JPS63234004A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a highly stereoregular polymer of high molecular weight in high yield, by (co)polymerization of olefin(s) in the presence of a catalyst prepared using, as the external electron donor, a combination of specific ether compound and carboxylic ester, etc. CONSTITUTION:The objective polymer can be obtained by (co)polymerization of olefin(s) in the presence of a catalyst prepared from (A) a highly active catalytic component comprising (i) Mg component (e.g. magnesium halide), (ii) Ti component (e.g. TiCl4), (iii) halogen and (iv) an electron donor (e.g., dimethyl phthalate), (B) an organoaluminum compound (e.g., trimethylaluminum) and (C) an external electron donor, i.e., a combination of C1: an ether compound of formula I (R<1>-R<4> are each 1-7C aliphatic hydrocarbon; where R<3> may be H) or formula II (R<5> is divalent group similar to R<3>; R<6> is the same as R<4>) (e.g., tert-butylmethyl ether) and C2: at least one kind of compound selected from carboxylic esters, organosilicon compounds and azo compounds.

Description

Detailed Description of the Invention r Industrial Application Field] This invention is applicable to polypropylene, polybutene-1, etc.
Regarding the manufacturing method of olefin polymers such as olefin polymers, to be more specific, they have good stereoregularity.

The present invention also relates to a method for producing an olefin polymer that can produce a high molecular weight olefin polymer in high yield.

[Prior art and its problems] Conventionally, high-temperature catalysts are prepared by combining a solid catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components with an external electron donor such as an organoaluminum compound and an ester or an organosilicon compound. Using an active catalyst,
Methods for producing olefin polymers are known (Japanese Patent Publication No. 5B-311767, Japanese Patent Application Laid-open No. 55-10430).
No. 3, JP-A-58-115301, JP-A-57-83
No. 312, JP-A-59-8205, etc.).

However, in most of these methods, not only has it not been possible to completely omit the washing step and deashing step for removing atactic polymers, but also the catalytic activity is not satisfactory, and the physical properties of the resulting polymers are also poor. Further improvements in regularity, molecular weight, etc. have been desired.

On the other hand, a method using a phosphite as an internal or external electron donor in a catalyst (Japanese Patent Application Laid-Open No. 55-104303
JP-A-58-138711) is also known, but this method also had insufficient catalyst activity, stereoregularity of the polymer, etc.

In addition, methods using ethers containing aromatic hydrocarbon groups as external electron donors (Japanese Patent Application Laid-Open No. 61-78804, Japanese Patent Application Laid-Open No. 81-145208) are known, but the persistence of activity is low. It has the disadvantage that it is insufficient and the cost of the catalyst is high, which is industrially disadvantageous.

This invention has been made based on the above circumstances.

In other words, the purpose of this invention is to provide a method for efficiently producing olefin polymers with high stereoregularity in high yield and in a stable process by using a catalyst with high activity and excellent long-lasting activity. The goal is to provide the following.

[Means for solving the above problems] The outline of the present invention for solving the above problems is as follows: a highly active catalyst component (A) containing magnesium, titanium, halogen, and an electron donor as essential components; In the method for producing an olefin polymer in the presence of a catalyst obtained from an aluminum compound (B) and an external electron donor (C), as the external electron donor (C), the following formula [1alH -1, R1-C -0-R4 ■R3] (However, in the formula [1a], 1lzl, li2 and R4 represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and R3 is a hydrogen atom or Carbon number 1-7
represents a saturated or unsaturated aliphatic hydrocarbon group) or the following formula [1b]; (wherein R5 represents a divalent aliphatic hydrocarbon group having 1 to 7 carbon atoms, R5 represents 1 formula [1a] R6 represents a group similar to R4 in formula [1a],
) and at least one compound (C2) selected from the group consisting of carboxylic acid esters, organosilicon compounds, and azo compounds to carry out homopolymerization or copolymerization of olefins. This is a method for producing an olefin polymer characterized by the following.

The catalyst used in the method of this invention is a solid catalyst component (A) containing magnesium, titanium, halogen and an electron donor as essential components, and an organoaluminum compound (B).
, a specific ether compound (CI) as an external electron donor (CC), and a specific compound (C2).

It can be obtained as follows.

Regarding one solid catalyst component (Todoroki) - The solid catalyst component (^) is a magnesium compound (Todoroki).
), halogenated titanium compound (A-2), and electron da body (
A-3). Examples of the magnesium compound (A-1) include magnesium cybaride, magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, Examples include reactants of alkylmagnesiums, alkylmagnesium halides, organomagnesium compounds and electron donors, halosilanes, alkoxysilanes, silanols, and aluminum compounds.

Among these various magnesium compounds, magnesium halide and alkoxymagnesium.

Alkylmagnesium and alkylmagnesium halides are preferred.

Specifically, the titanium compound (A-2), which is one of the raw materials for the solid catalyst component (A), is as follows.

Tetrahalogenated titanium such as TiCls, TiBra, TiI4; T'i(OCH3)C
fL3, T i (OC2Hs) CfL3, (n-
CaH90) Ti CjLa, Ti (OC2I
s ) Trihalogenated alkoxytitanium such as B r3 * T s (OCHi)2 C12,Ti (O
C2H5)2 C z, (n-C4Hs O)2 Ti
dihalogenated alkoxy titanium such as c, Ti (QCs H7) 2CJL2; Ti (OCH3)
3 C sentence, Ti (OC2HshCl, (n-C
4H90)3 T i CfL, T i (OCH
3) Monohalogenated trialkoxytitanium such as 3Br, Ti (OCH3)4, Ti (OC2Hs)
Examples include tetraflukoxytitanium such as a, Ti(n-C4H90)s, and the like.

These may be used alone or in combination of two or more.

Among these, it is preferable to use high halogen content,
It is particularly preferable to use titanium tetrachloride.

Electron donor (＾-
As 3), organic compounds containing oxygen, nitrogen, phosphorus or sulfur can be used.

Examples of the electron donor (3) include esters, thioesters, amines, 7 amides, ketones,
Examples include nitriles, phosphines, ethers, thioethers, esters, thioesters, acid anhydrides, acid halides, acid amides, aldehydes, and organic acids.

More specifically, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, di Propyl terephthalate, diimbutyl terephthalate, methyl ethyl terephthalate, methylpropyl terephthalate, methylimbutyl terephthalate, ethylpropyl terephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl inphthalate, diethyl isophthalate,
Diethyl isophthalate, diisobutyl isophthalate.

Aromatic dicarboxylic acid diesters such as methyl ethyl isophthalate, methyl propyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and propyl isobutyl isophthalate, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, acetic acid propyl, octyl acetate,
Cyclohexyl acetate, ethyl propionate, ethyl acetate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, butyl benzoate , propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl anisate, ethyl ethoxybenzoate,
Monoesters such as ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, esters having 2 to 18 carbon atoms such as γ-butyrolactone, δ-valerotectone, coumarin, phthalide, ethylene carbonate, etc. 5I
f; Organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; succinic anhydride, benzoic anhydride,
Acid anhydrides such as p-toluic anhydride; 3 carbon atoms such as acetone, methyl ethyl ketone, methyl imbutyl ketone, acetraenone, hensifhenone, benzoquinone, etc.
~15 ketones: carbon a2-15 such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthylaldehyde, etc.
Aldehydes; C2-15 acid halides such as acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride; methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether , ethers having 2 to 20 carbon atoms such as ethylene glycol butyl ether; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; nitributylamine, N,N'-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline , amines such as tetramethylethylenediamine; and nitriles such as acetonitrile, benzonitrile, and tolnitrile.

Among these, preferred are esters, ethers, ketones, acid anhydrides, and the like. In particular, diesters of aromatic dicarboxylic acids such as diisobutyl phthalate or alkyl esters of aromatic carboxylic acids, such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid having a carbon number of 1 ~
Preferred are alkyl esters of No. 4 and the like. Note that aromatic dicarboxylic acid diesters are particularly preferred because they can improve the catalytic activity and activity persistence, and can also improve the stereoregularity of the resulting polymer.

Regarding the preparation of the m-solid catalyst component (A), the m-solid catalyst component (A) is prepared according to Japanese Patent Application Laid-Open No. 53-43094 and Japanese Patent Application Laid-open No. 55-
135102, JP-A-55-135103, JP-A-58=811. It can be prepared according to the methods described in JP-A-58-11908 and JP-A-56-18808.

Several examples of the five methods for producing the solid catalyst component (A) will be briefly described below.

(1) A magnesium compound (1) or a complex compound of a magnesium compound and an electron donor (^-3).

'if in the presence or absence of a child donor, grinding aid, etc.
The titanium compound (A-2) is reacted with the titanium compound (A-2) which forms a liquid phase under the reaction conditions without being pulverized or pulverized. However, the electron donor is used at least once.

(2) Magnesium compound without reducing ability (A-
The liquid material of 1) and the liquid titanium compound (A-2) are reacted in the presence of an electron donor (A-3) to precipitate a solid titanium complex.

(3) React the titanium compound (A-2) with the material obtained in (1) or (2).

(4) React the electron donor (A-3) and the titanium compound (A-2) with the material obtained in (1) or (2).

(5) A magnesium compound (A-1) or a complex compound of a magnesium compound (A-1) and an electron donor (A-3) in the presence or absence of an electron donor, a grinding aid, etc. and a titanium compound (A-2), and treated with a halogen or a halogen compound.

However, the above electron donor (A-3) is used at least once.

(8) The compound obtained in (4) above is treated with a halogen or a halogen compound.

Further, for example, JP-A-58-168205, JP-A-57-83309, JP-A-57-19000,
The preparation methods described in JP-A No. 4, JP-A-57-300407, JP-A-58-47003, etc. may also be included as preferred methods for preparing the solid catalyst component (A) in the present invention. can.

Also, oxides of elements belonging to groups ■ to ■ of the periodic table.

For example, oxides such as silicon oxide, magnesium oxide, and aluminum oxide, preferably silicon oxide, or composite oxides containing at least one of the oxides of elements belonging to groups ■ to ■ of the periodic table, such as silica-alumina, and magnesium oxide. A solid catalyst component is produced by contacting a solid material containing a compound, an electron donor, and a titanium halide in a solvent at a temperature of θ to 200°C, preferably 10 to 150°C for 2 minutes to 24 hours. (^) can also be prepared (wJ* method described in Japanese Patent Application No. 131-43870).

In preparing the solid catalyst component (A), an organic solvent inert to the magnesium compound, electron donor and titanium compound, such as an aliphatic hydrocarbon such as hexane or heptane, or an aromatic solvent such as benzene or toluene, is used as a solvent. or halogenated hydrocarbons such as mono- and poly/\halogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having carbons a1 to a12.

m-Composition of solid catalyst component (A)-1 Regarding the composition of the solid catalyst component (A), the magnesium/titanium atomic ratio is 2 to 100. Halogen/titanium atomic ratio is 5-20G, electron donor/titanium (molar ratio) is 0.
1 N10.

About the organoaluminum compound (B) - The organoaluminum compound (B) is not particularly limited and has the general formula % [where R3 is an alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms] , Ma is a real number from 1 to 3, and X represents a halogen atom such as chlorine or bromine.
] is widely used.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride,
Dialkyl aluminum monohalides such as diisobutyl aluminum monochloride and dioctyl aluminum monochloride, and alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride are suitable for IIf, and mixtures thereof are also suitable.

Regarding the external electron donor (C) - One of the important points of this invention is the external electron donor (C).
), the ether compound (C) substituted by the formula [1a] or the formula [1b] is used.
Specific examples of each include, for example, a methyl group, an ethyl group, and an n-propyl group.

Isopropyl group, n-butyl group, isobutyl group.

Alkyl groups such as l-methylpropyl group, t-butyl group, pentyl group, hexyl group, heptyl group; alkenyl groups such as vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, etc. 173
In addition to these alkyl groups and alkenyl groups, a hydrogen atom can be mentioned.

Among these, lower alkyl groups such as methyl group and ethyl group, particularly methyl group, are preferable as ill and R2, and as R3, hydrogen atom, methyl group, ethyl group, n-propyl group, n- Butyl, n-pentyl or n-hexyl, especially methyl or ethyl, are preferred.

R4 is a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, pentyl group, l-methylbutyl 2&, hexyl group, particularly methyl group and ethyl group are preferred.

Note that R1, R2, R3 and R4 may be the same type of group or different types of groups.

Specific examples of the divalent carbonized wood Jl:Ali of carbons Al to 7 of R5 in the formula [1b] include methylene group, ethylidene group, bripylidene group, fullkylidene group such as butylidene group, tetramethylene group, pentamethylene group, etc. Examples include fullylene groups such as methylene group and heptamethylene group, and fullylene groups such as 1-penten-1,5-diyl.

Further, as R6 in the above formula [1b], the same groups as the above R3 can be mentioned, and as 71F, the above R
Groups similar to 4 can be mentioned.

The ether compound represented by the formula [1b] or the formula [1b] can be used alone or in combination of two or more as the component (C1).

Specific examples of the ether compound represented by the formula [1al include isopropyl methyl ether, isopropylethyl ether, isopropyl n-propyl ether, diisopropyl ether, isopropyl n-butyl ether, isopropyl-1-methylpropyl ether, and isopropyl pentyl. ether, isopropyl hexyl ether, isopropyl hexyl ether, tar
t-butyl methyl ether, tert-butyl ethyl ether, tart-butyl-n-propyl ether, t
ert-butyl isopropyl ether, tert-butyl n-butyl ether, tert-butyl-! -Methylpropyl ether, tart-butyl-2-methylpropyl ether, di-tart-butyl ether.

tert-butyl-n-pentyl ether, tart
-butyl-1-methylbutyl ether, tart-butyl-2-methylbutyl ether, tart-butyl-3
-methyl butyl ether, tart-butyl-tert
-amyl ether, tert-butyl neopentyl ether, tart-butyl-1-ethylpropyl ether, tert-butylhexyl ether, tert
-butyl isohexyl ether, tert-butyl neohexyl ether, tert-butyl heptyl ether, tert-amyl methyl ether, tert-amyl ethyl ether, tart-7 mil-n-propyl ether, tert-7 mil-impropyl ether,
tert-7mil-n-butyl ether, tert
-7mil-1-methylpropyl ether, tart-
7mil-2-methylpropyl ether, tart-amyl-n-pentyl ether, tart-amyl-!
-methyl butyl ether, tert-7mil-2-methylbutyl ether, tert-7mil-3-methylbutyl ether, tert-7mil-1-ethylpropyl ether, tart-7mil neopentyl ether, di-tart-amyl ether, tart-amyl xyl ether, tart-7 mil-inhexyl ether tert-7 mil-butyl ether, l-methylpropyl methyl ether, l-methylpropylethyl ether, l-methylpropylpropyl ether, 1-
Methylpropylpentyl ether, l-methylbutyl methyl ether, l-methylbutyl ethyl ether, 1-
Ethylpropyl methyl ether, l-ethylpropyl ethyl ether, tart-hexyl methyl ether.
tert-hexyl ethyl ether, 1-methylpentyl methyl ether, 1-methylpentyl ethyl ether, tert-heptyl methyl ether, tert-
Hebutyl ethyl ether, 1-methylhexyl methyl ether, 1-methylhexyl ethyl ether, tar
t-octyl methyl ether, tart-octyl ethyl ether, 1-methyl hebutyl methyl ether, l
- Saturated ether compounds such as methylheptyl ethyl ether; isopropyl vinyl ether, isopropyl allyl ether, isopropyl butenyl ether, ter
tert-butyl vinyl ether, tert-butyl allyl ether, tert-butyl crotyl ether
t-butyl butenyl ether, tart-amyl vinyl ether, t@rt-7 methylallyl ether, Le
rt-7 milbutenyl ether, (1-methyl-2-propenyl)methyl ether, (1-methyl-2-propenyl)ethyl ether, (1.

Mention may be made of unsaturated ether compounds such as l-dimethyl-2-propenyl) methyl ether.

Specific examples of the ether compound represented by the formula [1b] include l-methylcyclopentyl methyl ether, l-methylcyclopentyl ethyl ether, l-
Methylcyclohexyl methyl ether, l-methylcyclohexyl ethyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, cyclohexyl methyl ether, lopentyl isopropyl ether, cyclohexyl JL/
- Saturated ether compounds such as tert-ethyl ether, cyclohexyl-tsrt-amyl ether; vinyl methyl ether, vinyl ethyl ether, divinyl ether, vinyl allyl ether.

Vinyl propyl ether, vinyl butyl ether, l-
Propenyl methyl ether, l-methyl-1-propenyl methyl ether, l-propenyl ethyl ether, l
-Methyl-1-propenyl ethyl ether, l-methyl-1-propenyl allyl ether, and other unsaturated ethers.

Among these, saturated aliphatic ethers represented by the formula "], specifically, isopropyl methyl ether, isopropylethyl ether, tart-butyl methyl ether, tert-butyl ethyl ether, tert-butyl-n-propyl ether , tert-butyl-n-butyl ether, tert-amyl methyl ether,
Preferred are tart-7mil ethyl ether, tert-7mil-n-propyl, tert-7mil-n-butyl ether, and especially.

tsrt-butyl methyl ether, tart-butyl ethyl ether, tert-amyl methyl ether,
jerk-7 methyl ethyl ether is preferred.

In the method of this invention, when an ether compound other than the ether compound represented by the above formula [1a] or the above formula [1b] is used alone as the external electron donor (C), the activity of the catalyst is reduced. It is undesirable because it may be insufficient, the persistence of activity may be insufficient, or the stereoregularity of the resulting polymer may be low.

However, the formula [1a
] Or ether compounds other than the ether compound represented by [1b] above, or other electron-donating compounds such as organic phosphorus compounds.

It is also possible to use it in combination with the above (C) 1&min.

Regarding the Compound (C2) - One of the important points of this invention is that, as the external electron donor (C), the ether compound (C2), the carboxylic acid ester (02-1), the organosilicon compound (C2), etc. -2) and one or more compounds (C2) selected from the group consisting of azo compounds (C2-3).

As the carboxylic acid ester (C2-1), for example, mono- or polyvalent esters of saturated or unsaturated aliphatic acids, rubonic acids, alicyclic carboxylic acids, or aromatic carboxylic acids may be used. Can be done. Specific examples include butyl formate, ethyl acetate, butyl acetate, inbutyl isoacetate, propyl piperate, isobutyl piperate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, Diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate,
Diisobutyl adipate, dibutyl sebacate, diimbutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, methyl p-)rulyate, ethyl p-tert-butylbenzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-7toate, ethyl cinnamate, Monomethyl phthalate.

Monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate,
Di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate,
Triethyl trimellidate, tributyl trimellidate, tetramethyl pyromellitate, tetraethyl pyromellitate,
Examples include tetrabutyl pyromellitate.

Examples of the organosilicon compound (C2-2) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra(p-methylphenoxy)silane, tetrabenzyloxysilane, and methyltrisilane. Methoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane , butyltriphenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltriphenoxysilane, methyltriallyloxysilane, dimethyldimethoxysilane, dimethyl Jetoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyljethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxythene, dibutyldiisopropoxysilane, dibutylene dibutoxysilane, dibutyldiphenoxysilane, diynebutyljethoxysilane,
Diisobutyldiisoptoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, diphenyldibutoxysilane, dibenzyljethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane.

Disilane, methylphenyldimethoxysilane.

Examples include lelorophenyldiethoxysilane.

Examples of the azo compound (11:2-3) include aliphatic azo compounds, alicyclic azo compounds, and aromatic azo compounds that are usually used as initiators for radical synthesis. the bond (-N=N-), at least 11, preferably 241 tertiary carbon atoms, a benzene ring,
Azo compounds formed by bonding substituents with steric hindrance such as diarylmethyl can be suitably used, and specific examples thereof include 2,2'-azobis(2-methylpropane), 2,2'-azobis, (2-ethylpropane),
2.2”-azobis(2-methylpentane), 2.2”
-7zobis(2-ethylbutane), α,α'-7zobisisobutyronitonyl, 1,1'-azobis(1-cyclohexanecarbonitrile), 1-tert-butylazo-1-cya)cyclohexane, (1 -phenylmethyl)
-Azodiphenylmethane, 2-phenylazo-2,4-
Dimethyl-4-methoxypentanenitrile and the like can be mentioned.

Composition of hitch component - As for the composition of each component of the catalyst for olefin polymerization, the solid catalyst component (A) is usually as follows.

0.000 per reaction volume 11 in terms of titanium atoms
The amount is 5 to 1 mmojL, and for the organoaluminum compound (B), the aluminum/titanium atomic ratio is 1.
-toooo, preferably 5-50G.

Regarding the external electron donor (C), the molar ratio of the ether compound represented by the formula [1al and the formula (total amount of the ether compound represented by 1bl)/titanium] is usually 0.
．． 1 to 50G, preferably IN100. If this molar ratio is less than 0.1, the sustainability of the catalytic activity will be insufficient or the stereoregularity of the resulting polymer will be insufficient, while if it exceeds 500, the catalytic activity will decrease. Sometimes.

Regarding the fourth component (C2), [the above (C2-1)
j & minute and the above (02-2) component and the above (Ll:2-3)
The total amount of components]/titanium (mole ratio) is usually 1 to 20
0. Preferably it is 5-100. This molar ratio improves the catalyst activity and the stereoregularity of the resulting polymer within this range.

Regarding Itsupopolymerization - The method of the present invention is a method for producing an olefin homopolymer or copolymer in which olefins are homopolymerized or olefins are copolymerized with each other in the presence of the catalyst.

When producing a homopolymer, a single olefin is fed into a polymerization vessel at a temperature of 40 to 90°C and a pressure of 1 to 100 kg/kg.
It is sufficient to polymerize at 2G.

When producing a random copolymer, a plurality of types of olefins may be supplied to a polymerization vessel and copolymerized.

When producing a so-called block copolymer, a first stage polymerization treatment of homopolymerizing olefins is carried out, and then a second stage polymerization treatment is carried out.
As a stage polymerization treatment, the olefin homopolymer obtained in the first stage can be copolymerized with another single olefin or a plurality of types of olefins.

The olefin may be represented by, for example, the general formula: % formula % [wherein R8 represents hydrogen, an alkyl group having 1.3 to 12 carbon atoms, or a cycloalkyl group, and can be represented by 1, specifically ethylene , propylene, butene-1,
Penten-1. Examples include linear monoolefins such as ocf7-1, branched monoolefins such as 4-methyl-pentene-1, and vinylcyclohexene.

The multi-table format may be any of slurry polymerization, gas phase polymerization, bulk polymerization using the liquid monomer itself as a solvent, and the like.

When producing so-called block copolymers! ±.

il and a second polymerization vessel are connected in series, and a single olefin is supplied under a pressure of 1 to 100 kg/cm2 G while heating to a temperature of 80 ° C. or less to carry out the first stage polymerization reaction, The polymer is produced in an amount of 1 to 20% of the total polymer amount finally obtained, and in the second polymerization vessel, it is added to the reaction product transferred from the first polymerization vessel or together with the first polymerization vessel. A degassing device is installed in the I① with the second polymerization vessel, and only a single other olefin is added to the product obtained by degassing the vaporized component of unreacted olefin from the reaction product of the first stage. or multiple other olefins, while keeping the reaction system in a fluid state at a temperature of 80°C or less and a pressure of 1-100 kg.
A second stage polymerization reaction is carried out under /c12G to produce a copolymer containing 1 to 30 ffl of other olefins. Note that, if necessary, prepolymerization in which a small amount of other olefin is polymerized can be performed before the first stage polymerization reaction.

The molecular weight of the polymer can be controlled by adjusting the hydrogen concentration in the polymerization vessel. Further, the catalyst component can be supplied suspended in an inert solvent, olefin, or the like.

In the method of this invention, post-treatment after polymerization is carried out.

This can be done by conventional methods. That is, in the gas phase polymerization method, after 5 g of 1 is combined, it is derived from the i1 combiner. A stream of nitrogen or the like may be passed through the polymer powder to remove olefins and the like contained therein.

Further, if desired, it may be pelletized using an extruder, and in this case, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst.

Further, in the bulk polymerization method, after polymerization, the monomer can be completely separated from the polymer derived from the polymerization vessel and then pelletized.

As described above, the olefin polymer obtained by the method of the present invention usually has an intrinsic viscosity [η] (tetralin solution, 135°C) of 1.0 to 6 dll/g, particularly t, 3 dJl/g. The stereoregularity is 1.1. (
The extraction residue after Soxhlet extraction of the obtained polymer with n-hebutane for 6 hours is 96% or more.

[Effects of the Invention] According to the present invention, (1) the resulting polymer has excellent stereoregularity, so it can be made into a molded product with a good appearance, and (2) it has a high molecular weight and a polymer powder. Since it is possible to obtain an olefin polymer with excellent flow characteristics, it is convenient for powder transportation, and (3) it is economical because the yield of the olefin polymer is high.

(5) Furthermore, if the gas phase polymerization method is used, The step of recovering the polymerization solvent can be omitted, and the step of drying the produced polymer can be greatly simplified.

It is possible to provide a method for packaging olefin polymers having the following advantages.

[Examples] Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention.

(Example 1) ■ Preparation of solid catalyst component 200 mal of butyloctylmagnesium (20% hebutane solution, manufactured by Schering AG, West Germany) and 150 mJl of heptane were placed in a two-liter flask purged with argon, and approximately 41 kg of chlorine gas was added at room temperature for 30 mJl. Added in minutes.

- This was heated to 30°C, 24 ml of ethanol was added, and 10 volumes were stirred at 90°C. The product was washed twice with 200 mJl heptane and the supernatant was removed. Add 400m of kerosene to this
Al and 24ml of ethanol were added and stirred at 100°C for 2 hours to obtain a dispersion. This dispersion was cooled to -20°C using a siphon and mixed with TiCJL4500ml/heptane200ml.
jL solution. After raising the temperature to room temperature, 3 ml of di-n-butyl phthalate was stirred at 100° C. for 1 hour. After removing the supernatant TiCls 800
mjl was added, and the mixture was further stirred at 110°C for 1 hour. After removing the supernatant, wash thoroughly with heptane,
A solid catalyst component was obtained.

■ Production of olefin polymer 1! Add 40 liters of hebutane to a stainless steel autoclave.
0ml, then 1■ triimbutylaluminum
Crow o1. tart-butyl methyl ether 00lts
ol, dilobitylphthalate 0.088 ama1,
and 0.0 when the above solid catalyst component is converted into titanium atoms.
025 smol, put in this order, hydrogen pressure 0.2Kg/
cm2c Otori 2. Flit polymerization was carried out at 70° C. for 4 hours while maintaining the propylene pressure at 7 kg/cs+2. Results first
Shown in the table.

(Examples 2 to 5, Comparative Examples) The same procedures as in Example 1 were carried out except that the external electron donor and the fourth component shown in Table 1 were changed.

(J!Bottom, margin)

Claims (1)

[Claims] (1) Olefin In the method for producing a polymer, the external electron donor (C) is represented by the following formula [
1a]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼[1a] (However, in formula [1a], R^1, R^2, and R^4
represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and R^3 represents a hydrogen atom or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 7 carbon atoms. ) or the following formula [1b]; ▲Mathematical formulas, chemical formulas, tables, etc.▼[1b] (However, R^5 represents a divalent aliphatic hydrocarbon group having 1 to 7 carbon atoms, and R^5 is , represents a group similar to R^3 in formula [1a], and R^6 represents a group similar to R^4 in formula [1a].) An ether compound (C^1) represented by Production of an olefin polymer, characterized by carrying out homopolymerization or copolymerization of an olefin using at least one compound (C^2) selected from the group consisting of carboxylic acid esters, organosilicon compounds, and azo compounds. Method.