JPS58225105A - Preparation of improved ethylenic polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having a uniform particle size, by using a catalyst prepared by grinding a specific Al compound in combination with a compound containing an Si-O bond and Mg alcoholate, bringing the ground material into contact with a halogen-containing tetravalent compound to give a solid, blending it with an organoaluminum compound. CONSTITUTION:Ethylene alone is polymerized or ethylene is copolymerized with an alpha-olefin and/or diolefin in the presence of a catalytic system comprising (A) a solid catalytic component obtained by grinding (i) an aluminum trihalide (e.g., aluminum trichloride, etc.) in combination with an organic compound containing an Si-O bond (e.g., diphenylethoxysilane, etc.) and a magnesium alcoholate (e.g., magnesium ethylate, etc.) to give a ground material, bringing it into contact with (ii) a tetravalent titanium compound (e.g., titanium tetrachloride, etc.) containing at least one halogen atom in a liquid phase and (B) an organoaluminum compound.

Description

DETAILED DESCRIPTION OF THE INVENTION ■Object of the Invention The present invention relates to an improved method for producing ethylene polymers. More specifically, (A) (1) a co-pulverized product obtained by co-pulverizing (a) aluminum trihalide, (b) an organic compound having a Si-0 bond, and (C) magnesium alcoholade, and ( 2)
Homopolymerization of ethylene or ethylene with α-olefin and/or diolefin in the presence of a solid catalyst component obtained by contacting a tetravalent titanium compound in a liquid phase and a catalyst system obtained from an organoaluminum compound. The present invention relates to an improved method for producing an ethylene polymer characterized by copolymerization, and the object thereof is to provide an ethylene polymer with high activity and uniform particle size.

1], D Background of the Invention In recent years, there have been many solid catalyst components (so-called carrier-supported catalysts) obtained as olefin polymerization catalysts by co-pulverizing various magnesium compounds and transition metal compounds, substances, etc. by co-pulverizing or contacting them in a liquid phase. Proposed. Some of the inventors of the present invention also proposed various catalysts supported on carriers using magnesium alcolade as a magnesium compound (Japanese Patent Publication No. 56-39766, and Japanese Patent Application Laid-Open No. 53-132).
No. 082, No. 54-21483, No. 54-75491
No. 54-81190, No. 55-3459). Among them, in Japanese Patent Publication No. 56-39766, aluminum trihalide, an organic compound having an 8i-0 bond, and magnesium alcoholade are brought into contact simultaneously or in multiple stages in a slurry state (the two components are brought into contact in advance, and the obtained In the presence of a catalyst system obtained from a solid catalyst component obtained by contacting and supporting a tetravalent titanium compound on a solid product obtained by contacting the cloudy product with other components, and an organoaluminum compound, It has already been disclosed that ethylene-based polymers with very high polymerization activity can be obtained by homopolymerizing ethylene or copolymerizing ethylene and α-olefin.

Generally, in a catalyst system using a solid catalyst component obtained in a slurry state with a magnesium compound as one solid component, the shape is often influenced by the magnesium alcoholade used as a starting material or the manufacturing process of the resulting product.

That is, it has been found that the irregular shape and particle size of magnesium alcoholade, which is one of the starting materials, greatly influences the shape, particle size, and particle size distribution of the ethylene polymer obtained using it.

In other words, the particle size distribution is wide and the melting index (
This results in non-uniform polymer particles with different melt indexes. This results in undesirable post-polymerization processing such as gas transport of the polymer particles or classification during mixing in bulk tanks.

As a result, there is a possibility that a product having a molecular weight that deviates from the target molecular weight may be produced with a time lag due to classification.

In order to solve these problems, the present inventors have proposed a method for preparing a catalyst by pulverizing magnesium alcoholade to make the particle size and powder size distribution uniform. It can be said that by this method, the problems of uniformity of particle size and prevention of classification could be solved to some extent.

However, not only does one step of pulverizing the magnesium alcoholate increase, but the resulting polymerization activity is not much different from that of unpulverized magnesium alcoholate, and in addition, the n-hexane soluble content and cyclohexane content corresponding to the low molecular weight components are This is not a satisfactory catalyst system because the soluble content is still present in the polymer as a by-product.

10 Structure of the Invention Based on the above, the present inventors produced an ethylene polymer (post-treatment) using a catalyst system obtained from a support of a transition metal compound (solid catalyst component) and an organoaluminum compound. As a result of various searches to solve the problems mentioned above, (A) (1) (a) aluminum trihalide, (b)
A co-pulverized product obtained by co-pulverizing an organic compound having a Si-0 bond (hereinafter referred to as a "silicon-based compound") and (C) a magnesium alcoholade, and (2) a tetravalent product having at least one halogen atom. A solid catalyst component obtained by contacting a titanium compound (hereinafter referred to as a "titanium compound") in a liquid phase, and It was discovered that a uniform ethylene polymer with very high polymerization activity can be obtained by copolymerizing an olefin and/or a diene, and the present invention was achieved based on this finding.

Effects of the Invention When ethylene is homopolymerized or ethylene is copolymerized with α-olefin and/or diolefin using a catalyst system obtained from the solid catalyst and organoaluminum compound used in the present invention, the solid catalyst component It exhibits the following effects (characteristics) including manufacturing.

(1) By adopting the co-pulverization method, costs are significantly reduced when preparing the catalyst, such as by reducing the amount of catalyst raw materials, shortening the time required for preparation, and eliminating the need for solvents.

(2) The polymerized oil per catalyst is dramatically improved (approximately twice) compared to a catalyst produced by a slurry method (unpulverized).

(3) The particle size distribution of the obtained polymer becomes uniform, and the melt index for each particle size (measured according to JIS K-6760 at a temperature of 190°C and a load of 2.16 kg, hereinafter referred to as rM and IJ) The distribution of is also narrow and uniform.

(4) A polymer having a relatively low molecular weight (high M, I, ) can be obtained in a region where the relative concentration of hydrogen used as a chain transfer agent to the ethylene concentration is low. In particular, this point is important when applying continuous polymerization (so-called multi-stage polymerization) under different conditions of chain transfer agent concentrations to produce polymers with a wide molecular weight distribution. Advantageously, active, relatively low molecular weight polymers are obtained.

(5) Not only is it highly copolymerizable with conjugated or non-conjugated dienes such as butadiene and ethylidenenorbornene, but also a copolymer with high activity and high diene content can be obtained.

(6) The particle size distribution is also relatively narrow and uniform compared to solid catalyst components produced by the slurry method (unpulverized), which facilitates uniform dispersion of high-molecular-weight polymers and low-molecular-weight polymers in the multistage polymerization process. can get.

This results in a polymer mixture with excellent impact resistance.

(7) Extremely high polymerization activity, wide range of molecular weight from 10,000 to 500,000, and density from 0900 to 0.970g7c
When producing a copolymer of ethylene and α-olefin in the rio region, for example, if the ethylene partial pressure is 10 kg/
When carried out under conditions of cr/l (gauge pressure), 1 g of solid catalyst component and residence time of 1 hour"!r9.8X1
0'~'20x10'90x'f-vy system
1 polymer is obtained. Furthermore, the proportion of transition metals (titanium atoms) that cause coloration and deterioration of polymers remaining in the polymer is 0.5 to 2, even without refining the polymer.
I)I)m, and the amount is extremely small.

(8) Very little soluble content (very low molecular weight components) that can be extracted by solvents such as n-hexane.

DETAILED DESCRIPTION OF THE INVENTION Co-milled product The co-milled product of the present invention is obtained by co-milling aluminum trihalide, a silicon-based compound, and magnenium alcoholate.

(1) Aluminum trihalide Aluminum trihalide is an anhydride, and includes aluminum trichloride, aluminum tribromide, and aluminum trifluoride. Particularly preferred is aluminum trichloride. The aluminum trihalide may be in the form of powder or granules.

(2) Silicon-based compound Also, silicon thread compound tis used in the present invention
It is an organic compound having an i-0 bond, among which the general formulas of typical compounds are those represented by the following formulas [formulas D to (III)].

Si (OR')mR2n (I)
R3 (R: 810M5 i R;
(11) (RffSIO)p(Ill) In the formula, R1%R2 and R6 may be the same or different, and are a group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group having at most 20 carbon atoms. A hydrocarbon group (even if unsaturated) selected from the following, which may be substituted with a rogen atom or an alkoxide group having at most 20 carbon atoms, or may have an epoxy ring such as a glycidyl group) can be(
R2 may be a hydrogen atom or a halogen atom, R6 may be a hydrogen fragment -r), R3, R4 and R5 may be the same or different, and the above hydrocarbon group (konera may be unsaturated,
) or a halogen atom, m-1
-n is 4 (where m''-,,o) and l is 1
is an integer from 2 to 1000, and p is an integer from 2 to 1000.

(Representative silicon compounds represented by formula I3 include tetramethoxysilane, dimethyldimethoxysilane, dimethylshedoxinlan, tetraethoxysilane, triethoxyethylsilane, jetoxydiethylsilane, ethoxytriethylsilane, and tetrapropolysilane. Quinsilane, dipropoxydipropylsilane, tetra-isopropoxysilane, di-isopropoquine-di-isoprobylsilane, dimethoxydiethyl 7rane, jetoxydibutylsilane, tetra-n-butoxysilane, di-n-butoxysilane 〇-Butylenerane, tetra-secondary-butoxysilane, tetrahexoxinerane, tetraoctoxinrane, tetraphenookiranrane, tetracresylsilane, diphenyldiethquinrane, diphenyldimethoxysilane, trimethoxychlorosilane, dimethoxycyclo Ronlan, dimethoxydibromosilane, triethquinchlorosilane, Shedquin dibromosilane, dibutoxydichlorosilane, dicyclobentoquine diethylsilane, Shedquin diphenylsilane, 3.5-dimethylphenoxytrimethylsilane, methylphenyl-bis(2
-chloroethquine) silane, dimethoxydibenzylsilane, tri-n propylallyloxysilane, allyl(a
Examples include lis(2-chloroethoxy)silane, trimethoxy-3-ethoxypropylsilane, vinyl(tributoxy)silane, and 3(glycidoxy)propyltrimethoxysilane.

In addition, typical silicon-based compounds represented by formula (1,1) include hexamethyldisiloxane, octaethyltrisiloxane, tetracosamethylundecacloxane, 8-hydroheptamethyltrisiloxane, hexamethyldisiloxane, Phenyldisiloxane, hexacyclohexyldisiloxane, 1,8-dimethyldinoxane, hexamethyldisiloxane, octaethyltrisiloxane, hexapropyldinsiloxane, 1,3-dichlorotetramethyldisiloxane, 1,3-bis( p-phenoquine diphenyl)-1,3-dimethyl-1,3-diphenylcycloxane, l,3-allyltetramethyldisiloxane, 1,3-dibenzyltetramethyldisiloxane, 2, 2,4,4-tetraphenyl-2,4-
Disilar 1-oxane clopentane, 1,1,3.
Mention may be made of 3-tetramethyldisiloxane and hexachlorodineroxane.

Furthermore, typical silicon-based compounds represented by the OID formula include 1,3.5-)limethylcyclotrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylchlorotrisiloxane, ],]3,5-trimethyltriphenylcyclotrisiloxanehexaphenylcyclotrisiloxane7.1,3,5-tribenzyltrimethylcyclotrisiloxane and],3,5-triallyl(al
lyl))limethylchlorotrisiloxane.

Among these silicon-based compounds, in the formula (I), R1 and R2 are alkyl groups having at most 8 carbon atoms,
Those represented by a phenyl group or an aralkyl group are preferred. Further, in the above formula (11), it is preferable that R3, R4 and R' are represented by an alkyl group having at most 4 carbon atoms, a phenyl group, or a nitrogen atom, and furthermore, 1 is 4 or less. Preferably. Moreover, the a1
In formula 1), R6 is preferably a hydrogen atom, an alkyl group having 4 or less carbon atoms, a phenyl group or a vinyl group, and further preferably p is 10 or less. These suitable silicon-based compounds include tetramethynesilane, tetraethquinsilane, tetracresylsilane, hexamethyldisiloxane, shedquin diphenylsilane, dimethoxydiphenylsilane, and vinyl(tryptoquine)silane.

(3) Magnesium alcoholade Further, among the magnesium alcoholades used to produce the co-pulverized product, the general formula of a typical one is represented by the following formula [Formula (IV)].

In the Mg(OR7)2 GV) GV) formula, R7 is an alkyl group having at most 8 carbon atoms, a cycloalkyl group, a cycloalkyl group having an alkyl group, an aryol (formerly °yl) group, and an aralkyl group. A hydrocarbon group selected from the group consisting of

Among these magnesium alcoholades, representative ones include magnesium methylate, magnesium ethylate, magnesium heptium (n-pubipyrate), magnesium butylade (impropilade), and magnesium hexylade. , magnesium phenolate, magnesium cyclohexaltate, alcoholade of benzyl alcohol of magnesium 7ium, and magnesium cresolate.

Among Konera's Magnesium Alcolade, Maemachi IV)
In the formula, R7 preferably represents an alkyl group having at most 3 carbon atoms or a phenyl group.

Suitable magnesium alcoholades include magnesium ethylate, magnesium butylade and magnesium phenolate.

(4) Ratio of co-pulverization In producing the co-pulverized product of the present invention, the addition ratio of aluminum trihalide and silicon-based compound to the magnesium alcoholade per mole is generally 0.02 to 1. 0 mol, especially 0.05
~0.20 mol is preferred. Furthermore, the ratio of aluminum atoms in the aluminum trihalide to silicon atoms in the silicon-based compound is important. The value is preferably 0.25 to 4, particularly preferably 0.5 to 2. If the ratio of aluminum trihalide and silicon-based compound added to 1 mol of magnesium alcoholade is less than 0.02 mol, flat polymers with mutual adhesion are formed, resulting in irregular particle sizes. On the other hand, if the amount exceeds 10 moles, the materials to be crushed will tend to agglomerate in the crushing mill.

Both methods are unfavorable because the recovery rate of the co-milled product is significantly reduced. Furthermore, even if the ratio of aluminum atoms in the aluminum trihalide to the silicon atoms in the silicon-based compound is less than 0.25 or more than 4,
This is undesirable because not only the polymerization activity of the catalyst system decreases, but also the bulk density of the resulting polymer decreases.
1(5) Co-pulverization method The above-mentioned method of co-pulverization of aluminum trihalide, silicon-based compound, and magnesium alcoholade can be carried out using a ball mill, a vibrating ball mill, or an impact type, which are commonly used in the production of this type of solid catalyst component. Conventional methods using grinders such as grinders and colloid mills may be applied. The co-pulverization may be carried out at room temperature, but if the heat generation is large, it may be cooled. Note that pulverization cannot be performed in an atmosphere of dry inert gas (for example, nitrogen or argon). The time required for co-pulverization cannot be determined unconditionally depending on the type and capacity of the pulverizer used, as well as the amount, type, and proportion of the materials to be pulverized, but it is important to ensure that the particle size and particle size distribution of the co-pulverized products are uniform. You just need to choose the grinding time to the extent that it will work. Therefore, even if co-pulverization is carried out for 20 hours or more, although it is generally 10 minutes or more, it is not expected that the effect will further improve, and the yield of the co-pulverization product may actually decrease. The co-milled product thus obtained is a complex containing aluminium, silicon and magnesium. The average particle size of the co-pulverized product thus obtained is usually 50 to 200 microns, and the specific surface area is 20 to 20 microns.
0 m'/g.

(2) Production of solid catalyst component The solid catalyst component of the present invention can be obtained by bringing the co-pulverized product obtained as described above into contact with a titanium-based compound in a liquid phase. In this case, it may be carried out in the presence of a hydrocarbon solvent, or if the titanium compound is liquid, it may be carried out without a solvent.

(1) Titanium compound The titanium compound used to produce the solid catalyst component of the present invention is a tetravalent titanium compound having at least one halogen atom, and its general formula is the following formula [Formula M]
This is shown in .

TiX'n(OR7)m (NR8R9)6 (OCO
In the Rlo)p (V)M formula, Xo is a chlorine atom, a bromine atom, or an iodine atom, and R7, R8, R9, and R10 are aliphatic, alicyclic, or aromatic carbon atoms having at most 12 carbon atoms. is a hydrogen group, n is a number from 1 to 4, In%11 and p are a number from 0 to 3, nl-
m+n+p is 4.

Typical examples of titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, dimethoxytitanium dichloride, trimethoxytitanium chloride, ethoxytitanium trichloride, jetoxytitanium trichloride, and triethoxytitanium. Titanium chloride, propoxytitanium trichloride, butoxytitanium trichloride, dimethylaminotitanium trichloride, bis(dimethylamino)titanium dichloride, diethylaminotitanium trichloride, titanium propionate trichloride and titanium benzoate trichloride. Among them, in the M formula, m, IJ and p are O, R7 is an alkyl group having at most 6 carbon atoms, and n is 3 or m is 0 (i.e. n is 4) are preferred, particularly titanium tetrachloride, metquin titanium trichloride, ethoxytitanium trichloride and butoxytitanium trichloride.

(2) Hydrocarbon solvent As mentioned above, in producing the solid catalyst component,
Although it does not necessarily have to be carried out in the presence of a hydrocarbon solvent, when carried out in the presence of a hydrocarbon solvent, the hydrocarbon solvent used is preferably one that is liquid at 0°C to 140°C. Representative examples include aliphatic hydrocarbons (e.g., isobutane, n-pentane, n-hexane, n-
hebutane, paraffin), alicyclic hydrocarbons (e.g.
cyclohexane, methylcyclohexane, dimethylcyclohexane) and aromatic hydrocarbons (eg benzene, toluene, xylene).

(3) Contact ratio The amount of titanium atoms on the co-pulverized product is generally 0.
Appropriate conditions may be selected such that a weight ratio of 5 to 10% is supported. Therefore, the ratio of the titanium compound to one atom of magnesium in the co-pulverized product is 0.5 to 50 moles, preferably 0.5 to 40 moles, and particularly preferably 1.0 to 20 moles.

(4) Contact ratio In producing the solid catalyst component of the present invention, the contact temperature is usually room temperature to 150°C, and preferably room temperature to 130°C. If the contact occurs below room temperature, the contact is insufficient. On the other hand, if the temperature is 150°C or higher, a satisfactory solid catalyst component cannot be obtained.

Further, the contact time is generally 10 minutes to 5 hours, but it is particularly desirable from the viewpoint of polymerization activity that the contact time is 10 minutes to 3 hours. If the contact time is 10 minutes or less, the contact is insufficient. On the other hand, even if the contact is carried out for 5 hours or more, the contact may not progress to completion, and the solid catalyst component obtained may be deactivated.

To carry out this contacting in the presence of said hydrocarbon solvent,
Depending on the solubility of the titanium-based compound, the amount of hydrocarbon solvent is at most 10 parts by weight per 1 part by weight of the co-milled product.

(5) Purification The contact product obtained in the above manner contains unreacted titanium compounds and the like in addition to the solid catalyst component.

The solid catalyst component of the present invention is obtained by purifying this contact product. To carry out this purification, the supernatant can be decanted or filtered using the hydrocarbon solvent used during contacting or another hydrocarbon solvent (especially preferably one with a relatively low boiling point). It is desirable to repeat the washing until the presence of no-rogen is no longer recognized in the washing liquid.The washing may be carried out using the hydrocarbon solvent mentioned above, and the obtained solid catalyst component may be washed. It is also possible to feed the slurry (substantially free of unreacted titanium compounds) to the polymerization vessel described below.In addition, after removing the hydrocarbon solvent used for washing under reduced pressure, the solid 1. (c) Organoaluminum compound The catalyst system used in the present invention is obtained from the solid catalyst component and organoaluminum compound obtained as described above.

The general formula of the organoaluminum compound used in the present invention is represented by the following formula [(VD formula and CVID formula)].

1'-e R” R” R” (VDR”R
"M-0-MR" R17 (VIDCVD style, R
`` , R12k j hiR'' C The same 't' may also be different, and is an aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms, ), a rogene atom or a hydrogen atom, At least one of them is the hydrocarbon group, and if it contains a halogen atom, there is only one halogen atom.

i ft (VID formula, R14, R15, R
16oxo: R17 is the above hydrocarbon group.

Among the organoaluminum compounds represented by the formula (■1),
Typical examples include trialkylaluminum such as triethylaluminum, tripropylaluminum, tributylaluminium, trihexylaluminum and trioctylaluminum, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum, lamb hydride, and diethylaluminum chloride. Examples include dialkyl aluminum hydride.

Further, among the organoaluminum compounds represented by the formula (2), representative examples include alkylalumones such as tetraethyldialumoxane and tetrabutyldialumoxane. Among these organoaluminum compounds, trialkylaluminums are preferred, and especially trialkylaluminums in which the alkyl group has at most 6 carbon atoms (for example, triethylaluminum,
Triisobutylaluminum) is preferred.

In obtaining the catalyst system used in the present invention, aluminum halide, silicon-based compound and magnesium alcoholate used to produce the co-milled product, co-milled used to produce the solid catalyst component The product, the titanium compound, the organoaluminum compound, and the solid catalyst component may each be used alone or in combination of two or more.

D Polymerization
11 In carrying out the present invention, the solid catalyst component and the organoaluminum compound not obtained as described above may be introduced into the polymerization container separately, but they may also be mixed in advance. It may be used after being diluted with a solvent in advance.

(1) Amount of solid catalyst component and organoaluminum compound used When carrying out the present invention, there is no restriction on the amount of the solid catalyst component and organoaluminum compound obtained as described above, but 1 - 1 g of solid catalyst component and 0.1 g of solid catalyst component per 11 of solvent
The proportion of the organoaluminum compound used is preferably 10 mm. In addition, the amount of organoaluminum compounds used is
For each atomic equivalent of titanium metal contained in the solid catalyst component,
Generally it is in the range of 1-1000 moles.

(2) Comonomer In carrying out the present invention, only ethylene may be homopolymerized, but ethylene and comonomer may be copolymerized. The α-olefin used as a comonomer is an olefin having at most 12 carbon atoms, and representative examples include propylene, butene-1, pentene-1,3-methylpentene-1, and hexene-1,4-methylpentene-1.
, heftene-1, octene-11 nonene-1, decene-1
1 and dodecene-1. In addition, diolefins are hydrocarbons containing two double bonds, such as butadiene, 1,4-pentadiene, I,5-hexadiene, and 3,3-dimethyl-1,5-hexadiene. Chained or branched diolefins containing terminal double bonds, 1,4-hexadiene and 6-methyl-1
, 5-hebutadiene, as well as bicyclo(2,2,1
)-Hebden-1 (norbornene) derivatives are mentioned.

The proportion of the comonomer in the ethylene-based polymer that cannot be obtained is α-olefin! In the case of 1'1, the molar ratio is usually at most 15 molar, and preferably 10 molar or less. Further, in the case of a diolefin alone, the molar ratio is generally 20 or less. Furthermore, in the case of a terpolymer of ethylene, an α-olefin, and a diolefin, although it varies depending on the purpose of use of the obtained polymer, it is generally preferred that the molar ratio is 8 or less for α-olefins and 10 or less for diolefins.

(3) Other polymerization conditions Polymerization can also be carried out by dissolving ethylene alone or ethylene, an α-olefin and/or a diolefin in an inert organic solvent. At this time, the inert organic solvent may be easily volatile hydrocarbons (e.g. propane, n
-butane, isobutane, n-pentane, isopentane)
is convenient for recovering or removing the inert organic solvent after polymerization. Furthermore, it can also be carried out by a so-called solution method, slurry method, gas phase method, or the like.

Furthermore, if necessary, a chain transfer agent (generally hydrogen) may be present.

The polymerization temperature is generally from -10°C to +300°C, and practically from room temperature to 300°C.

In addition, the type of polymerization solvent and the ratio of ethylene to olefin or ethylene to olefin are
The production of ethylene monopolymers, ethylene copolymers) is known.

Furthermore, the configuration of the polymerization reactor, polymerization control method, post-treatment method, the proportion of monomer (ethylene or ethylene and comonomer) and organoaluminum to the inert organic solvent used in the polymerization, the proportion of the inert organic solvent Regarding the type and post-treatment method after completion of polymerization, there are no limitations inherent to this catalyst system, and all known methods can be applied.

[VD Examples and Comparative Examples The present invention will now be explained in more detail with reference to Examples.

In the Examples and Comparative Examples, the melt index (hereinafter referred to as rM, 1.J) was determined according to JISK-6760 at a temperature of 190°C and a load of 2.16.
Measured under the following conditions. Density was measured according to JISK-6760. The soluble content was determined by extracting the obtained polymer with n=hexane for 6 hours. In addition, the high load melt index has a load of 21.6 according to JISK-6760.
Measurements were made under conditions of Kg and temperature of 190°C. Furthermore, the sieving of the polymer was measured according to JIS Z-8801, and the particle size (particle size) at which the integral value of the weight fraction of each division was 50 was defined as the average particle size.

In each Example and Comparative Example, each compound used in the production and polymerization of the co-pulverized product and solid catalyst component (for example, magnesium alcoholade, silicon-based compound, titanium-based compound, organoaluminum compound), co-pulverized product All co-milled products and solid catalyst components are substantially free of moisture, and the production and polymerization of each co-milled product and solid catalyst component is substantially moisture-free and conducted under a nitrogen atmosphere. did.

Example 1 [Production of co-pulverized product (1)] In a pot (grinding container) with an internal volume of 11 containing about 700 porcelain balls with a diameter of 10 mm, commercially available magnenium ethylate was placed in a nitrogen atmosphere. (Average particle size 860 microns) 20
．． 9 (17.5 mmol), 1.66 g (12.5 mmol) of granular aluminum trichloride and 2.72.9 (10 mmol) of diphenylshedkin silane.

These were co-pulverized for 3 hours using a vibrating ball mill under conditions of an amplitude of 6 mm and a vibration frequency of 301-1 z/min. After co-milling, the contents were separated from the porcelain balls under a nitrogen atmosphere.

When the co-pulverized product [hereinafter referred to as "co-pulverized product (1)"] was weighed, the recovery rate was 85:3 based on the amount charged.
It was q6.

[Production to 0 Solid Catalyst Component] 5 g of the co-pulverized product (1) obtained as described above and 20 ml of n-hebutane were added to a 200 ml three-necked flask. 10.4me at room temperature with stirring
of titanium tetrachloride was added dropwise, the reaction system was heated to 90°C,
Stirring was continued for 90 minutes. Then, after cooling the reaction system,
The supernatant was removed, and n-hexane was added. This operation was repeated three times. The obtained pale yellow solid was dried at 50° C. under reduced pressure for 6 hours. As a result, 7.2 g of solid material (hereinafter referred to as "solid catalyst component") was obtained. Elemental analysis of this solid catalyst component revealed that the content of magnesium atoms was 112% by weight, and the content of aluminum atoms was 0.7% by weight.
% by weight, the content of silicon atoms was 0.2% by weight, and the content of chlorine atoms was 54% by weight.

[Copolymerization of 0 ethylene and butene-1] A solution of triisobutylaluminum in n-heptane (concentration: 0.
1.4 ml of solid catalyst component (A) and 365 g of isobutane (as a solvent) were added, and the polymerization system was sealed. The polymerization system is 8
The temperature was raised to 5℃, and the hydrogen partial pressure was 0.32 K9/crA.
Add hydrogen so that the ethylene partial pressure becomes 50K.
Ethylene was continuously fed to give q/crA, and 4.6 g (total) of butene-1 (as comonomer) was sequentially fed.

After copolymerizing for 30 minutes, the solvent, hydrogen, unreacted monomers, etc. were released from the polymerization system through the relief line. After drying the contents (hereinafter referred to as "post-processing"), 1
76 g of white powdery polymer was obtained. That is, the polymerization activity of this catalyst is 6,980 g/g-solid catalyst component (
2)・Time・Ethylene partial pressure (Kg/Ca).

The bulk density of this copolymer powder is 0.32jj/crA
The HLMI was 0.23 g/10 minutes.

In addition, the true density of this copolymer is 0.9293 jj/c
It was rl.

Comparative Example 1 [8. Production of solid catalyst component 0] 0.583.9% of aluminum chloride in a 200-ml flask
(4.37 mmol) and 18 kol of toluene were added. Then diphenylshedkinsilane 0.952. !
i' (3.5 mmol) and at a temperature of 60 °C for 30
The reaction was carried out with stirring for a minute. 2.0 g (17.5 mmol) of magnesium ethylate was added to this reaction system, and the reaction was carried out for 1.5 hours with stirring. After the reaction, the reaction system was cooled, the supernatant liquid was taken out, 18-n-butane was added, and the mixture was sufficiently stirred and left to stand. This washing was performed three times.

5 md of tita tetrachloride was stirred into the solid product obtained.
1. .

The mixture was added with stirring, and the reaction was carried out at a temperature of 90°C for 15 hours with stirring. Then, washing and drying were carried out in the same manner as in Example 1 (2). As a result, 2.8g of solid matter [
Hereinafter referred to as "solid catalyst component 0"] was obtained.

[Copolymerization of ethylene and butene-1] Instead of the solid catalyst component used in O of Example 1, the solid catalyst component obtained as above (13'ff: 12.3
The copolymerization of ethylene and butene-1 and the post-treatment of the obtained copolymer were carried out in exactly the same manner as O in Example 1, except that the same procedure was used as in Example 1. As a result, the polymerization activity of this catalyst was 3.2
oo&/g - Solid catalyst component 0・Time・Ethylene pressure (Kq
/cni). HLM of the obtained copolymer
I is 0.28g/10min and density is 0.9290
g/crIl.

The respective powdered copolymers obtained in Example 1 and Comparative Example IK were sieved. The particle size distribution of the powder and the HLMI for each particle size were measured.

The results are shown in Table 1.

Table 1) 9/lo min Also, Example 1 (At and Comparative Example 10) at each particle size
The particle size distribution of the powdered copolymer obtained by the method is shown in FIG. In Figure 1, the vertical axis is the weight fraction,
The horizontal axis is the particle size (microns).

From Table 1 and FIG. 1, it can be seen that, in contrast to the copolymer obtained in Comparative Example 1, the copolymer obtained in Example IK has a narrower distribution of HLMI for each particle size and is only very uniform. It is clear that the particle size distribution is narrow.

Example 2% Comparative Example 2 The solid catalyst component IA) prepared in Example 1, 0.212,! ? ,6 MiI
J moles of triisobutylaluminum were added and isobutane 601 was charged as a solvent. The temperature of the polymerization system was raised to 80°C, 505.9 hexene-l (as a comonomer) was added, hydrogen was charged so that the hydrogen partial pressure was 05 Ky/cr/l, and the ethylene partial pressure was 5 Ethylene was continuously supplied so as to maintain 9/crl at .0, and copolymerization of ethylene and hexene-1 was carried out for about 1 hour. After the copolymerization was completed, post-treatment was carried out in the same manner as O in Example 1. As a result, 7.42 kg of powdered polymer [
A sample (hereinafter referred to as "sample A") was obtained. The n-hexane extraction valve of this sample A was 0.35 inches.

When manufacturing the above sample A, change the hydrogen partial pressure to "OK"
Copolymerization of ethylene and hexene-1 was carried out for 1.2 hours in the same manner as in the production of sample A, except that the y/cds polymerization temperature was changed to 90° C. and the amount of hexene-1 used was changed to 300 g. After the copolymerization was completed, fluidized drying was performed in the same manner. As a result, 6.30 kg of copolymer (hereinafter referred to as "Sample B") was obtained.
) was obtained. The n-hexane extraction valve of this sample B was 4.1q6.

As described above, 50 parts by weight of sample A and sample B, 0.1 part by weight of 2.6-di-tert-butyl-p-cresol (as a stabilizer) and 0.2 part by weight of calcium stearate were prepared. Tumbler in advance
Triblend was performed for 30 minutes using The resulting mixture was melt-kneaded using an extruder with a full-flight screw (diameter: 40) at a resin temperature of 200° C. to produce pellets. This process was repeated twice (
Example 2).

The reaction with ethylene was carried out under exactly the same conditions as in the production of Sample A, except that 0 of the solid catalyst components obtained in Comparative Example 1-8 was used instead of the solid catalyst component used in the production of Sample A. Copolymerization with xeno=1 was carried out. After the copolymerization was completed, fluidized drying was performed in the same manner as Sample 8 to obtain a copolymer (hereinafter referred to as "Sample C").

In addition, instead of the solid catalyst component ■ used in producing sample B, the solid catalyst component ■ obtained in Comparative Example 1-8 was used.
Copolymerization of ethylene and hexane-1 was carried out under exactly the same conditions as in the production of sample B, except that ethylene and hexane-1 were used.

After the copolymerization was completed, post-treatment was carried out in the same manner as in Example 1.
A copolymer (hereinafter referred to as "Sample D") was obtained.

The physical properties of Sample C and Sample D are shown in Table 2 as described above.

1), 9Zlo minute 2) Micron Sample A and Sample B used in Example 2
Instead, tri-blending and melt-kneading (twice) were performed under the same conditions and method as in Example 2, except that the same amounts of Sample C and Sample D were used to produce pellets (Comparative Example 2).

Each of the pellets obtained in Example 2 and Comparative Example 2 was placed in a 7L/- cylinder equipped with a screw having a diameter of 50 mm.
using a thin film machine (die diameter 70 mm).

A film with a thickness of 20 microns and a fold diameter of 400 scale was produced. The film impact, high-speed moldability, and IILMI of the resulting film were measured. The results are shown in Table 3.

1) Kg・tyn7' From the above results, when comparing Example 2 and Comparative Example 2, the particle size of the sample, high-speed formability during film production with an extruder, and the film impact and fish eyes of the obtained film were determined. It is clear that there is a big difference in the

Examples 3 to 6 [(f) Production of each co-pulverized product] Instead of the diphenylshedkin silane used as the silicon-based compound in (f) of Example 1, tetraeixisilane [hereinafter referred to as "compound (a)"] was used as the silicon-based compound. ] hexamethylcycloxane [hereinafter referred to as "compound (b)"] vinyltryptoxinlan [hereinafter referred to as "compound (C)"] and 3(glycidoxy)propyltrimethoxysilane [hereinafter referred to as "compound (d)"] Each co-milled product was prepared under all the same conditions and methods as in Example 1, except that 10 mmol of each of the co-milled products were used.

[■ Manufacture of each solid catalyst component]

5 g of each co-pulverized product obtained as above
into 200ml flasks, each with 20ml of n.
- hebutane and 12.5-0 tikutitan tetrachloride were obtained.

The temperature of each reaction system was raised to 90°C, and contact was carried out for 1.5 hours while stirring at this temperature. Subsequently, the solvent containing each product was washed repeatedly in the same manner as in Example 1 for purification. The same rod as in Example 1 was dried under reduced pressure to obtain each solid catalyst component (yields and abbreviations are shown in Table 4).

[Copolymerization of ethylene and butene-1] 1. Into each autoclave of 1.21, predetermined amounts of the solid catalyst components 0 to [F] obtained in the above-mentioned step 0 were added (the amounts used are shown in Table 5).
The thrust was 11 times under nitrogen flow.
0.7 mmol of triisobutylaluminum was injected and 346 g of isobutane (including solvent) was injected. Next, after raising the temperature of each polymerization system to 85°C, 5.0 g of butene-1 was injected at this temperature, hydrogen was added so that the hydrogen partial pressure became 0.40 KV/cJ, and the ethylene partial pressure was further increased. Ethylene was pressurized so that the pressure was 5 Kg/cJ (total pressure was 19.4 Kq/cd). Copolymerization of ethylene and butene-1 was carried out for 30 minutes while supplying a partial pressure of ethylene to maintain this total pressure. After each copolymerization was completed, post-treatment was carried out in the same manner as in Example 1. Table 5 shows the yield of the copolymer obtained and the polymerization activity obtained by division. Table 5 shows the average particle diameter (D5o) and bulk density determined by sieving the powdered copolymer.

Furthermore, the true density of each copolymer, M, 1. , and M determined by the total q, 1. The HLMIO ratio and cyclohexane solubles (boiling point extraction, 5 hours) are shown in Table 6.

From Tables 5 and 6, it can be seen that the copolymers obtained according to the present invention not only have a very uniform particle size distribution, but also have a low boiling cyclohexane soluble content (
It is also clear that the amount of very low molecular weight polymers is low.

Example 7 25.0 ■ of the solid catalyst component (■) prepared in (■) of Example 1 was placed in an autoclave manufactured by Nos. 1 and 21 which was sufficiently purged with nitrogen.
, 14 ml of n-hebutane solution of triisobutylaluminum (concentration 0.5 mol/l) and 365I isobutane were charged, and the polymerization system was sealed. The temperature of the polymerization system was raised to 85°C, and the hydrogen partial pressure was 2. Hydrogen was added until it reached OKq/ta, ethylene was supplied so that the ethylene partial pressure was maintained at 50Kg/crl, and 10g of butadiene was successively supplied while copolymerization of ethylene and butadiene was carried out for three times.
This was done for 0 minutes. After the copolymerization was completed, post-treatment was carried out in the same manner as in Example 1.

As a result, 158 g of a white powdery polymer was obtained.

That is, the polymerization activity is 2,530 g/jj-solid catalyst component (t)/time/ethylene pressure (Kg/ca).

M of this copolymer, 1. was 1.23 g/l o min. In addition, the unsaturated group content is 7 per 1000 carbon atoms.
Most of them were of internal transformer type.

[Brief explanation of drawings]

Figure 11 is a diagram showing the particle size distribution of the powder of each copolymer of ethylene and butene-1 obtained by Example 18 and Comparative Example 1 (Bl). In this figure, the vertical axis is the weight fraction. It is the integral value (a), and the horizontal axis is the particle size of the polymer (microns).
It is. Patent applicant Sei Kikuchi, patent attorney representing Showa Denko Co., Ltd.

Claims (1)

[Claims] (A) (1) (a) aluminum trihalide, (b)
An organic compound having a Si-0 bond and (c) a co-pulverized product obtained by co-pulverizing a magnesium alcoholade, and (2) a tetravalent titanium compound having at least one halogen atom are brought into contact in a liquid phase. Homopolymerization of ethylene in the presence of a solid catalyst component obtained by the method and a catalyst system obtained from an organoaluminum compound is an improved method characterized in that ethylene is copolymerized with α-olefins and/or diolefins. A method for producing an ethylene polymer.