^{Me 1 R 1 p R 2 q} (OR 3) r X 1 compound represented by the 4-pqr of the catalyst component (1) is shown Zr, Ti, and Hf. The type of these transition metals is not limited, and a plurality of transition metals can be used, but it is particularly preferable that Zr which is excellent in weather resistance of the copolymer is included. R ¹ and R ³ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group. Alkyl group such as butyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group and styryl Groups, aralkyl groups such as a benzhydryl group, a phenylbutyl group, and a neophyll group. These may be branched. R ² represents a 2,4-pentanedionate ligand or a derivative thereof (CH 3 COCHCOCH 3), and a derivative such as a dibenzoylmethanato ligand or a benzoylacetonate ligand. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r are in the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4 and 0 ≦ + q + r ≦ 4, respectively. is there.

  Examples of the compound represented by the above general formula (1) are tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tributoxymonochlorozirconium. , Dibutoxydichlorozirconium, tetrabutoxytitanium, tetrabutoxyhafnium and the like, and two or more of these may be used in combination.

General formula of the catalyst component ^{(2): Me 2 R 4} m (OR 5) n X 2 wherein Me ² in the compound represented by zmn represents the periodic table I~III group element, lithium, sodium, Potassium, magnesium, calcium, zinc, boron, aluminum and the like. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl group such as butyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group and styryl group Aralkyl groups such as benzhydryl group, phenylbutyl group and neophyll group. These may be branched. X ² represents a halogen atom or hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , and m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.

  Examples of the compound represented by the general formula of the catalyst component (2) include organic lithium compounds such as methyl lithium and ethyl lithium; organic magnesium compounds such as dimethyl magnesium, diethyl magnesium, methyl magnesium chloride, and ethyl magnesium chloride; dimethyl zinc Organic zinc compounds such as diethyl zinc; organoboron compounds such as trimethylboron and triethylboron; trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride , Organoaluminum such as diethylaluminum ethoxide and diethylaluminum hydride Derivatives such things like.

  The organic cyclic compound having two or more double bonds which are conjugates of the catalyst component (3) is two or more, preferably 2 to 4, more preferably 2 to 3 cyclic and conjugated double bonds. A cyclic hydrocarbon compound having one or two or more rings and a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially a hydrocarbon residue of 1 to 6 Cyclic hydrocarbon compound substituted with (typically an alkyl group or aralkyl group having 1 to 12 carbon atoms); 2 or more, preferably 2 to 4, more preferably 2 to 2 conjugated double bonds An organosilicon compound having a cyclic hydrocarbon group having 1 or 2 rings having 3 rings and a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon groups are partially 1 to 6 Hydrocarbon residues or alkali metal salts (Natri Organosilicon compounds substituted with arm or lithium salt) is included. Particularly preferred is one having a cyclopentadiene structure in any of the molecules.

  Suitable examples of the compound include cyclopentadiene, indene, azulene, or alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Moreover, the compound which these compounds couple | bonded (bridge | crosslinked) via the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.
A _L SiR _4-L
Here, A represents the cyclic hydrogen group exemplified by cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, and substituted indenyl group, and R represents methyl group, ethyl group, propyl group, isopropyl group, butyl group An alkyl group such as a group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group; To 24, preferably 1 to 12 hydrocarbon residues or hydrogen, L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

  Specific examples of the organic cyclic hydrocarbon compound of the above component (3) are cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethyl. Cyclopolyene having 5 to 24 carbon atoms such as indene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclopentadienyl Examples include silane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

  Catalyst component (4) A modified organoaluminum compound containing an Al—O—Al bond obtained by reacting an organoaluminum compound with water is a modification usually referred to as an aluminoxane by reacting an alkylaluminum compound with water. An organoaluminum is obtained and usually contains 1 to 100, preferably 1 to 50 Al—O—Al bonds in the molecule. The modified organoaluminum compound may be either linear or cyclic.

  The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferable.

  The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is usually 0.25 / 1 to 1.2 / 1, preferably 0.5 / 1 to 1/1.

In the present invention, the catalyst obtained by bringing the catalyst components (1) to (4) into contact with each other can be supported on an inorganic carrier and / or a particulate polymer carrier (5) and used for the polymerization reaction. . The inorganic carrier of component (5) may be in any shape such as powder, granule, flake, foil, and fiber as long as it retains its original shape at the stage of preparing the catalyst of the present invention. However, in any shape, the maximum length is usually in the range of 5 to 200 μm, preferably 10 to 100 μm. The inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m ² / g and a pore volume of 0.05 to ³ cm ³ / g.
As the inorganic carrier of the present invention, carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof can be used. These are usually in the air at 200 to 900 ° C. or in the form of nitrogen, argon or the like. Used by firing in an inert gas.

Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like. Examples of the metal oxide include single oxides or double oxides of groups I to VIII of the periodic table. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , _{ZrO 2, Fe 2 O 3,} SiO3-Al 2 O 3, Al 2 O 3 -MgO, Al 2 O 3 -CaO, Al 2 O 3 -MgO-CaO, Al 2 O 3 -MgO-SiO 2, Al 2 Examples include O ₃ —CuO, Al ₂ O ₃ —Fe ₂ O ₃ , Al ₂ O ₃ —NiO, and SiO ₂ —MgO. In addition, said formula represented with the oxide represents not a molecular formula but only a composition. That is, the structure and component ratio of the double oxide used in the present invention are not particularly limited. In addition, the metal oxide used in the present invention may adsorb a small amount of moisture or may contain a small amount of impurities.

As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples include magnesium carbonate, calcium carbonate, and barium carbonate. Examples of the carbonaceous material include carbon black and activated carbon.
Any of the above inorganic carriers can be suitably used in the present invention, but the use of metal oxides such as silica and alumina is particularly preferable.

On the other hand, as the particulate polymer carrier, any one of a thermoplastic resin and a thermosetting resin can be used as long as it is kept in a solid state without melting during the catalyst preparation and the polymerization reaction. Is usually in the range of 5 to 2000 μm, preferably 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can be present as a solid substance at the time of catalyst preparation and polymerization reaction, and can be arbitrarily selected from low molecular weight to ultra high molecular weight. It can be used.
Specifically, various polyolefins represented by particulate ethylene polymer, ethylene / α-olefin copolymer, propylene polymer or copolymer, poly 1-butene, etc. (preferably having 2 to 12 carbon atoms) , Polyester, polyamide, polyvinyl chloride, poly (meth) acrylate methyl, polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

  The inorganic carrier and / or the particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are contacted with an organoaluminum compound or a modified organoaluminum compound containing an Al—O—Al bond. After that, it can also be used as component (V).

  The method for producing the ethylene / α-olefin copolymer of the present invention is produced by a gas phase method, a slurry method, a solution method or the like, and is not particularly limited to a one-stage polymerization method, a multi-stage polymerization method, etc. Preferably, it is manufactured by.

  The ethylene / α-olefin copolymer of the present invention is excellent in heat by satisfying the properties (A) to (D), (A) to (E) or (A) to (F). Show chemical and chemical stability. In addition, the value of the rust test of the ethylene / α-olefin copolymer of the present invention is preferably 5.0 mg or less, and more preferably 3.0 mg or less. This value is smaller than the value of the conventional Ziegler-Natta resin, indicating that it is thermally and chemically stable. That is, in the ethylene / α-olefin copolymer of the present invention, by making an ethylene / α-olefin copolymer substantially free of halogen (such as chlorine), the copolymer with less rust is obtained. Excellent performance in applications such as packaging materials and containers related to microwave ovens, electric wire members, and electrical cords. In addition, the chemical stability required for general applications is excellent, and it is suitable for food, hygiene and medical related applications.

  In the present invention, as long as the characteristics of the invention are not essentially impaired, an antioxidant, as well as a nucleating agent, a lubricant, an antistatic agent, an antifogging agent, a pigment, an ultraviolet absorber, a dispersion, as necessary. Known additives such as an agent can be added. The ethylene / α-olefin copolymer of the present invention can also be used by blending with other thermoplastic resins such as polyolefins such as low density polyethylene, medium density polyethylene, high density polyethylene, and polypropylene.

Example:
EXAMPLES Next, although an Example demonstrates this invention in more detail, this invention is not limited by these.

The test method used in this experimental example is as follows.
(Physical property test method)
(1) Density: Conforms to JIS K6760.
(2) MFR: Conforms to JIS K6760.
(3) Melting point (measured by DSC): A sheet having a thickness of 0.2 mm was formed by hot pressing, a sample of about 5 mg was punched out, held at 230 ° C. for 10 minutes, cooled to 0 ° C. at 2 ° C./minute, and then again 10 ° C. The temperature is increased to 170 ° C./min, and the peak temperature of the re-high temperature peak that appears is defined as the maximum peak temperature Tm.
(4) Mw / Mn: GPC Waters 150 type was used under the following conditions.
Solvent: ODCB 135 ° C
Column: Toso-GMHHR-H (S)
Detector: Differential refractometer

(T-die film molding conditions)
Equipment: Union Plastic Co., Ltd. Extruder screw diameter: 30mmφ
T die: surface length 300 mm Screw rotation speed: 50 r. p. m Die lip gap: 1.2mm
Take-off speed: 6 m / min Molding resin temperature: 210-220 ° C. Film thickness: 50 μm

(Film performance evaluation)
(5) Haze (%): Conforms to ASTM D1003-61.
(6) Gross (%): compliant with JIS Z8741.
(7) Low-temperature heat-sealing property: Using a heat sealer manufactured by Tester Sangyo Co., Ltd., heat-sealed at several selected temperatures at a pressure of 2 kg / cm ² and a sealing time of 1 second. The film was subjected to a peel test with a test piece width of 15 mm and a peel test speed of 300 mm / min.
The temperature at which the peel strength of the test piece at this time was 500 g was represented by a value obtained by interpolation.
The lower this temperature, the better the low temperature heat sealability.

(Sheet molding method)
After homogenizing the copolymer with a roll, it was cut into chips, and this was press-molded at 180 ° C. to obtain a sheet.
(Evaluation of sheet sample)
(8) Tensile impact test: Determined according to ASTM D1822.
(9) Tensile modulus: The sample was mounted on a tensile tester, pulled at a rate of 5 mm / min, and the tensile modulus was determined from the stress and cross-sectional area when stretched by 1%.

(Rust test method)
Tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl) -4′-hydroxy-phenyl) propionate] methane (trade name: Irganox 1010), a phenolic antioxidant, was added to the sample powder. 10% by weight and 0.10% by weight of tris (2,4-di-t-butylphenyl) phosphite (trade name Irgaphos 168) which is a phosphite antioxidant were added and granulated.
After the pellets were melted in a 230 ° C. oil bath in a nitrogen stream for 3 hours, a soft iron plate having a surface area of 50 cm ² was immersed in the molten resin for 2 hours, the soft iron plate was taken out, and the resin adhered to the iron plate was peeled off. The iron plate is allowed to stand for 20 hours in a constant temperature and humidity chamber at 90 ° C. and a relative humidity of 90% to promote rust. Furthermore, it was dried in a desiccator containing silica gel for 1 day, and the weight increase (mg) of the soft iron plate was used as the amount of rust generation.

(Volume resistance measurement)
A sample was formed into a sheet having a thickness of 0.3 mm by hot pressing, and the electrode system shown in FIGS. 3A and 3B was used. In the figure, number 11 is a main electrode (50 mmφ), 12 is a guard electrode (inner diameter 75 mmφ), 13 is a sample, 14 is a high voltage electrode (80 mmφ), the main electrode is a vibration capacity type ammeter, and the high voltage electrode is a high voltage. Connected to the source with a cable. The electrode material was a stainless steel plate, and the surface in contact with the sample was polished to a mirror surface state by a buffing device.
The measurement was performed after the sample was placed in an electrode system in a nitrogen atmosphere at 90 ° C., the sample was uniformly heated to 90 ° C., and the lower electrode was short-circuited for 7 minutes to remove the charge charged on the sample surface. That's what I did.
The applied voltage is 3300V direct current from the battery. As a measuring instrument, a vibration capacity type ammeter (TR8411 manufactured by Advantest) was used. The cable connecting the measuring instrument and the electrode was a pipe cable to remove external noise. In this measurement system, at room temperature 3 × 10 ¹⁷ Ωcm, it can be measured stably to 3 × 10 ¹⁶ Ωcm at 90 ° C.. The thickness of the sample was about 0.3 mm, and each sample was measured up to 2 digits after the decimal. The effective electrode area is 19.6 cm ² . From the investigation of the current-time characteristics, after voltage application, the current decrease due to the absorbed current disappeared and the current could be measured stably after 10 minutes. Therefore, the current value 10 minutes after the voltage application is taken as the measured value. If the current is not stable even after 10 minutes, it was measured while waiting for about 2 minutes to stabilize. Removed from measurement. The volume resistance was determined based on the current value obtained from the measurement.
The measurement was performed 10 times, and the average value was used as data.

  Samples A1 to A9 used in Examples 1 to 9 were polymerized by the following method.

(Preparation of solid catalyst C1)
Under nitrogen, 150 ml of purified toluene is added to a 500 ml eggplant type flask equipped with an electromagnetic induction stirrer, and then 2.6 g of tetrapropoxyzirconium (Zr (On-Pr) 4) and 1.3 g of methylcyclopentadiene are added, followed by stirring at room temperature for 30 minutes. Thereafter, while maintaining the system at 0 ° C., 3.2 g of triisobutylaluminum [Al (iBu) 3] was added dropwise over 30 minutes. After completion of the addition, the system was brought to room temperature and stirred for 24 hours. Next, 200 ml of a toluene solution of methylalumoxane (concentration 1 mmol / ml) was added to this solution and reacted at room temperature for 1 hour.
Separately, 50 g of silica (Fuji Tebison, grade # 952, surface area 300 m ² / g) previously calcined at 600 ° C. for 5 hours was added to a 1.5 l three-necked flask equipped with a stirrer under nitrogen, and the total amount of the solution was added. And stirred at room temperature for 2 hours. Subsequently, the solvent was removed by nitrogen blowing to obtain a powdery solid catalyst C1 having good fluidity.

(Polymerization of sample A1)
Ethylene and 1-butene were copolymerized at a polymerization temperature of 70 ° C. and a total pressure of 20 kgf / cm ² G using a continuous fluidized bed gas phase polymerization apparatus. The gas composition in the system was a 1-butene / ethylene molar ratio of 0.10 and an ethylene concentration of 60 mol%. In order to continuously supply the catalyst C1 and keep the gas composition in the system constant, polymerization was performed while continuously supplying each gas. MFR was prepared by adjusting the hydrogen concentration in the system. Table 1 shows the physical properties of the polymer produced.

(Polymerization of sample A2)
Polymerization was carried out in the same manner as in (Sample A1) except that the molar ratio of 1-butene / ethylene was changed. The physical properties of the copolymer are shown in Table 1.

(Preparation of solid catalyst C2)
Purified toluene was added to a catalyst preparation apparatus equipped with an electromagnetic induction stirrer under nitrogen, and then 0.55 g of dipropoxydichlorozirconium (Zr (OPr) ₂ Cl ₂ ) and 1.6 g of methylcyclopentadiene were added, and the system was maintained at 0 ° C. While dropping 9.0 g of tridecylaluminum, the reaction system was maintained at 50 ° C. and stirred for 16 hours. Next, 200 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added to this solution and reacted at room temperature for 1 hour. Separately, purified toluene was added to a catalyst preparation device equipped with a stirrer under nitrogen, and then 50 g of silica (Fuji Devison, grade # 952, surface area 300 m ² / g) previously calcined at 400 ° C. for a predetermined time was added. The whole amount was added and stirred at room temperature. Next, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder (C2) having good fluidity.

(Polymerization of sample A3)
Ethylene and 1-butene were copolymerized at a polymerization temperature of 70 ° C. and a total pressure of 20 kgf / cm ² G using a continuous fluidized bed gas phase polymerization apparatus. The gas composition in the system was a 1-butene / ethylene molar ratio of 0.10 and an ethylene concentration of 60 mol%. In order to continuously supply the catalyst C2 and keep the gas composition in the system constant, polymerization was performed while continuously supplying each gas. MFR was prepared by adjusting the hydrogen concentration in the system. Table 1 shows the physical properties of the polymer produced.

(Polymerization of samples A4 to A5)
Samples A4 and A5 were polymerized in the same manner as Sample A1, except that the comonomer was 1-hexene. The physical properties of the copolymer are shown in Table 1.

(Preparation of catalyst component C3)
Under nitrogen, 100 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and then 4.9 g of tetrakis (2,4-pentanedionate) zirconium (Zr (acac) 4) and 1,3-dimethylcyclopentadiene. After adding 7.4 g and stirring at room temperature for 30 minutes, 20 ml of triisobutylaluminum [Al (iBu) 3] was added dropwise thereto at room temperature over 30 minutes. After completion of the dropwise addition, the mixture was reacted at room temperature for 1 hour to obtain a solution C3 containing the catalyst component of the present invention. The Zr concentration in this solution is 0.076 mmol / ml.

(Polymerization of sample A6)
A 200-liter stainless steel autoclave with a stirrer capacity was purged with nitrogen and 200 g of dried sodium chloride was added. Then, 0.29 ml of the above-mentioned catalyst component C3 solution and 2.2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml were added. Heated to ° C. Next, a mixed gas of ethylene and 1-butene (molar ratio of 1-butene / ethylene = 0.25) was put into an autoclave at a pressure of 9 kg / cm ² G to start polymerization, and the polymerization of eletin and 1-butene While continuously supplying a mixed gas (1-butene / ethylene molar ratio = 0.05), polymerization was carried out for 1 hour while maintaining a total pressure of 9 kg / cm ² G.
After the polymerization was completed, excess gas in the reactor was discharged, and the reactor was cooled to remove sodium chloride to obtain 81 g of a white polymer. The catalyst efficiency was 40,000 g / gZr. Table 1 shows the physical properties of the polymer produced.

(Preparation of catalyst component C4)
Under nitrogen, add 100 ml of purified toluene to a 100 ml three-necked flask equipped with an electromagnetic induction stirrer, then add 4 g of tributoxymono (trimethylsilanolate) zirconium and 12 g of butylcyclopentadiene, stir at room temperature for 30 minutes, and then add trihexyl. 34 ml of aluminum [Al (n-Hx) 3] was added dropwise at room temperature over 30 minutes. After completion of the dropping, the mixture was reacted at room temperature for 1 hour to obtain a solution C4 containing the catalyst component of the present invention. The Zr concentration in this solution is 0.101 mmol / ml.

(Polymerization of sample A7)
Under nitrogen, 0.11 ml of the catalyst component C4 solution (1 mg as Zr) and 1 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml were added to a 50 ml flask and stirred.
A 200-liter stainless steel autoclave with a stirrer was purged with nitrogen and 200 g of dried sodium chloride was added, and the whole catalyst component solution was added and heated to 60 ° C. with stirring. Next, a mixed gas of ethylene and 1-butene (molar ratio of 1-butene / ethylene = 0.25) was put into an autoclave at a pressure of 9 kg / cm ² G to initiate polymerization, and ethylene and 1-butene While continuously supplying a mixed gas (1-butene / ethylene molar ratio = 0.05), polymerization was carried out for 1 hour while keeping the total pressure at 9 kg / cm ² G.
After completion of the polymerization, excess gas in the reactor was discharged, and the reactor was cooled to remove sodium chloride to obtain 190 g of a white polymer. The catalyst efficiency was 190,000 g / gZr. Table 1 shows the physical properties of the polymer produced.

(Preparation of catalyst component C5)
Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and then 3.9 g of tetrabutoxyzirconium and 6.4 g of methylcyclopentadiene were added. After stirring at room temperature for 30 minutes, this was cooled to 0 ° C. Then, 27.5 ml of trihexylaluminum [Al (n-Hx) 3] was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at room temperature for 24 hours. 3 ml of the solution obtained in the 50 ml flask purged with nitrogen (0.2 mmol as Zr) and 4 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml were added and stirred at room temperature for 30 minutes. Next, 0.16 g (0.2 mmol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added, and the mixture was stirred at room temperature for 3 hours to react to obtain a solution C5 containing the catalyst component of the present invention.

(Polymerization of sample A8)
1000 ml of toluene produced by replacing a 3 l stainless steel autoclave with a stirrer with nitrogen was added, 0.2 ml of the catalyst component solution C5 (0.5 mg as Zr) was added, and the mixture was heated to 60 ° C. with stirring. Next, a mixed gas of ethylene and 1-butene (molar ratio of 1-butene / ethylene = 0.25) was put into an autoclave at a pressure of 9 kg / cm ² G to initiate polymerization, and ethylene and 1-butene While continuously supplying a mixed gas (1-butene / ethylene molar ratio = 0.05), polymerization was carried out for 1 hour while keeping the total pressure at 9 kg / cm ² G.
After the polymerization was completed, excess gas in the reactor was discharged, the reactor was cooled, and the contents were taken out to obtain 72 g of a white polymer. The catalyst efficiency was 36,000 g / gZr. Table 1 shows the physical properties of the polymer produced.

(Preparation of catalyst component C6)
Under nitrogen, add 150 ml of purified toluene to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, then add 3.9 g of tetrabutoxyzirconium and 11 g of cyclopentadienyltrimethylsilane, and stir at room temperature for 30 minutes. After cooling and holding, 9.1 g of triethylaluminum was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at room temperature for 24 hours. The solution obtained in the 50 ml flask purged with nitrogen was added with 3.4 ml (0.2 mmol as Zr) and 4 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml, and stirred at room temperature for 30 minutes. Next, 0.16 g (0.2 mmol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added and stirred at room temperature for 3 hours to react, thereby obtaining a solution C6 containing the catalyst component of the present invention.

(Polymerization of sample A9)
A polymerization reaction was performed in the same manner as in Example 3 except that 0.19 ml of the catalyst component C6 was added. The catalyst efficiency was 150,000 g / gZr. Table 1 shows the physical properties of the polymer produced.

  Sample (B1) was obtained by copolymerizing ethylene and 1-butene by a vapor phase method using titanium tetrachloride and a triethylaluminum catalyst. The physical properties are shown in Table 2 together with the evaluation results.

  Sample (B2) is an ethylene / 1-butene copolymer (LLDPE) obtained by copolymerizing ethylene and 1-butene by a slurry method using titanium tetrachloride and a triethylaluminum catalyst. The physical properties are shown in Table 2 together with the experimental results.

  Sample (B3) is an ethylene / 1-hexene copolymer (LLDPE) obtained by copolymerizing ethylene and 1-hexene by a vapor phase method using titanium tetrachloride and a triethylaluminum catalyst. The physical properties are shown in Table 2 together with the experimental results.

(Polymerization of sample B4)
25 L of purified toluene was placed in a 50 L pressure reactor equipped with a stirrer substituted with nitrogen. Next, 330 g of 1-butene was added, and a mixed liquid of bis (n-butylcyclopentadienyl) zirconium dichloride and methylalumoxane [MAO] (Al / Zr molar ratio = 500) as Zr was 0.33 mmol. Then, the temperature was raised to 80 ° C. to prepare a metallocene catalyst. Next, the superposition polymerization was started so as to be 9 kg / cm ² G of ethylene. While continuously polymerizing ethylene, the total pressure was maintained at 6 kg / cm ² G and polymerization was carried out for 1 hour to produce an ethylene / 1-butene copolymer. The physical properties of the copolymer are shown in Table 2.

Evaluation results:
Examples 1 and 2 of the present invention are ethylene / 1-butene copolymers obtained by using a catalyst containing 1-butene as a comonomer and containing no chlorine, less rusting, dart impact strength, transparent It can be seen that the properties and the low temperature heat seal temperature are excellent. Example 3 is an ethylene / 1-butene copolymer of the present invention using 1-butene as a comonomer and using a halogen (chlorine) -containing catalyst. Comparative Examples 1 and 2, which are ethylene / 1-butene copolymers with a Ziegler-type catalyst using 1-butene as a comonomer containing the same halogen, have a lot of rust generation, dirt impact strength, transparency, and low-temperature heat. The sealing temperature is inferior.
Examples 4 and 5 are ethylene / 1-hexene copolymers obtained by using 1-hexene as a comonomer and a catalyst containing no chlorine, and Comparative Example 3 is a Ziegler type using 1-hexene as a comonomer. Catalytic LLDPE. When these were compared, the comparative example 3 had much generation | occurrence | production of rust, and dart impact strength, transparency, low temperature heat seal temperature, etc. were inferior.
Comparative Example 4 is an ethylene / 1-butene copolymer obtained by using 1-butene as a comonomer and polymerized with a metallocene-based catalyst. It had a difficulty in sex.
Examples 5 to 9 of the present invention were ethylene / 1-butene copolymers obtained by bulk polymerization using an autoclave as a polymerization reactor, 1-butene as a comonomer, and bulk polymerization. Thus, the generation of rust is small, the dart impact strength, the transparency, the low temperature heat seal temperature and the like are excellent, and the physical properties of the polymer according to the present invention are excellent regardless of the production method.

The elution temperature-elution amount curve (TREF curve) of the copolymer of this invention is shown. The elution temperature-elution amount curve (TREF curve) of a copolymer by a metallocene catalyst is shown. 1 shows an electrode system for measuring volume resistance.

Explanation of symbols

11 Main electrode 12 Guard electrode 13 Sample 14 High voltage electrode

Claims (4)

(A) Density 0.86 to 0.96 g / cm ³
(B) Melt flow rate (MFR) 0.01-200 g / 10 min
(C) Molecular weight distribution (Mw / Mn) 1.5-4.5
(D) Composition distribution parameter Cb 1.08 to 2.00
A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms satisfying the above (A) to (D) and having an electrical activation energy of 0.4 eV or less. (A) Density 0.86 to 0.96 g / cm ³
(B) Melt flow rate (MFR) 0.01-200 g / 10 min
(C) Molecular weight distribution (Mw / Mn) 1.5-4.5
(D) Composition distribution parameter Cb 1.08 to 2.00
(E) The amount X (wt%) of the orthodichlorobenzene (ODCB) soluble component at 25 ° C. and the density d and MFR satisfy the following relationship (A) or (B): (A) Values of density d and MFR When d-0.008 × logMFR ≧ 0.93
X <2.0
(B) Density d and MFR values are d−0.008 × log MFR <0.93
X <9.8 × 10 ³ × (0.9300−d + 0.008 × log MFR) ² +2.0
A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms satisfying the above (A) to (E) and having an electrical activation energy of 0.4 eV or less. (A) Density 0.86 to 0.96 g / cm ³
(B) Melt flow rate (MFR) 0.01 to 200 g / 10 min (C) Molecular weight distribution (Mw / Mn) 1.5 to 4.5
(D) Composition distribution parameter Cb 1.08 to 2.00
(E) The amount X (wt%) of the orthodichlorobenzene (ODCB) soluble component at 25 ° C. and the density d and MFR satisfy the following relationship (A) or (B): (A) Values of density d and MFR Is d−0.008 × logMFR ≧ 0.93
X <2.0
(B) Density d and MFR values are d−0.008 × log MFR <0.93
X <9.8 × 10 ³ × (0.9300−d + 0.008 × log MFR) ² +2.0
Multiple peaks in the elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF)
A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms satisfying the above (A) to (F) and having an electrical activation energy of 0.4 eV or less. The ethylene and carbon number according to claims 1 to 3, obtained by polymerizing or copolymerizing olefins in the presence of a catalyst obtained by contacting at least the following components (1) to (4) with each other: Copolymer with 3-20 alpha olefins.
(1) Compound represented by general formula Me ¹ R ¹ pR ² q (OR ³ ) X ¹ _4-pqr
(In the formula, R ^1, R ³ is independently a hydrocarbon group or a trialkylsilyl group having 1 to 24 carbon atoms, R ² is 2,4-pentanedionato ligand or a derivative thereof (CH3COCHCOCH3) and its derivatives, X ¹ represents a halogen atom, Me ¹ represents Zr, Ti, or Hf, and p, q, and r are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4)
(2) Compound represented by the general formula: Me ² R ⁴ m (OR ⁵ ) nX ² _zmn
(In the formula, Me ² is a group I-III element in the periodic table, R ⁴ and R ⁵ are individually hydrocarbon groups having 1 to 24 carbon atoms, X ² is a hydrogen atom or a halogen atom (when X ² is a hydrogen atom) Me ² is the periodic table group III element) is, z represents the valence of Me ^2, m, n is 0 ≦ m ≦ z, 0 ≦ n ≦ z, 0 ≦ m + n ≦ z)
(3) Organocyclic compound having two or more double bonds that are conjugated (4) Modified organoaluminum compound and / or boron compound containing Al—O—Al bond

Images