JP2775501B2 - Propylene-silicon compound random copolymer and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a propylene random copolymer having an alkenylsilyl group in a side chain.

2. Description of the Related Art As one of techniques for modifying a polyolefin, there is a method of producing a polymer having an alkenyl group in a side chain by copolymerizing an olefin and a diene. For example, ethylene,
Terpolymers of propylene and ethylidene norbornene (EPDM) and copolymers of propylene and dienes are known.

When a conjugated diene is used in the copolymerization of propylene and a diene, only a polymer having a low polymerization activity and a small amount of an alkenyl group can be produced. Therefore, a method using a non-conjugated diene such as 1,4-hexadiene or α, ω-diene instead of the conjugated diene has been attempted. However, even when copolymerization with propylene is performed using a non-conjugated diene, the polymerization activity is not high, and it is difficult to increase the content of the alkenyl group.

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a propylene copolymer having a high alkenyl group content with a high yield.

Means for Solving the Problems As a result of intensive studies, the present inventors have used an organosilicon compound having an alkenyl group at least at both terminals instead of a non-conjugated diene, and co-existed with propylene using a Ziegler-Natta type catalyst. It has been found that the object of the present invention can be achieved by polymerization.

SUMMARY OF THE INVENTION The present invention provides (1) the following repeating unit (A) and the following repeating unit (B)
A propylene-silicon compound random copolymer comprising:

Wherein R ² , R ³ and R ⁴ are the same or different hydrogen atoms, aliphatic or aromatic hydrocarbons having 1 to 8 carbon atoms, or -C _m H _2m
-CH = CH _2, n is 0-8 integer, m is an integer of 0 to 8, provided that at least one of R ^2, R ³ and R ⁴ are -C _m H
It is a _2m -CH = CH _2. ] (2) activated titanium trichloride catalyst component chloride or magnesium-supported titanium catalyst component and the general formula R _n AlX _3-n [where, R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom , N is an arbitrary number in the range of 1 ≦ n ≦ 3. Propylene and a general formula SiR ¹ R ^{2 in} the presence of a catalyst containing an organoaluminum compound represented by the formula
R ³ R ⁴ (where R ¹ is -C _n H _2n -CH = CH ₂ and R ² , R ³ and R
^{4 and} n are as defined above. ] The method for producing a copolymer according to claim (1), comprising copolymerizing the silicon compound of (1).

Copolymer The propylene random copolymer of the present invention is obtained by randomly bonding the repeating unit (A) and the repeating unit (B). R ² and R ³ in the above formula of the repeating unit (B)
And R ⁴ are the same or different hydrogen atoms, an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms, or —C _m H _2m —CH ＝ CH ₂ . Provided that at least one of R ² , R ³ and R ⁴ is -C _m H _2m -CH =
It is CH _2. As the aliphatic hydrocarbon group, an alkyl group,
The alkenyl group may be an aromatic hydrocarbon group such as an aryl group or an aralkyl group. Of these hydrocarbon groups, preferred are those having 1 to 6 carbon atoms, and particularly preferred are those having 1 to 4 carbon atoms. Alkyl groups. Also, −C _m H _2m −C
For _{H = CH 2, -C m H} 2m - are alkylene groups may be straight-chain or branched, straight-chain is preferable.

-C _n H _2n in Formula of the repeating unit (B) -
May be linear or branched, but is preferably linear. Further, n is an integer of 0 to 8, particularly 0 to 8.
An integer of 4 is preferred. Further, m is an integer of 0 to 8,
Particularly, an integer of 0 to 4 is desirable.

The copolymer of the present invention usually has a weight average molecular weight (w) of 10,000 to 1,000,000, preferably 100,000 to 400,000.

The copolymer of the present invention is a copolymer in which the repeating unit (A) and the repeating unit (B) are randomly bonded. In the copolymer, the repeating unit (B) is usually 0.01 to 20 mol%, preferably 0.02 mol%. 1010 mol%, the remainder being repeating units (A).

Method for Producing Copolymer The copolymer of the present invention can be produced by copolymerizing propylene and a silicon compound of the above general formula in the presence of the catalyst.

(1) Silicon compound The silicon compound is represented by the general formula SiR ¹ R ² R ³ R ⁴ . In the formula, R ¹ represents a _{-C n H 2n -CH = CH 2} , n is an integer of 0-8. R ² , R ³ and R ⁴ are the same or different, a hydrogen atom, an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms or-
A _{C m H 2m -CH = CH 2} , m is an integer of 0-8. However, at least one of R ² , R ³ and R ⁴ is -C _m H _2m -CH =
It is CH _2.

As the aliphatic hydrocarbon group for R ^{2 to} R ⁴ , an alkyl group or an alkenyl group is used, and as an aromatic hydrocarbon group, an aryl group or
An aralkyl group may be mentioned, and among these hydrocarbon groups, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. Also, -C _m H _2m -CH = C
For H _2, -C _m H _2m - are alkylene groups may be straight-chain or branched, straight-chain is preferable. m is particularly preferably an integer of 0 to 4.

Moreover, -C _n H of -C _n H _2n -CH = CH ₂ of R ¹ _2n - alkylene groups may be straight-chain or branched, but straight chain is preferable.
n is particularly preferably an integer of 0 to 4.

As the silicon compound, dimethyldivinylsilane, dimethyldiallylsilane, dimethyldibutenylsilane, ethylmethyldivinylsilane, ethylmethyldiallylsilane, diethyldivinylsilane, diethyldiallylsilane, ethylpropyldivinylsilane, ethylpropyldiallylsilane, divinylsilane, Diallyl silane,
Dibutenylsilane and the like. Particularly, dialkyldialkenylsilane is preferable.

(2) Catalyst The catalyst used in the present invention contains a titanium catalyst component and an organoaluminum compound as essential components. Examples of the titanium catalyst component include those used in ordinary (co) polymerization of propylene, ethylene and the like. Can be used.

Titanium catalyst component The titanium catalyst component includes titanium halide compounds such as titanium trichloride, titanium tetrachloride, trichloroethoxytitanium, dichlorodiethoxytitanium, dichlorodibutoxytitanium, dichlordiphenoxytitanium, and chlorotributoxytitanium.

Three as titanium chloride, titanium tetrachloride and TiCl ₃ · 1 / 3AlCl ₃ eutectic which was reduced with metallic aluminum, was reduced with an organoaluminum compound titanium tetrachloride, heat treatment,
Active titanium trichloride treated with an electron donating compound such as an ether or an ester, and further a halogen element and / or a halogen-containing compound such as a halogenated hydrocarbon, titanium tetrachloride or silicon tetrachloride can be used.

Moreover, the general formula MgR ⁵ _n magnesium represented by R ⁶ _2-n compound or component containing them (hereinafter, referred to these magnesium-containing compound.) May be used in contact of the said titanium halide compound. In the above general formula, R ⁵ and R ⁶ are a halogen atom, an OH group, a hydrocarbon group, OR
^And an alkoxy group represented by ⁷ . When 0 <n <2, R ⁵ and R ⁶ may be the same or different.

Examples of the halogen atom include chlorine, bromine and iodine.

As the hydrocarbon group, an alkyl group having 1 to 20 carbon atoms,
Cycloalkyl group, aryl group, aralkyl group and the like are mentioned, and as the alkyl group, methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl, decyl, etc., and as the cycloalkyl group, cyclopentyl, cyclohexyl, methylcyclohexyl As an aryl group, phenyl, tolyl, xylyl, naphthyl and the like,
As the aralkyl group, benzyl, phenethyl, 3-
Phenylpropyl and the like can be exemplified.

R ⁷ of the alkoxy group represented by OR ⁷ represents a hydrocarbon group, which may be the same as the above-mentioned hydrocarbon group.

Specific examples of the magnesium compound include MgCl ₂ , MgBr ₂ ,
_{ClMgOH, MgEt 2, MgBu 2,} MgHe 2, MgPh 2, EtMgBu, EtMgCl, BuMgC
l, BuMgBr, HeMgCl, PhMgCl, Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (O
He) ₂ , Mg (OPh) ₂ , EtOMgCl, BuOMgCl and the like. In the above compound, Et: ethyl, Bu: butyl, He:
Hexyl and Ph: phenyl are shown respectively. The magnesium-containing compound can be prepared from metallic magnesium by a conventional method.

As the titanium catalyst component, in addition to the titanium halide compound, the magnesium-containing compound, the electron-donating compound and / or the halogen-containing compound, and the above three or four components, those obtained by contacting a metal oxide are also used. can do.

Examples of the electron donating compound include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, Phosphorus bonded to an organic group via carbon or oxygen,
Examples include arsenic and antimony compounds, phosphoamides, thioethers, thioesters, carbonate esters and the like.

Examples of the halogen-containing compound include a metal halide, a non-metal halide, a halogenated hydrocarbon, a silicon halide compound, and a halogen-containing alcohol.

AlCl ₃ , SiCl ₄ , SnCl ₄ etc. as metal halides, BCl ₃ , PCl ₅ , SOCl etc. as non-metal halides, dichloroethane, tetrachloroethane, hexachloroethane, trichloride as halogenated hydrocarbons Ethylene, tetrachloroethylene, dichloropropane, octachloropropane, trichlorocyclohexane, dichlorobenzene, hexachlorobenzene and the like, as silicon halide compounds, dichlorosilane, trichlorosilane, methyldichlorosilane, ethyldichlorosilane, dimethyl Chlorosilane, diethylchlorosilane, ethylchlorosilane, butylchlorosilane, phenyldichlorosilane, and the like include halogen-containing alcohols such as 2-chloroethanol, 2,2,2-trichloroethanol, and 1,1,1-trichloro-. 2-propanol, p-co Tetrazole, 1-bromo-2-butanol.

Examples of the metal oxide include silica and alumina.

The following can be exemplified as desirable titanium catalyst components.

a) Activated titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound and then treating with an electron donating compound and a halogen-containing compound.

b) Mg (OR ⁷ ) (OR ⁸ ) [provided that R ⁷ and R ⁸ are R ⁵ and
A hydrocarbon group having the same meaning as R ⁶ . The catalyst component obtained by contacting the magnesium dialkoxide of the present invention with a halogenated hydrocarbon or a halogen-containing alcohol, and further contacting with an electron-donating compound and a titanium halide.

c) MgR ⁹ X [where R
⁹ is a hydrocarbon group of the same meaning as the R ^5, X is a halogen atom. ], And R ¹⁰ _m C (OR ¹¹ ) _4-m or R ¹⁰ _m Si (OR ¹¹ ) _4-m [where R ¹⁰
Is a hydrogen atom or a hydrocarbon group having the same meaning as R ⁵ above, R ¹¹
The hydrocarbon group of the same meaning as the R ^5, 0m <3. And Mg (OR ¹¹ ) X, followed by contact with a halogenated hydrocarbon or a halogen-containing alcohol, and further contact with an electron-donating compound and a titanium halide.

d) Metal oxide and MgR ¹² R ¹³ [where R ¹² and R ¹³ are the same hydrocarbon groups as R ⁵ and R ⁶ above. And then contacting with or without contacting the alkoxy-containing compound used in c) above with a halogen-containing compound, especially a halogen-containing alcohol, followed by an electron-donating compound and halogenation A catalyst component obtained by contacting with a titanium compound.

Organoaluminum compound As the organoaluminum compound, the general formula R _n AlX
_3-n (where R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n represents 1
Any number in the range of n3. And C1 to C18 such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride.
Preferably, an alkylaluminum compound having 2 to 6 carbon atoms or a mixture or complex compound thereof is particularly preferred.

The catalyst used in the present invention comprises the above-mentioned titanium catalyst component and the organoaluminum compound as essential components, and may further contain an electron-donating compound and / or an organosilicon compound.

The electron donating compound is selected from compounds that can be used when preparing the titanium catalyst component.
Examples of the organosilicon compound include tetraalkyloxysilane, tetraaryloxysilane, tetraalkyloxysilane, alkyltrialkyloxysilane, alkyltriaryloxysilane, aryltrialkyloxysilane, aryltriaryloxysilane, and dialkyldialkyl. Examples include hydrocarbyloxy group-containing organosilicon compounds such as oxysilane, dialkyldiaryloxysilane, diaryldialkyloxysilane, and diaryldiaryloxysilane.

The organoaluminum compound is usually used in an amount of 0.5 to 1,000 g mol per gram atom of titanium in the titanium catalyst component. The electron donating compound and / or the organosilicon compound, which may be used as needed, is used in an amount of 0.01 to 50 mol per 1 mol of the organic aluminum compound.

(3) Copolymerization method The copolymerization reaction between propylene and a silicon compound is carried out in a gas phase,
Any of the liquid phase may be used, when polymerizing in the liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, inactive hydrocarbons such as xylene or in liquid propylene It can be carried out. The copolymerization temperature is usually in the range of -80C to + 150C, preferably 40 to 120C. The copolymerization pressure may be, for example, 1 to 60 atm.
The molecular weight of the obtained copolymer is controlled by the presence of a molecular weight regulator such as hydrogen. The proportion of propylene (A) and silicon compound (B) used is
(B) / (A) (molar ratio) is from 0.0001 to 10. The copolymerization reaction may be continuous or batchwise, and may be performed in one stage or in two or more stages.

Effects of the Invention According to the method of the present invention, a propylene copolymer having a higher alkenyl group content can be produced as compared with the case where a conventional dialkenyl group-containing compound is used.

The copolymer of the present invention is rich in reactivity because it has an unsaturated double bond in the side chain, and therefore, by utilizing this property, it can be applied to a coated, printable polypropylene molded product, a polyolefin such as polypropylene. Adhesives with other plastics, glass, metals, wood, etc., compatibilizers with polyolefins and polymers having functional groups, vulcanizing agents for synthetic or natural rubber, materials for cross-linked foam moldings, etc. Can be. Further, since the copolymer can easily introduce a functional group, it can be used as an intermediate of a functional polymer.

Examples Hereinafter, the present invention will be described specifically with reference to examples.

The structure of the copolymer was measured by ¹³ C-NMR. The concentration of the repeating unit (B) contained in the copolymer is ¹ H-
Measured by NMR. The measurement conditions are as follows.

The molecular weight was measured by GPC. The melt flow rate (MFR) of the copolymer is ASTM-D1238 (230 ° C, load 216
0g).

Example 1 Preparation of titanium catalyst component A 200-ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. Add silicon oxide (DA
VISON, trade name G-952) in nitrogen stream for 200
5 g of calcined at 700C for 2 hours and further at 700C for 5 hours and 40 ml of n-heptane were added. Further, 20 ml of a 20% n-heptane solution of n-butylethylmagnesium (manufactured by Texas Alkyls, trade name: MAGALA BEM) was added, and the mixture was stirred at 90 ° C. for 1 hour.

After the suspension was cooled to 0 ° C, a solution of 11.2 g of tetraethoxysilane dissolved in 20 ml of n-heptane was dropped from the dropping funnel over 30 minutes. After completion of the dropwise addition, the temperature was raised to 50 ° C. over 2 hours, and stirring was continued at 50 ° C. for 1 hour. After completion of the reaction, the supernatant was removed by decantation, and the resulting solid was washed with 60 ml of n-heptane at room temperature.
Further, the supernatant was removed by decantation. This n
-Washing treatment with heptane was further performed four times.

To the above solid, 50 ml of n-heptane was added to form a suspension, and a solution of 8.0 g of 2,2,2-trichloroethanol dissolved in 10 ml of n-heptane was added thereto at 25 ° C for 15 minutes from a dropping funnel. Hanged and dropped. After completion of the dropwise addition, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, 60 ml of n-
The solid was obtained by washing twice with heptane and three times with 60 ml of toluene, respectively.

10 ml of n-heptane and titanium tetrachloride were added to the obtained solid.
40 ml was added, the temperature was raised to 90 ° C., and 0.6 g of di-n-butyl phthalate dissolved in 5 ml of n-heptane was added over 5 minutes.
Thereafter, the temperature was raised to 115 ° C., and the reaction was performed for 2 hours. After cooling to 90 ° C., the supernatant was removed by decantation, and n-
Washing was performed twice with 70 ml of heptane. Further, n-heptane
15 ml and 40 ml of titanium tetrachloride were added and reacted at 115 ° C. for 2 hours. After the completion of the reaction, the obtained solid substance was washed eight times at room temperature with 60 ml of n-hexane. Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a titanium catalyst component.
This component contained 3.1% by weight titanium.

Copolymerization of propylene In a 1.5 stainless steel autoclave equipped with a stirrer and a catalyst component introduction equipment, under a nitrogen atmosphere, 4 ml of a n-heptane solution (0.1 mol /) of triethylaluminum (hereinafter referred to as TEAL), 4 ml of a solution of n-hexyldimethoxysilane in n-heptane (0.1 mol /) and 270 ml (1.48 mol) of diallyldimethylsilane were charged. Next, 600 ml of hydrogen gas and 730 ml (8.9 mol) of liquid propylene as a molecular weight controlling agent were injected (the molar ratio of diallyldimethylsilane / propylene was 0.17).
The temperature was raised to 80 ° C., and 11.4 mg of the titanium catalyst component obtained above was added to the reaction system from the introduction equipment, and copolymerization was performed for 1 hour.

After purging the remaining propylene and hydrogen, the produced polymer was taken out, washed three times with a mixed solution of an equal weight of isopropyl alcohol and n-heptane, and dried in vacuum at 70 ° C.

The obtained white powder product was completely dissolved in hot xylene, injected into a large amount of chloroform, and purified by reprecipitation. This operation was repeated twice, and finally, the resultant was washed three times with chloroform, filtered, and vacuum-dried for 10 hours or more. The yield of the produced polymer was 23.9 g. Therefore, the polymerization activity (CE)
Is 2.1 kg / g-catalyst component-hour.

The result of analyzing the obtained copolymer by ¹³ C-NMR was as follows.

Also, by ¹ H-NMR measurement, 0p derived from (—Si—CH ₃ )
4.8-5.0pp derived from peak intensity around pm and side chain end
From the ratio of the integral value of the peak intensity around m and the integral value of the peak intensity around 0.9 to 1.0 ppm corresponding to the propylene chain, the content of the repeating unit (B) in the copolymer was 0.3 mol%. It turned out to be.

The MFR of the obtained copolymer was 4.2 g / 10 min, the weight average molecular weight (w) was 198,700, and the number average molecular weight (n) was 40,
It was 600.

Example 2 Preparation of Titanium Catalyst Component In a single reaction vessel equipped with a reflux condenser, 8.3 g of chip-shaped metal magnesium (purity 99.5%, average particle size 1.6 mm) and 250 ml of n-hexane were placed under a nitrogen gas atmosphere. After stirring at 68 ° C. for 1 hour, metallic magnesium was taken out and dried at 65 ° C. under reduced pressure to obtain pre-activated metallic magnesium.

Next, n-butyl ether was added to the metallic magnesium.
A suspension containing 140 ml and 0.5 ml of an n-butyl ether solution of n-butylmagnesium chloride (1.75 mol /) was maintained at 55 ° C., and a solution obtained by dissolving 38.5 ml of n-butyl chloride in 50 ml of n-butyl ether was further added for 50 minutes. Was dropped. After conducting the reaction at 70 ° C for 4 hours with stirring, the reaction solution was cooled to 25 ° C.
Held.

Next, 55.7 ml of HC (OC ₂ H ₅ ) _{3 was} added dropwise to the reaction solution over 1 hour. After the completion of the dropwise addition, the reaction was carried out at 60 ° C. for 15 minutes, and the solid produced by the reaction was washed six times with 300 ml each of n-hexane and dried under reduced pressure at room temperature for 1 hour to recover a magnesium-containing solid.

300ml equipped with reflux condenser, stirrer and dropping funnel
In a reaction vessel, a solid containing magnesium under a nitrogen gas atmosphere
6.3 g and 50 ml of n-heptane were put into a suspension, and a mixed solution of 20 ml (0.02 mmol) of 2,2,2-trichloroethanol and 11 ml of n-heptane was dropped from the dropping funnel over 30 minutes while stirring at room temperature. The mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was separated by filtration, washed four times with 100 ml each of n-hexane at room temperature, and twice with 100 ml each of toluene to obtain a solid component.

40 ml of toluene was added to the above solid component, and titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. Under stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. The obtained solid substance is 90
It was filtered off at 90 ° C. and washed at 90 ° C. twice with 100 ml each of toluene. In addition, a new titanium tetrachloride / toluene volume ratio of 3 /
Titanium tetrachloride was added so as to obtain 2, and the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was filtered off at 110 ° C.
After washing 7 times with 00 ml of n-hexane, the titanium catalyst component 5.
5 g were obtained.

Propylene copolymerization In a 200 ml reactor equipped with a stirrer, under a nitrogen gas atmosphere, 121.6 mg of the catalyst component obtained above, 100 ml of n-heptane
And 0.31 g (2.2 mmol) of diallyldimethylsilane and stirred at 25 ° C. Subsequently, 0.6 mmol of TEAL was added. Next, after the pressure in the system was reduced to 50 mmHg, propylene gas was continuously supplied. The molar ratio of diallyldimethylsilane / propylene in the liquid phase at the start of the polymerization was 0.03. After 1.5 hours, ethanol was added to the system to terminate the polymerization. The obtained polymer was washed with dilute hydrochloric acid, washed with a large amount of ethanol, and vacuum-dried at 70 ° C. for 8 hours. The yield of the produced polymer was 20.1 g. Therefore, CE is 0.11
It is.

The copolymer obtained in the same manner as in Example 1 was characterized, and the results are shown in Table 1.

Example 3 Titanium catalyst component Two flasks equipped with a stirrer were placed in a thermostatic water bath maintained at 0 ° C., and 700 ml of purified heptane and 250 ml of titanium tetrachloride were added to the flask and mixed. Then, while maintaining the temperature of the heptane solution in titanium tetrachloride at 0 ° C., 315 ml of diethyl aluminum chloride (hereinafter referred to as DEA)
C), 117 ml of ethyl aluminum dichloride and
A mixture consisting of 400 ml of purified heptane was mixed dropwise over 3 hours. After completion of the dropwise addition, the content was heated with stirring, and after one hour, the temperature was raised to 65 ° C., and further stirred at this temperature for one hour to obtain a reduced solid. The obtained reduced solid was separated, washed with purified heptane, and dried under reduced pressure at 65 ° C. for 30 minutes.

Next, a suspension was prepared by dispersing 25 g of the reduced solid in 100 ml of purified heptane, and then the suspension was added with an amount of hexachloroethane equivalent to 1 gram mole of hexachloroethane per gram atom of titanium in the reduced solid. Ethane was added in the form of a solution containing 25 g of hexachloroethane in 100 ml, and dinormal butyl ether in an amount equivalent to 0.6 gmol / g atom of titanium in the reduced solid was added and mixed with stirring.

Next, this mixture was heated with stirring and stirred at 80 ° C. for 5 hours, and the obtained solid was washed 5 times with 100 ml of purified heptane and dried at 65 ° C. for 30 minutes to obtain a titanium catalyst. The components were prepared.

Propylene copolymerization In a 3.0 stainless steel autoclave equipped with a stirrer and catalyst component introduction equipment, under nitrogen atmosphere, DEAC
Of n-heptane solution (1.2 mol /) and 150 ml (0.82 mol) of diallyldimethylsilane. Next, hydrogen gas 1.2 and liquid propylene 1 as molecular weight control agents
850 ml (22.6 mol) is injected (diallyldimethylsilane /
After adjusting the propylene molar ratio to 0.04), the temperature of the reaction system was raised to 70 ° C., and 102.4 mg of the titanium catalyst component obtained above was added to the reaction system from the introduction equipment, and copolymerization was performed for 1 hour. Next, the same treatment as in Example 1 was performed to obtain 174.1 g of a copolymer. Therefore, CE is 1.7.

The copolymer obtained in the same manner as in Example 1 was characterized, and the results are shown in Table 1.

Example 4 Example 1 was repeated except that the catalyst component used in Example 2 was used as the catalyst component and triisobutylaluminum was used as the organoaluminum compound in the amounts shown in Table 1 and the polymerization conditions were as shown in Table 1. In the same manner as in the above, copolymerization of propylene and divinyldimethylsilane was performed. Next, the same treatment as in Example 1 was performed to obtain a copolymer.

The result of analyzing the obtained copolymer by ¹³ C-NMR was as follows.

Further, from the result of analysis by ¹ H-NMR, it was found that the amount of the repeating unit (B) contained in the copolymer was 0.4 mol%.

The MFR of the obtained copolymer was 4.9 g / 10 minutes, and w
Was 189,500 and n was 31,100.

Example 5 Copolymerization of propylene and dibutenyldimethylsilane was carried out in the same manner as in Example 3, except that the amount of the catalyst component used and the polymerization conditions were as shown in Table 1. Next, the same treatment as in Example 1 was performed to obtain a copolymer.

The result of analyzing the obtained copolymer by ¹³ C-NMR was as follows.

From the result of analysis by ¹ H-NMR, it was found that the amount of the repeating unit (B) contained in the copolymer was 5.6 mol%.

The MFR of the obtained copolymer was 5.1 g / 10 minutes,
w was 187,900 and n was 30,700.

Reference Example 1 In Example 1, copolymerization with propylene was carried out using ethylidene norbornene instead of diallyldimethylsilane.

As a result of analyzing the obtained polymer by ¹ H-NMR, it was found that copolymerization with ethylidene norbornene was not performed.

Reference Example 2 In Example 2, copolymerization with propylene was performed using 1,13-tetradecadiene instead of diallyldimethylsilane.

The obtained copolymer was subjected to ¹ H-NMR analysis and GPC analysis, and the results are shown in Table 1.

Reference Example 3 In Example 5, copolymerization with propylene was performed using 1,4-hexadiene instead of dibutenyldimethylsilane.

The obtained copolymer was subjected to ¹ H-NMR analysis and GPC analysis, and the results are shown in Table 1.

Continuing from the front page (72) Inventor Satoshi Ueki 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Within Tonen Co., Ltd. (72) Koji Maruyama 1-3-3 Nishitsurugaoka, Oimachi, Iruma-gun, Saitama No. 1 Inside the Tonen Research Laboratory (56) References JP-B-39-27763 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70 C08F 10 / 06,210 / 06 C08F 30 / 08,230 / 08

Claims (2)

(57) [Claims] 1. A propylene-silicon compound random copolymer comprising the following repeating unit (A) and repeating unit (B). [Wherein, R ² , R ³ and R ⁴ are the same or different hydrogen atoms, aliphatic or aromatic hydrocarbons having 1 to 8 carbon atoms, or -C _m H
_2m -CH = CH _2, n is an integer of 0-8, m is 0-8 integer.
However, at least one of R ² , R ³ and R ⁴ is -C _m H _2m-
It is a CH = CH _2. ] 2. An activated titanium trichloride catalyst component or a magnesium-supported titanium catalyst component and (b) a general formula R _n AlX
_{3-n wherein} R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n represents 1 ≦
It is an arbitrary number in the range of n ≦ 3. Propylene and the general formula SiR ¹ R ² R ³ R ⁴ [where R ¹ is -C _n H _2n -CH = CH ₂
And R ² , R ³ and R ⁴ and n are as defined above. The method for producing a copolymer according to claim 1, wherein the silicon compound is copolymerized.