JPH04264108A - Method for polymerizing alpha-olefin - Google Patents

Abstract

PURPOSE:To produce a poly-alpha-olefin having a high stiffness without detriment to the properties of a polymn. catalyst giving a high polymn. degree and a high steroregularity and excellent particle properties of the poly-alpha-olefin. CONSTITUTION:An alpha-olefin is polymerized in the presence of a polymn. catalyst which comprises a catalyst component obtd. by prepolymerizing a solid catalyst essentially consisting of Mg, Ti, a halogen, and an electron-donating compd. with an olefin in the presence of a cyclic amine having an alkylene group substd. by an alkenylcarbonyloxy group, an organoaluminum compd., and an organosilicon compd.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for (co)polymerizing α-olefins such as propylene.

0002

[Prior Art] Many α-olefin polymerization methods using polymerization catalysts consisting of a titanium catalyst component, an organometallic compound, and an alkoxysilane have been proposed for some time (Japanese Patent Application Laid-open Nos. 55-36203 and 57-63310). No. 58-
83006, etc.). However, when industrially advantageous continuous polymerization is carried out using conventional methods, fully satisfactory results have not been obtained in terms of catalyst polymerization activity, stereoregularity, polymer particle properties, etc.

Furthermore, Si-O-C bonds or Si-N-
An attempt is made to solve the above problems by using a titanium catalyst component obtained by prepolymerizing an α-olefin in the presence or absence of a compound selected from an organic silicon compound having a C bond and a sterically hindered amine. A polymerization method has also been attempted (Japanese Unexamined Patent Publication No. 59-206407). However, with conventional techniques, sufficient results have not been achieved even when trying to improve the mechanical properties, especially the rigidity, of the resulting polyα-olefin while maintaining high polymerization activity, high stereoregularity, and excellent particle properties. do not have.

0004

SUMMARY OF THE INVENTION The present invention is an α-olefin that can produce highly rigid polyα-olefins while maintaining the high polymerization activity and stereoregularity of the polymerization catalyst and the excellent particle properties of the resulting polymer. - To provide a method for (co)polymerizing olefins.

[0005]

[Means for Solving the Problems] As a result of extensive research, the present inventors have developed a catalyst component obtained by prepolymerizing an olefin in the presence of a cyclic amine compound having an unsaturated group. The present invention was completed by discovering that the object of the present invention can be achieved by (co)polymerizing an α-olefin using a polymerization catalyst in combination with an organosilicon compound.

SUMMARY OF THE INVENTION That is, the gist of the present invention is that (A) (a) a solid component containing (a) magnesium, titanium, halogen, and an electron-donating compound as essential components, (b) an organoaluminum compound and (
c) General formula

[Formula 2] [However, R1 is a hydrogen atom or an alkyl group, R2
is an alkenylcarbonyloxy group-substituted alkylene group, R
3 to R6 represent a hydrogen atom or an alkyl group. ]
In the presence of a cyclic amine compound represented by (d) a catalyst component brought into contact with an olefin, (B) an organoaluminum compound and (C) an organosilicon compound, an α-olefin is homopolymerized. Or there is a method of copolymerizing with other olefins.

Solid component The solid component used in the present invention (hereinafter referred to as component a) contains magnesium, titanium, halogen, and an electron-donating compound as essential components, but such components usually contain magnesium compounds, titanium compounds, and When the electron-donating compound and each of the above-mentioned compounds are halogen-free, they are prepared by contacting each with a halogen-containing compound.

(1) Magnesium Compound Magnesium compounds are represented by the general formula MgR1 R2. In the formula, R1 and R2 are the same or different hydrocarbon groups,
It represents an OR group (R is a hydrocarbon group), an RCOO group (R is a hydrocarbon group), and a halogen atom. More specifically, the hydrocarbon groups for R1 and R2 include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups, aryl groups, and aralkyl groups, and the hydrocarbon groups for R in OR and RCOO groups include , an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
In the aryl group and the aralkyl group, examples of the halogen atom include chlorine, bromine, iodine, and fluorine. Specific examples of these compounds are shown below, and in the chemical formula, Me: methyl,
Et: ethyl, Pr: propyl, Bu: butyl, He:
hexyl, Oct: octyl, Ph: phenyl, cyH
e: Indicates cyclohexyl. MgMe2,M
gEt2, Mgi-Pr2, MgBu2, MgH
e2, MgOct2, MgEtBu, MgPh2
, MgcyHe2 , Mg(OMe)2 , Mg(OE
t)2, Mg(OBu)2, Mg(OHe)2,
Mg(OOct)2, Mg(OPh)2, Mg(O
cyHe)2, (MeCOO)2Mg, (n-Pr
COO)2 Mg, (C17H35COO)2 Mg,
EtMgCl, BuMgCl, HeMgCl, i-Bu
MgCl, t-BuMgCl, PhMgCl, PhCH
2 MgCl, EtMgBr, BuMgBr, PhMg
Br, BuMgI, EtOMgCl, BuOMgCl,
HeOMgCl, PhOMgCl, EtOMgBr, B
uOMgBr, EtOMgI, (MeCOO)MgCl
, (n-PrCOO)MgCl, (C17H35COO
) MgCl, MgCl2, MgBr2, MgI2
.

The above magnesium compounds may be used alone or in combination of two or more. When using two or more types,
They may be used separately, simply mixed, or brought into contact by mechanical co-grinding in the presence or absence of a medium.

Furthermore, as the magnesium compound, a complex with an organic compound of a metal (M) of Group II or Group IIIa of the periodic table can also be used. The complex has the general formula MgR
It is expressed as 1 R2 ·n (MR3 m ). The metals include aluminum, zinc, calcium, etc., and R
3 is an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms. Further, m represents the valence of the metal M, and n represents a number from 0.1 to 10. MR3
Specific examples of compounds represented by m include AlMe3
, AlEt3 , Ali-Bu3 , AlPh3 , Z
nMe2, ZnEt2, ZnBu2, ZnPh2
, CaEt2, CaPh2, etc.

(2) Titanium compounds Titanium compounds are divalent, trivalent, and tetravalent titanium compounds, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorobutylene titanium. Examples include chlordiethoxytitanium, dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorextititanium, dichlorodibutoxytitanium, and dichlordiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred.

(3) Electron-donating compounds Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to organic groups via carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic esters and the like. Among these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid, and malonic acid. , aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2
-Alicyclic carboxylic acids such as dicarboxylic acids, aromatic monocarboxylic acids such as benzoic acid, toluic acid, anisic acid, p-tertiary butylbenzoic acid, naphthoic acid, cinnamic acid, phthalic acid,
Examples include aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, and mellitic acid. As the carboxylic acid anhydride, acid anhydrides of the above-mentioned carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyhydric esters of the above-mentioned carboxylic acids can be used, and specific examples include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, and pivalate. Isobutyl, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate,
Diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, disobutyl glutarate, diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, maleic acid Dibutyl, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, p-tertiary Butyl ethyl benzoate, p-ethyl anisate, α-ethyl naphthoate, α-isobutyl naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, phthalate Dioctyl acid, di2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate,
Tributyl trimellitate, tetramethyl pyromellitate,
Examples include tetraethyl pyromellitate and tetrabutyl pyromellitate.

As the carboxylic acid halide, acid halides of the above-mentioned carboxylic acids can be used,
Specific examples include acetic acid chloride, acetic bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride,
Butyric acid bromide, butyric acid iodide, pivalic acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, Succinic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride, sebacic acid chloride, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride , tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride, benzoyl bromide, p- Toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, Examples include isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Monoalkyl halides of dicarboxylic acids such as monomethyl adipate chloride, monoethyl maleate chloride, monomethyl maleate, and butyl phthalate chloride may also be used.

Alcohols are represented by the general formula ROH. In the formula, R is alkyl, alkenyl, cycloalkyl, aryl, or aralkyl having 1 to 12 carbon atoms. Specific examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol,
- Ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol, and the like.

Ethers are represented by the general formula ROR1. In the formula, R and R1 are alkyl, alkenyl, cycloalkyl, aryl, and aralkyl having 1 to 12 carbon atoms, and R and R1 may be the same or different. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether,
These include diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, and the like.

The method for preparing component a is as follows: (1) A magnesium compound (component 1), a titanium compound (component 2) and an electron-donating compound (component 3) are brought into contact in that order. (2) After component 1 and component 3 are brought into contact, component 2 is brought into contact. (2) A method such as bringing component 1, component 2, and component 3 into contact at the same time can be adopted. It is also possible to contact with a halogen-containing compound before contacting with component 2.

Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, halogenated silicon compounds having a hydrogen-silicon bond, Group IIa of the periodic table, and IV
Examples include halides of group A and Va group elements (hereinafter referred to as metal halides).

[0020] The halogenated hydrocarbon has 1 to 1 carbon atoms.
It is a mono- and polyhalogen-substituted product of 12 saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons. Specific examples of these compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,2
-Tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane, and chlorinated paraffins are alicyclic compounds. Chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane, and aromatic compounds such as chlorobenzene, bromobenzene, o-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzene Examples include trichloride, p-chlorobenzotrichloride, and the like. Not only one kind but also two or more kinds of these compounds may be used.

[0021] The halogen-containing alcohol is a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule, in which one or more hydrogen atoms other than the hydroxyl group are substituted with a halogen atom. means a compound. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, with chlorine atoms being preferred. Examples of these compounds include 2-chloroethanol, 1-chloro-2
-propanol, 3-chloro-1-propanol, 1-
Chlor-2-methyl-2-propanol, 4-chloro-
1-butanol, 5-chloro-1-pentanol, 6-
Chlor-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m,o,p)-chlorobenzyl alcohol, 4-chlorocatechol, 4-chlor −(
m,o)-cresol, 6-chloro-(m,o)-cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m,o,p)-
Chlorphenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-
Chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo-2-butanol, 2
-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m,o,p)-bromophenol, 4-bromoresorcin, (m,o,p)
)-Fluorophenol, p-iodophenol: 2,2
-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro-1-(α-chloromethyl)-1-propanol,
2,3-dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol,
2,4-dibromo-1-naphthol: 2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, β,β,β-trichloro-tert-butanol, 2,3,4-trichlor Phenol, 2,4,5
-Trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,3,
5-tribromo-2-hydroxytoluene, 2,3,5
-tribromo-4-hydroxytoluene, 2,2,2-
Trifluoroethanol, α, α, α-trifluoro-
m-cresol, 2,4,6-triiodophenol:
2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorbisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,3,5,6-tetra Examples include fluorophenol and tetrafluororesorcin.

Examples of the halogenated silicon compound having a hydrogen-silicon bond include HSiCl3, H2 SiCl2,
H3 SiCl, HCH3 SiCl2, HC2 H
5 SiCl2,H(t-C4H9)SiCl2
,HC6 H5 SiCl2 ,H(CH3)2
SiCl,H(i-C3H7)2SiCl,H2
C2 H5 SiCl, H2 (n-C4 H9)
SiCl, H2 (C6 H4 CH3)SiCl,
Examples include HSiCl(C6H5)2.

[0023] Examples of metal halides include B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
Examples include chloride, fluoride, bromide and iodide of i, especially BCl3, BBr3, BI3, AlCl3,
AlBr3, GaCl3, GaBr3, InCl
3, TlCl3, SiCl4, SnCl4, S
bCl5, SbF5, etc. are suitable.

[0024] Components 1, 2, and 3, and the halogen-containing compound that can be brought into contact as necessary, are mixed and stirred in the presence or absence of an inert medium, but not mechanically. This is done by co-grinding. Contact can be performed under heating at 40-150°C. As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene can be used.

As a specific method for preparing component a used in the present invention, for example, the method disclosed in the following patent publication can be adopted. JP-A-55-36203, 1982-127406, 1982-63310, 1982
-83006, 1985-198503, 1982-2
No. 06407, No. 115603 of 1982, No. 61 of 1983
No. 04, No. 62-146904, No. 63-26460
No. 7 publications

Organoaluminum compound The organoaluminum compound (hereinafter referred to as component b) is:
It is represented by the general formula Rn AlX3-n (wherein, R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, and n is an arbitrary number within the range of 1 n 3). 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, and alkyl aluminum monohydride. Alkylaluminum compounds or mixtures or complexes thereof are particularly preferred. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminium, tributylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum ionic acid, etc. dialkylaluminum monohalides, such as dydo, diisobutylaluminum chloride,
Monoalkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, dimethylaluminum methoxide , diethylaluminum ethoxide, diethylaluminium phenoxide,
Examples include dialkyl aluminum monoalkoxides such as dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, and diisobutyl aluminum phenoxide, and dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, and diisobutyl aluminum hydride. Among these, trialkylaluminum is preferred, particularly triethylaluminum and triisobutylaluminum.

The cyclic amine compound (hereinafter referred to as component c) used when the cyclic amine compound component a is brought into contact with the olefin is represented by the above general formula. In the formula, R1 is a hydrogen atom or an alkyl group. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is desirable. R2 is an alkenylcarbonyloxy group-substituted alkylene group, specifically

[C3
] Represented by . R7 is an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms. m and n are preferably 1 or 2, and m+n is preferably 3 or 4. R3 to R6 are hydrogen atoms or alkyl groups. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms. R3 to R6 may be the same or different at the same time.

Representative examples of component c include compounds of the following structural formula.

[C4]

embedded image However, R1, R3 to R6 and R7 have the same meanings as above.

Further, R7 may be an alkenyl group having a carbonyloxy group, and in this case, compounds having the following structural formula can also be exemplified. However, R8 is an alkelene group.

[C6]

[Chemical 7]

Specific examples of component c include the following compounds. 2,2,6,6-tetramethyl-4-piperidyl-crotonate, 1,2,6,6-pentamethyl-
4-piperidyl-crotonate, 2,2,6,6-tetramethyl-4-piperidyl-isocrotonate, 1,2
, 2,6,6-pentamethyl-4-piperidyl-isocrotonate, 2,2,6,6-tetramethyl-4-piperidyl-methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl -methacrylate, 1,2,2
, 6,6-pentamethyl-4-piperidylolelate,
Bis(2,2,6,6-tetramethyl-4-piperidyl)-maleate, 2,5-dimethyl-4-pyrrolidyl-
Crotonate, 1,2,5-trimethyl-5-pyrrolidyl-isocrotonate, 1,2,5-trimethyl-4-
Pyrrolidyl-methacrylate, bis(1,2,5-trimethyl-4-pyrrolidyl)-maleate.

Prepolymerization The solid component (component a) is prepolymerized by contacting it with an olefin in the presence of an organoaluminum compound (component b) and a cyclic amine compound (component c). Examples of olefins include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and other α-
Olefins can be used. Prepolymerization is preferably carried out in the presence of the aforementioned inert medium. Prepolymerization is usually 10
It is carried out at a temperature of 0°C or lower, preferably -30°C to +30°C, more preferably -20°C to +15°C. The polymerization method may be either a batch method or a continuous method, or may be carried out in multiple stages of two or more stages. When carrying out multi-stage polymerization, it is natural that the polymerization conditions can be changed in each stage.

Component b has a concentration of 50 to 5 in the prepolymerization system.
00 mmol/l, preferably 80-200 mmol/l
per gram atom of titanium in component a, preferably from 4 to 50,000 mol, preferably from 6 to 1,
000 moles.

Component c has a concentration in the prepolymerization system of 1 to 10
It is used at a concentration of 0 mmol/l, preferably 5 to 50 mmol/l. The prepolymerization incorporates an olefin polymer into component a, and the amount of polymer is desirably 0.1 to 200 g, particularly 0.5 to 50 g, per gram of component a.

The catalyst component (hereinafter referred to as component A) prepared as described above can be diluted or washed with the above-mentioned inert medium, but from the viewpoint of preventing storage deterioration of component A, It is especially advisable to wash it. After washing, it may be dried if necessary. In addition, when storing component A, it is desirable to store it at the lowest temperature possible, from -50℃ to
A temperature range of +30°C, especially -20°C to +5°C is recommended.

(Co)polymerization of α-olefin The present invention comprises a component A obtained as described above, an organoaluminum compound (hereinafter referred to as component B), and an organosilicon compound (hereinafter referred to as component C). This is a method in which α-olefin is homopolymerized or copolymerized with other olefins in the presence of a polymerization catalyst.

Component B is appropriately selected from the compounds of component b used in preparing component A, but
Trialkylaluminum, particularly triethylaluminum and triisobutylaluminum, are preferred. In addition, these trialkylaluminums may be combined with other organoaluminum compounds such as industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or mixtures or complex compounds thereof. Can be used in combination with etc. Furthermore, an organic aluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example

[Chemical formula 8] etc. can be exemplified.

[0037] As component C, Si-O-C bond or S
Examples include organic silicon compounds having an i-N-C bond, and preferably compounds having a Si-O-C bond. Such compounds have the general formula Rn Si(OR
1) 4-n [However, R is a hydrocarbon group or a halogen atom, R1 is a hydrocarbon group, and 0≦n≦3. ] Compounds represented by: Examples of the hydrocarbon group for R in the above general formula include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkadienyl group, a cycloalkenyl group, and a cycloalkadinyl group. As the halogen atom of R, chlorine, bromine,
Examples include iodine. Examples of the hydrocarbon group for R1 include an alkyl group, a cycloalkyl group, an aryl group, and an alkenyl group. Furthermore, n R hydrocarbons and (
The hydrocarbon groups of R1 in 4-n) OR1 may be the same or different.

Specific examples of component C include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra(p-methylphenoxy)silane, tetrabenzyloxysilane, and methyltrimethoxysilane. , methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane,
Ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane,
Dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxy Silane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxy Examples include silane, chlorophenyldiethoxysilane, and the like.

The polymerization catalyst used in the present invention consists of a combination of component A, component B and component C described above. The amount of component B used relative to component A is usually 1 to 2,000 g mol, especially 20 to 50 g mol, per 1 gram atom of titanium in component A.
0 gmol is desirable. The ratio of component B to component C is selected within the range of 0.1 to 40 gram atoms, preferably 1 to 25 gram atoms of component B as aluminum atoms per mole of component C.

The (co)polymerization of α-olefins is carried out in the presence of the above-mentioned polymerization catalyst.
- By homopolymerizing methyl-1-pentene, 1-hexene, etc., or by random or block copolymerization of these α-olefins with other α-olefins and/or ethylene or diolefins having 3 to 10 carbon atoms. It will be done.

The polymerization reaction of α-olefin may be carried out in either gas phase or liquid phase. When polymerizing in liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene are used. , in inert hydrocarbons such as xylene and in liquid monomers. The polymerization temperature is usually in the range of -80°C to +150°C, preferably 40 to 120°C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The molecular weight of the resulting polymer can also be controlled by the presence of hydrogen or other known molecular weight regulators. In addition, the amount of other olefin to be copolymerized with α-olefin in copolymerization is usually 3% to α-olefin.
It is chosen up to 0% by weight, especially in the range from 0.3 to 15% by weight. The polymerization reaction may be carried out continuously or batchwise, and the conditions may be those commonly used. Further, the copolymerization reaction may be carried out in one stage, or may be carried out in two or more stages.

[0042]

[Examples] The present invention will be specifically explained using examples and application examples. Note that percentages (%) in the examples are based on weight unless otherwise specified. Heptane insoluble content (hereinafter abbreviated as HI), which indicates the proportion of crystalline polymer in the polymer, is:
6 with boiling n-heptane in a modified Soxhlet extractor.
This is the remaining amount when time is extracted. The melt flow rate (MFR) of the polymer was measured according to ASTM D1238, and the bulk density was measured according to ASTM D1895-69 Method A. In addition, the measurement of the flexural modulus of the polymer is
Based on ASTM D790.

Example 1 Preparation of component a Component a was prepared according to the method described in Example 1 of JP-A-55-83006. That is, after stirring 0.95 g of anhydrous magnesium chloride, 10 ml of decane, and 4.7 ml of 2-ethylhexanol at 125°C for 2 hours, 0.55 g of phthalic anhydride was added and stirred for another 1 hour at the same temperature to form a homogeneous solution. did. After cooling to room temperature, the entire amount was dropped over 1 hour into 40 ml of titanium tetrachloride maintained at 120°C. After dropping, add the mixture for 2 hours.
The temperature was raised to 10°C, then diisobutyl phthalate 0.5
4 ml was added and stirred at the same temperature for 2 hours. The solid portion separated by hot filtration was suspended in 200 ml of titanium tetrachloride, and stirred at 110° C. for 2 hours. After the reaction was completed, the solid portion separated by hot filtration was thoroughly washed with decane and hexane until no free titanium compound was removed in the washing solution. Component a prepared by the above method is titanium 2
．． 0%, 62.5% chlorine, 18.7% magnesium and 15.2% diisobutyl phthalate.

Prepolymerization: Into a 500 ml glass flask purged with nitrogen gas, were added 250 ml of purified hexane, 25 mmol of triethylaluminum, 12.5 mmol of 1,2,2,6,6-pentamethyl-4-piperidylcrotonate and the product obtained above. After charging 1.6 mmol of component a in terms of titanium atoms, propylene was continuously supplied and prepolymerization was carried out for 1 hour. During this time, the temperature was maintained at 5°C. After the reaction was completed, the obtained solid portion was washed with 100 ml of hexane six times at room temperature by a decantation method to obtain a catalyst component. This catalyst component contained 2 g of polypropylene per gram of component a.

Polymerization of propylene 1 liter of liquefied propylene, 0.4 mmol of triethylaluminum, 0.08 mmol of diphenyldimethoxysilane, and 0.6 liter of hydrogen gas (NTP
) in that order, then lower the internal temperature of the autoclave to 6.
The temperature was raised to 5° C., and the catalyst component obtained above was charged in an amount of 4.2×10 3 mmol in terms of titanium atoms. Next, the internal temperature of the autoclave was raised to 70°C, and propylene was polymerized for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain 205 g of a white powdery polymer. Therefore, the polymerization activity (CE) of the catalyst component was 20,500 g.polypropylene/g.component a.time. Also, the HI of the polymer
is 98.4%, MFR is 7.0g/10min, bulk density is 0
．． It was 46g/cc. Furthermore, an antioxidant (BHT: 3,5-di-t-butyl-4
- hydroxytoluene) and mixed thoroughly,
When the flexural modulus of a test piece made from the pellets made from the pellets was measured, it was found to be 15,000 kgf/
cm2.

Examples 2 to 7 In the prepolymerization of Example 1, the cyclic amine compounds shown in Table 1 were used instead of 1,2,2,6,6-pentamethyl-4-piperidylcrotonate. A catalyst component was obtained in the same manner as in Example 1, and then propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1.

[Table 1]

Comparative Examples 1 to 3 In the prepolymerization of Example 1, 1,2,2,6,6-pentamethyl-4-piperidyl crotonate was not used, or in place of the piperidyl crotonate, the compounds shown in Table 2 were used. A catalyst component was obtained in the same manner as in Example 1, except that a cyclic amine compound was used, and then propylene was polymerized in the same manner as in Example 1. The results are shown in Table 2.

[Table 2]

[0048]

Effect of the invention: By the method of the present invention, highly stereoregular α
- An olefin (co)polymer can be produced in high yield, and the obtained (co)polymer exhibits high rigidity.

[Brief explanation of the drawing]

FIG. 1 is a flowchart diagram illustrating the method of the invention.

Claims (1)

[Claims] Claim 1: (A) A solid component comprising (a) magnesium, titanium, halogen, and an electron-donating compound as essential components, (b) an organoaluminum compound, and (c) the general formula [Formula 1] [However, R1 is a hydrogen atom or an alkyl group, R2
is an alkenylcarbonyloxy group-substituted alkylene group, R
3 to R6 represent a hydrogen atom or an alkyl group. ]
In the presence of a cyclic amine compound represented by (d) a catalyst component brought into contact with an olefin, (B) an organoaluminum compound and (C) an organosilicon compound, an α-olefin is homopolymerized. Or a method of copolymerizing with other olefins.