JP2004143435A - Method for producing olefinic graft copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefinic graft copolymer capable of producing a high effect when used as a compartibilizer, etc. <P>SOLUTION: A method for producing the graft copolymer, for example, producing the olefinic graft copolymer comprising a 3-20C α-olefin and a polyene, includes at least a polymerization process [I], a washing process, and a polymerization process [II] as follows: the polymerization process [I] comprises, for example, producing an olefinic polymer by using a catalyst composed of (A) a catalyst component containing titanium trichloride as an essential component and (B) an organoaluminum compound and copolymerizing the 3-20C α-olefin and the polyene; the washing process comprises removing the polyene from the reaction mixture of the olefinic polymer obtained by the polymerization process [I]; and the polymerization process [II] comprises, for example, polymerizing the 3-20C α-olefin in the presence the olefinic polymer given through the washing process. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to an olefin-based graft copolymer useful as a melt fluidity improver for enhancing extrusion moldability by increasing the melt tension, or as a compatibilizer for facilitating the design of polyolefin-based composite materials and composite materials. And a method for producing the same.

The olefin-based graft copolymer has a possibility of being applied as a melt fluidity improver for enhancing melt moldability, particularly extrusion moldability, or as a compatibilizer for incompatible composite materials. However, the conventional method for producing an olefin-based graft copolymer requires a complicated production process, is simpler, and is a method for producing an olefin-based graft copolymer that exhibits a high effect when used as a compatibilizer or the like. Has not yet been established.
For example, a method of producing an olefin-based graft copolymer by graft-polymerizing styrenes onto a graft precursor composed of ethylene / α-olefin / polyene is disclosed (for example, see Patent Documents 1 and 2). ). Since this production method is a production method in which the production of a graft precursor and the production of a graft polymer using the same are completely separated, the production steps are complicated.
Further, a method of producing an olefin-based graft copolymer by performing graft polymerization following production of a graft precursor is disclosed (for example, see Patent Document 3). In this production method, since the polyene component used during the production of the graft precursor remains, there is a limit in achieving higher graft efficiency during graft polymerization.
Furthermore, there is disclosed a method for producing an olefin-based graft copolymer by graft-polymerizing an ethylenically unsaturated monomer onto a styrene-based graft precursor having a syndiotactic structure (for example, see Patent Document 4). . However, although there is a description that washing is performed before graft polymerization, a specific method of washing is not disclosed, and the catalyst used for graft polymerization is different from the catalyst used for precursor polymerization.
Further, a method for producing an olefin-based graft copolymer using a radical polymerization catalyst or an anion polymerization catalyst on a graft precursor comprising an α-olefin and divinylbenzene is disclosed (for example, Patent Document 5, Patent Document 6). reference). However, although there is a description that washing is performed before graft polymerization, a specific method of washing is not disclosed, and the catalyst used for graft polymerization is different from the catalyst used for precursor polymerization.

JP-A-5-295042 (pages 12 and 19) JP-A-5-247147 (pages 12-14) JP-A-5-262817 (pages 14 to 15) JP-A-5-17533 (pages 15-22) JP-A-1-123811 (pages 1 and 4-7) JP-A-1-118510 (pages 1, 8-10)

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for more easily producing an olefin-based graft copolymer having a high effect when used as a compatibilizer or the like. .

The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that an olefin comprising one or more monomers selected from ethylene, α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrenes, and a polyene. In the method for producing the graft copolymer, the olefin polymer produced in the specific polymerization step [I] is washed to remove the polyene, and then the same or different monoolefins used in the polymerization step [I] are used. It has been found that the above object is achieved by producing an olefin-based graft copolymer by a polymerization step [II] of polymerizing a monomer. The present invention has been completed based on such findings.

That is, the present invention provides a method for producing an olefin-based graft copolymer comprising a polyene and one or more monomers selected from ethylene, α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrenes, at least the following: Which comprises a polymerization step [I], a washing step and a polymerization step [II].
Polymerization Step [I]: Using a catalyst comprising (A) a titanium trichloride compound or a catalyst component containing titanium, magnesium and a halogen element as essential components and (B) an organoaluminum compound, ethylene, a C3-20 a step of producing an olefin polymer by copolymerizing at least one monomer selected from α-olefins, cyclic olefins and styrenes with a polyene.
Washing step: a step of removing the polyene from the reaction mixture of the olefin polymer obtained in the polymerization step [I].
Polymerization step [II]: one or more monomers selected from ethylene, α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrenes in the presence of an olefin polymer having undergone a washing step, A step of polymerizing monomers of the same or different type as those used in step [I].

オ レ フ ィ ン The olefin-based graft copolymer of the present invention is excellent in the effect as a compatibilizer and the effect of improving melt fluidity.

In the production method of the present invention, at least one selected from ethylene, α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrenes is used as a monomer. Α-olefins having 3 to 20 carbon atoms and styrenes are preferred, ethylene and α-olefins having 3 to 12 carbon atoms are more preferred, and ethylene, propylene and α-olefins having 4 to 12 carbon atoms are most preferred.
As the α-olefin having 3 to 20 carbon atoms used in the production method of the present invention, for example, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 4-phenyl-1-butene , 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene , 1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Α-olefins such as -octadecene, 1-eicosene, vinylcyclohexane, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, And halogen-substituted α-olefins such as 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene and 3,4-dichloro-1-butene.
As the cyclic olefins, for example, those represented by the general formula (I)

（式中、Ｒ¹ 〜Ｒ¹²はそれぞれ水素原子、炭素数１〜２０の炭化水素基又はハロゲン原子、酸素原子もしくは窒素原子を含む置換基を示し、ｍは０以上の整数を示す。Ｒ⁹ 又はＲ¹⁰とＲ¹¹又はＲ¹²とは互いに環を形成してもよい。また、Ｒ¹ 〜Ｒ¹²はそれぞれ互いに同一でも異なっていてもよい。）

(Wherein, R ^{1 to} R ¹² each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and m represents an integer of 0 or more. R ⁹ Alternatively, R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. Also, R ^{1 to} R ¹² may be the same or different from each other.)

Can be mentioned.
In the general formula (I), examples of the hydrocarbon group having 1 to 20 carbon atoms among R ^{1 to} R ¹² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. A C 1-20 alkyl group such as a group, a t-butyl group, and a hexyl group; a C 6-20 aryl group such as a phenyl group, a tolyl group and a benzyl group; an alkylaryl group or an arylalkyl group; a methylidene group; Examples thereof include an alkylidene group having 1 to 20 carbon atoms such as an ethylidene group and a propylidene group. However, R ¹ , R ² , R ⁵ and R ⁶ exclude an alkylene group. When any of R ³ , R ⁴ , and R ^{7 to} R ¹² is an alkylidene group, the carbon atom to which it is bonded has no other substituent.

Examples of the substituent containing a halogen atom include, for example, halogen groups such as fluorine, chlorine, bromine and iodine, and halogen-substituted alkyl groups having 1 to 20 carbon atoms such as chloromethyl group, bromomethyl group and chloroethyl group. Can be.
Examples of the substituent containing an oxygen atom include, for example, a methoxy group, an ethoxy group, a propoxy group, a carbonyl group having 1 to 20 carbon atoms such as a phenoxy group, an aryloxy group, a methoxycarbonyl group, and a carbon atom having 1 to 20 carbon atoms such as an ethoxycarbonyl group. And 20 alkoxycarbonyl groups.
Examples of the substituent containing a nitrogen atom include an alkylamino group having 1 to 20 carbon atoms, such as a dimethylamino group and a diethylamino group, and a cyano group.

Specific examples of the cyclic olefin represented by the general formula (I) include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, and 7-methylnorbornene. 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a -Octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8 -Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8- Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1, 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydro Phthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrocyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxyl norbornene anhydrate, Examples thereof include 5-dimethylaminonorbornene and 5-cyanonorbornene.

On the other hand, as styrenes, for example, styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methyl Styrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene, 2,4-dimethylstyrene, 2, Alkylstyrenes such as 5-dimethylstyrene and 3,5-dimethylstyrene, alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene and m-methoxystyrene, p-chlorostyrene, m-chlorostyrene and o-chloro Styrene, p-bromostyrene, m Halogenated styrenes such as bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, and further include trimethylsilylstyrene, vinyl benzoate, and the like. Can be.
In the present invention, the monomer used in the polymerization step [I] and the polymerization step [II] may differ from one or more monomers, or may be the same as the polymerization step [I] and the polymerization step [II]. When a monomer is used, one having at least one of a monomer composition ratio, a stereoregularity, and a molecular weight of a polymer to be produced is different.

Examples of the polyene used in the present invention include a polyene having two or more polymerizable carbon-carbon double bonds in a molecule, a polyene having an α-olefin skeleton / α-olefin skeleton in the molecule, and a styrene skeleton / styrene skeleton. In the molecule, polyene having a cyclic olefin skeleton / cyclic olefin skeleton in the molecule, polyene having a styrene skeleton / α-olefin skeleton in the molecule, polyene having a cyclic olefin skeleton / α-olefin skeleton in the molecule, and styrene skeleton / Polyenes having a cyclic olefin skeleton in the molecule are preferable, and at least one selected from these is used. Preferred polyenes include, for example, compounds (i) to (vi) shown below.

(I) α-olefin skeleton / polyene having α-olefin skeleton in the molecule General formula (i)
_{CH 2 = CH-Q-CH} = CH 2 ··· (i)
(In the formula, Q represents a single bond or an alkylene group having 1 to 20 carbon atoms.)
Can be mentioned. Specific examples of the polyene include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadienes, 1,13-tetradecadienes, 1,15-hexadecadienes, 4-methyl-1,9-decadienes, 4,4-dimethyl-1,9-decadienes, 5-allyl-1, Examples thereof include 9-decadiene and 1,19-ecodiene.

(Ii) Styrene skeleton / Polyene having styrene skeleton in molecule General formula (ii)

（式中、Ｒ¹³は水素原子、ハロゲン原子あるいは炭素原子及び／又はケイ素原子を含む置換基、Ｒ¹⁴はα−オレフィン残基を有する置換基、ａは１〜４の整数を示し、ａが２以上の場合、複数のＲ¹³は同一でも異なっていてもよい。）

(Wherein, R ¹³ represents a hydrogen atom, a halogen atom or a substituent containing a carbon atom and / or a silicon atom, R ¹⁴ represents a substituent having an α-olefin residue, a represents an integer of 1 to 4, and a represents In the case of two or more, a plurality of R ¹³ may be the same or different.)

Can be mentioned. Specific examples of the polyene include p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, di (p-vinylphenyl) methane, 1,3-bis (p-vinylphenyl) propane, 1,5-bis (P-vinylphenyl) pentane and the like.

(Iii) Cyclic olefin skeleton / polyene having cyclic olefin skeleton in the molecule General formula (iii-1)

（式中、Ｒ¹⁵〜Ｒ²⁴はそれぞれ水素原子、炭素数１〜２０の炭化水素基又はハロゲン原子を示し、ｎは０以上の整数を示す。Ｒ¹⁹とＲ²⁰はたがいに環を形成していてもよい。また、Ｒ¹⁵〜Ｒ²⁴はたがいに同一でも異なっていてもよい。）

(Wherein, R ^{15 to} R ²⁴ each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, and n represents an integer of 0 or more. R ¹⁹ and R ²⁰ each form a ring. And R ^{15 to} R ²⁴ may be the same or different.

And a compound comprising a norbornene skeleton and a cyclopentene skeleton.
Examples of the halogen atom in R ^{15 to} R ²⁴ include a chlorine atom, a fluorine atom, and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, tetradecyl, pentadecyl, and heptadecyl. Groups, octadecyl groups, and corresponding alkoxy groups. The R ^{15 to} R ²⁴ may be the same or different.

Examples of the compound represented by the general formula (iii-1) include dicyclopentadiene, dimethyldicyclopentadiene, diethyldicyclopentadiene and the like.
In addition, the general formula (iii-2)

（式中、ｂは０，１又は２を示す。）

(In the formula, b represents 0, 1 or 2.)

Can be mentioned. Examples of the compound represented by the general formula (iii-2) include bicyclo [2.2.1] hept-2,5-diene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3,8-dodecadiene, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 0 ^9,14] 4,11 Heputadekajien and the like.
General formula (iii-3)

（式中、ｅは０〜６の整数を示す。）

(In the formula, e represents an integer of 0 to 6.)

Can be mentioned. Examples of the compound represented by the general formula (iii-3) include 1,1-bis (5-bicyclo [2.2.1] hept-2-enyl) methane and 1,2-bis (5- Bicyclo [2.2.1] hepta-2-enyl) ethane, 1,6-bis (5-bicyclo [2.2.1] hepta-2-enyl) hexane and the like can be mentioned.

(Iv) Polyene having a styrene skeleton / α-olefin skeleton in the molecule General formula (iv)

（式中、Ｒ²⁵は、炭素数１〜２０の二価の炭化水素基を示し、Ｒ²⁶は、ハロゲン原子又は炭素数１〜８の炭化水素基を示し、Ｒ²⁷及びＲ²⁸は、それぞれ水素原子、ハロゲン原子又は炭素数１〜８の炭化水素基を示す。ｆは、０〜４の整数である。）

(Wherein, R ²⁵ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, R ²⁶ represents a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ²⁷ and R ²⁸ each represent A hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and f is an integer of 0 to 4.)

Can be mentioned. In the general formula (iv), the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ²⁵ includes, for example, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and a C 7 to C 20 group. 20 alkylarylene groups or arylalkylene groups, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a phenylene group, and a tolylene group. Examples of the halogen atom in R ²⁶ include chlorine, bromine, fluorine, and iodine, and examples of the hydrocarbon group having 1 to 8 carbon atoms include methyl, ethyl, propyl, butyl, and pentyl groups. Examples thereof include a saturated hydrocarbon group represented by an alkyl group and an unsaturated hydrocarbon group such as a vinyl group. Examples of the halogen atom and the hydrocarbon group having 1 to 8 carbon atoms in R ²⁷ and R ²⁸ include the same as those described above. As the compound represented by the general formula (iv), specifically, when R ²⁵ in the general formula (iv) is an alkylene group, for example, p- (2-propenyl) styrene, m- (2 -Propenyl) styrene, p- (3-butenyl) styrene, m- (3-butenyl) styrene, o- (3-butenyl) styrene, p- (4-pentenyl) styrene, m- (4-pentenyl) styrene, o- (4-pentenyl) styrene, p- (7-octenyl) styrene, p- (1-methyl-3-butenyl) styrene, p- (2-methyl-3-butenyl) styrene, m- (2-methyl -3-butenyl) styrene, o- (2-methyl-3-butenyl) styrene, p- (3-methyl-3-butenyl) styrene, p- (2-ethyl-3-butenyl) styrene, p- (2 -Ethyl-4-pen (Tenyl) styrene, p- (3-butenyl) -α-methylstyrene, m- (3-butenyl) -α-methylstyrene, o- (3-butenyl) -α-methylstyrene and the like.

When R ²⁵ in the general formula (iv) is an arylene group, for example, 4-vinyl-4 ′-(3-butenyl) biphenyl, 4-vinyl-3 ′-(3-butenyl) biphenyl, -Vinyl-4 '-(4-pentenyl) biphenyl, 4-vinyl-2'-(4-pentenyl) biphenyl, 4-vinyl-4 '-(2-methyl-3-butenyl) biphenyl and the like. .

(V) Polyene having cyclic olefin skeleton / α-olefin skeleton in the molecule General formula (v-1)

（式中、Ｒ¹⁵〜Ｒ²⁴はそれぞれ水素原子、ハロゲン原子又は炭素数１〜２０の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、Ｒは炭素数２〜２０のアルケニル基で、ｎは０又は３以上の整数を示す。）

(Wherein, R ^{15 to} R ²⁴ each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R is an alkenyl having 2 to 20 carbon atoms) And n represents 0 or an integer of 3 or more.)

And a compound comprising a norbornene skeleton and an unsaturated group.
Examples of the compound represented by the general formula (v-1) include 5-vinyl-2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (allyl) -2-norbornene, (4-pentenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, and the like.
Furthermore, the general formula (v-2)

（式中、ｃは１又は２、ｄは０〜１１の整数を示す。）

(In the formula, c represents 1 or 2, and d represents an integer of 0 to 11.)

Can be mentioned. Examples of the compound represented by the above general formula (v-2) include 5-vinylbicyclo [2.2.1] hept-2-ene and 5-allylbicyclo [2.2.1] hept-2-ene. Ene, 5- (3-butenyl) bicyclo [2.2.1] hept-2-ene, 8-vinyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 11-vinylhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, and the like.

(Vi) Polyene having styrene skeleton / cyclic olefin skeleton in the molecule General formula (vi-1)

（式中、Ｒ¹ は水素原子又は炭素数１〜１０の炭化水素基、Ｒ² は水素原子、炭素数１〜１０の炭化水素基、エーテル基又はエステル基、Ｒ³ は炭素数１〜２０の炭化水素基、ケイ素原子、エーテル基又はエステル基、Ｒ⁴ は水素原子、炭素数１〜１０の炭化水素基又はケイ素原子を示す。ただし、芳香環と環状オレフィンとが直接結合している場合、Ｒ³ は不要である。）

(Wherein, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an ether group or an ester group, and R ³ is a carbon atom having 1 to 20 carbon atoms. R ⁴ represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a silicon atom, provided that an aromatic ring is directly bonded to a cyclic olefin. , R ³ is not required.)

Or a compound represented by the general formula (vi-2)

（式中、Ｒ¹ 、Ｒ² 、Ｒ³ 及びＲ⁴ 上記と同様であり、ｎは０以上の整数である。）

(Wherein, R ¹ , R ² , R ³ and R ⁴ are the same as described above, and n is an integer of 0 or more.)

Can be mentioned. Specific examples of these compounds include those represented by the following formula.

In the catalyst used in the production method of the present invention, the catalyst component (A) contains (A-1) a titanium trichloride-based compound or (A-2) titanium, magnesium and a halogen element as essential components. (A-1) Titanium trichloride-based compounds obtained by reducing TiCl ₄ with a hydrogen atom [TiCl ₃ (H)], those reduced with titanium metal [TiCl ₃ (T)], and those reduced with aluminum metal There are many types including [TiCl ₃ (A)] and those reduced with an organoaluminum metal (eg, TiCl ₃ by reduction with diethylaluminum chloride). In the present invention, a difference in catalytic activity may occur depending on the type of TiCl ₃ used, and the obtained catalytic performance is not necessarily the same. However, _three types of so-called Ziegler catalysts (including Ziegler-Natta catalysts) are used. Everything that can be used as a titanium chloride-based catalyst component can be used. Therefore, the titanium trichloride-based catalyst component does not need to be pure TiCl ₃ , but may be, for example, one obtained by adding 1/3 mol of AlCl ₃ to TiCl ₃ (A). A component may be introduced, or it may inevitably or intentionally contain a small amount of unreduced TiCl ₄ , overreduced TiCl _2, or an oxidation product of a reducing agent.

(A-2) Examples of the catalyst containing titanium, magnesium and a halogen element as essential components include JP-A-53-45688, JP-A-54-3894, JP-A-54-31092, and JP-A-54-31092. JP-A-54-39483, JP-A-54-94591, JP-A-54-118484, JP-A-54-131589, JP-A-58-5309, and JP-A-58-5310. JP-A-58-5311, JP-A-58-8706, JP-A-58-27732, JP-A-58-32604, JP-A-58-32605, and JP-A-58-32605 -67703, JP-A-58-117206, JP-A-58-127708, JP-A-58-183708, JP-A-58-183709, and JP-A-59-1 9905 JP, Sho 59-149906, JP-Sho 64-69608 discloses, it is possible to use those described in JP-A-10-25318 JP and Hei 11-269218 Patent Publication.
In a catalyst containing titanium, magnesium and a halogen element as essential components, at least one of the titanium compound and the magnesium compound may contain a halogen element, or any other component may contain a halogen element. Examples of titanium compounds include tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium. A tetrahalogenated titanium such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; a trihalide such as methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride and ethoxytitanium tribromide; Halogenated alkoxytitaniums such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium dibromide, etc. Halogenated dialkoxytitanium; monohalogenated trialkoxytitanium such as trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride, and tri-n-butoxytitanium chloride. it can. Among these, a titanium compound having a high halogen content, particularly titanium tetrachloride, is preferable from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more.

Examples of the magnesium compound include alkyl magnesium and aryl magnesium such as dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, diphenyl magnesium and dicyclohexyl magnesium; dimethoxy magnesium, diethoxy magnesium and dipropoxy magnesium. Magnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium, dicyclohexyloxymagnesium, etc., alkoxymagnesium, allyloxymagnesium; ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, isopropylmagnesium Alkyl magnesium halides such as chloride, isobutyl magnesium chloride, t-butyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium chloride, and butyl magnesium iodide; aryl magnesium halide; Alkoxymagnesium halides such as cyclohexyloxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide, and ethoxymagnesium iodide, allyloxymagnesium halides; and magnesium halides such as magnesium chloride, magnesium bromide, and magnesium iodide. This Can.
Among these magnesium compounds, from the viewpoint of polymerization activity and stereoregularity, magnesium halide, alkoxymagnesium, alkylmagnesium, and alkylmagnesium halide can be preferably used. The above magnesium compound can be prepared from metallic magnesium or a compound containing magnesium.

The catalyst component (A-2) may contain (iii) an electron donating compound (a) in addition to (i) a titanium compound and (ii) a magnesium compound. Examples of the electron donating compound (a) include alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, esters of organic or inorganic acids, and ethers such as monoethers, diethers and polyethers. And nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates. Of these, esters of polycarboxylic acids are preferred, and esters of aromatic polycarboxylic acids are more preferred. From the viewpoint of polymerization activity, monoesters and / or diesters of aromatic dicarboxylic acids are particularly preferred. Further, an aliphatic hydrocarbon in which the organic group in the ester portion is linear, branched or cyclic is preferred.
Specifically, phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid, 5,6,7, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl of dicarboxylic acids such as 8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid and indane-5,6-dicarboxylic acid; t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl , 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methyl Dialkyl esters such as syl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl, and 3-ethylpentyl. . Among these, phthalic acid diesters are preferable, and a linear or branched aliphatic hydrocarbon having 4 or more carbon atoms in the organic group in the ester portion is preferable.
Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, and diethyl phthalate. These compounds may be used alone or in combination of two or more.

The catalyst component (A-2) may contain (iv) a silicon compound in addition to (i) a titanium compound, (ii) a magnesium compound, and (iii) an electron donating compound (a). Examples of the silicon compound include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane, diethoxydichlorosilane, triethoxychlorosilane, propoxytrichlorosilane, dipropoxydichlorosilane, and tripropoxychlorosilane. Can be. Among these, silicon tetrachloride is particularly preferred. These silicon compounds may be used alone or in combination of two or more.
The catalyst component (A-2) may further contain (v) an organoaluminum compound. As the organic aluminum compound, those having an alkyl group, a halogen atom, a hydrogen atom, or an alkoxy group, aluminoxane, and a mixture thereof can be preferably used. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum and trioctylaluminum; dialkyls such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride and dioctylaluminum monochloride Aluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; and chained aluminoxanes such as methylaluminoxane. Among these organic aluminum compounds, trialkyl aluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethyl aluminum, triethyl aluminum, tripropyl aluminum and triisobutyl aluminum are preferred. These organoaluminum compounds may be used alone or in combination of two or more.

The catalyst component (A-2) may further contain (vi) an electron donating compound (b). As the electron donating compound (b), an organic silicon compound having a Si—O—C bond, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among them, from the viewpoint of polymerization activity and stereoregularity, it is preferable to use an organic silicon compound having a Si-OC bond, ethers and esters, and particularly to use an organic silicon compound having a Si-OC bond. Is preferred.
Specific examples of the organosilicon compound having the Si-OC bond include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane , Ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyl Dimethoxysilane, t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane, t-butylisobutyldimethoxysilane Toxysilane, t-butyl (s-butyl) dimethoxysilane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t-butyl Butyldecyldimethoxysilane, t-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, cyclohexyl-t- Butyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis ( , 3-dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, t- Butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane , Cyclopentyl (t-butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t-butyl (Isobutoxy) dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, texyltrimethoxysilane, texylisopropoxydimethoxysilane, texyl (t-butoxy) dimethoxysilane, texylmethyldimethoxysilane, texylethyldimethoxysilane , Texylisopropyldimethoxysilane, texylcyclopentyldimethoxysilane, texylmyristyldimethoxysilane, texylcyclohexyldimethoxysilane, bis (3-methylcyclopentyl) dimethoxysilane, bis (2-ethylcyclopentyl) dimethoxysilane, bis (2,3 -Diethylcyclopentyl) dimethoxysilane, bis (2,4-dimethylcyclopentyl) dimethoxysilane, bis (2,5-dimethylcyclopentyl) dimethoxy Orchid, bis (2,3,4-trimethylcyclopentyl) dimethoxysilane, bis (2,3,4-triethylcyclopentyl) dimethoxysilane, bis (2,3,5-trimethylcyclopentyl) dimethoxysilane, bis (tetramethylcyclopentyl) Dimethoxysilane and the like. These organic silicon compounds may be used alone or in combination of two or more.

Specific examples of the nitrogen-containing compound include 2,6-substituted piperidines such as 2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl 2,2,6,6-tetramethylpiperidine. 2,5-substituted azolidines such as 2,5-diisopropylazolidine and N-methyl 2,2,5,5-tetramethylazolidine; N, N, N ′, N′-tetramethylmethylenediamine, N , N, N ′, N′-tetraethylmethylenediamine and the like; substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine.

Specific examples of the phosphorus-containing compound include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite, and the like. Phosphites and the like. Specific examples of the oxygen-containing compound include 2,6-substituted tetrahydrofurans such as 2,2,6,6-tetramethyltetrahydrofuran and 2,2,6,6-tetraethyltetrahydrofuran; 1,1-dimethoxy-2,3 , 4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, dimethoxymethane derivatives such as diphenyldimethoxymethane, and the like.
Here, (i) the titanium compound is used in an amount of usually 0.5 to 100 mol, preferably 1 to 50 mol, per 1 mol of the (ii) magnesium compound. If this molar ratio is outside the above range, the catalytic activity may be insufficient. Further, (iii) the electron-donating compound (a) or (vi) the electron-donating compound (b) is usually 0.01 to 10 mol, preferably 1 to 10 mol, per 1 mol of magnesium of the magnesium compound. 0.05 to 1.0 mol is used. If the molar ratio deviates from the above range, catalytic activity and stereoregularity may be insufficient. Further, when (iv) a silicon compound is used, it is usually used in an amount of 0.001 to 100 mol, preferably 0.005 to 5.0 mol, per 1 mol of magnesium of the (ii) magnesium compound. If the molar ratio deviates from the above range, the effect of improving catalytic activity and stereoregularity may not be sufficiently exhibited, and the amount of fine powder in the produced polymer may increase.

As a method for preparing the catalyst component (A-2), (1) (i) a titanium compound, (ii) a magnesium compound, and (iii) an electron-donating compound (a) are brought into contact at 120 to 150 ° C to obtain a mixture of 100 to 150. (2) (i) a titanium compound, (ii) a magnesium compound, (iii) an electron donating compound (a) and (iv) a silicon compound at 120 to 150 ° C. (3) contacting (i) a titanium compound, (ii) a magnesium compound and (iii) an electron donating compound (a) to obtain a solid catalyst component, and (vi) an electron donating compound ( b) and (v) a method of contacting an organoaluminum compound, (4) contacting (i) a titanium compound, (ii) a magnesium compound and (iii) an electron-donating compound (a) at 120 to 150 ° C. Clean at 150 ° C After obtaining a catalyst component, a method of contacting (vi) electron-donating compound (b) and (v) an organoaluminum compound.
In addition, (ii) ethoxymagnesium of the magnesium compound is suspended in (vii) alkylbenzene, and thereafter, a titanium tetrachloride and (iii) of (i) titanium compound having a volume ratio to the alkylbenzene of 1/2 or less. ) The solid substance obtained by contacting the phthalic acid diester of the electron-donating compound (a) at 80 to 135 ° C is washed with alkylbenzene, and the solid substance is further subjected to a volume ratio to the alkylbenzene in the presence of alkylbenzene. A method prepared by reacting す る or less of titanium tetrachloride (method described in JP-A-64-69608) can be used. Examples of the alkylbenzene include toluene, xylene, ethylbenzene, propylbenzene, and trimethylbenzene.

In the catalyst used in the production method of the present invention, as the organoaluminum compound (B), the same compounds as those exemplified above as the (v) organoaluminum compound can be used. Specifically, trialkylaluminum, dialkylaluminum monochloride, and alkylaluminum sesquichloride are preferable, and trialkylaluminum is particularly preferable. As trialkylaluminum, triethylaluminum and triisobutylaluminum can be mentioned as preferred compounds.
In the preparation of the catalyst used in the production method of the present invention, (C) an electron donating compound as the third component is used, if necessary. As the electron donating compound (C) as the third component, the same compounds as those exemplified as the above (vi) electron donating compound (b) can be used.
The amount of the catalyst component (A) is usually in the range of 0.00005 to 1 mmol per liter of reaction volume in terms of titanium atom, and the organoaluminum compound (B) is The amount used is such that the aluminum / titanium atomic ratio is usually in the range of 1 to 1000, preferably 10 to 500. If this atomic ratio is outside the above range, the catalytic activity may be insufficient. When (C) an electron donating compound as the third component is used, the molar ratio of (C) the electron donating compound / (B) the organoaluminum compound is usually 0.001 to 5.0, preferably 0.1 to 5.0. An amount is used so as to be in the range of 01 to 2.0, more preferably 0.05 to 1.0. If the molar ratio is outside the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when pre-polymerization is performed, it can be further reduced.

The catalyst can be pre-polymerized before the graft copolymerization is performed. Examples of monomers used in the prepolymerization include ethylene, α-olefins having 3 to 20 carbon atoms, cyclic olefins, styrenes, and polyenes. Specifically, the same as those described above can be used. Among these, the same monomer species as used in the polymerization step [I], ethylene and α-olefins having 3 to 20 carbon atoms are preferred, and more preferably the same as the monomer species used in the polymerization step [I]. Or ethylene and propylene. The concentration of the monomer is preferably from 10 mmol / L to 20 mol / L.

The pre-polymerization amount is usually 0.01 to 200 g / g catalyst (catalyst refers to the sum of all catalyst components such as a catalyst component and an organoaluminum compound), preferably 0.1 to 150 g / g catalyst, more preferably Is a catalyst of 0.3 to 50 g / g. The conditions for the prepolymerization are as follows: a temperature of -30 to 80 ° C, preferably -10 to 40 ° C; The catalyst component is in the range of 2 × 10 ^{−7 to} 2 × 10 ⁻² mol, preferably 2 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol. It is preferable to perform the reaction for a time of 1 second to 8 hours.

The proportions of the catalyst component (A) and the organoaluminum compound (B) used in the catalyst used in the prepolymerization can be the same as those described above, and it is also possible to use (C) an electron donating compound in the same manner as described above. it can. That is, the amount of the catalyst component (A) is usually in the range of 0.00005 to 1 mmol per liter of reaction volume in terms of titanium atom, and the organoaluminum compound (B) is used. Is used in such an amount that the aluminum / titanium atomic ratio is usually in the range of 1 to 1000, preferably 10 to 500. The molar ratio of (C) the electron donating compound / (B) the organoaluminum compound is usually 0.001 to 5.0, preferably 0.01 to 2.0, more preferably 0.05 to 1.0. An amount that is in the range is used.
The prepolymerization method may be any of a slurry polymerization method, a bulk polymerization method and a gas phase polymerization method, and the reactor may be any of a batch type and a continuous type.
The produced prepolymerized catalyst may be stored as it is, may be washed with a solvent and separated as a solid substance, or may be stored again in a state of being dispersed in a solvent. Storage is preferably performed at a low temperature of 30 ° C. or lower and in an inert atmosphere. Further, the prepolymerization can be carried out in the same reactor as that used in the polymerization step [I], and then can be supplied to the polymerization step [I].

Examples of the polymer produced in the polymerization step [I] include the following polymers (a) to (e) each containing a polyene. In the present invention, (a), (b) and (c) are preferred.
(A) an ethylene homopolymer or a copolymer containing 50 mol% or more of ethylene units (b) a propylene homopolymer or a copolymer containing 50 mol% or more of propylene units (c) α having 4 to 20 carbon atoms -Homopolymer of olefin or copolymer containing 50 mol% or more of α-olefin having 4 to 20 carbon atoms (d) Homopolymer or copolymer of styrene [Copolymer of plural types of styrenes] , A copolymer comprising styrenes (≧ 50 mol%) and another monomer]
(E) Homopolymers or copolymers of cyclic olefins [Copolymers of plural types of cyclic olefins, copolymers of cyclic olefins (≧ 50 mol%) and other monomers]

Specific examples of the polymer (a) include HDPE (high-density polyethylene), ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / octene copolymer, and ethylene / decene copolymer. Polymers, ethylene / eicosene copolymers, ethylene / styrene copolymers, ethylene / p-methylstyrene copolymers, ethylene / p-phenylstyrene copolymers, and ethylene / norbornene copolymers Copolymers containing a polyene may be mentioned.
Specific examples of the polymer (b) include isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, low stereoregular isotactic polypropylene, propylene / ethylene copolymer, propylene / butene copolymer, propylene / Hexene copolymer, propylene / octene copolymer, propylene / decene copolymer, propylene / eicosene copolymer, propylene / norbornene copolymer, propylene / styrene copolymer, propylene / p-methylstyrene copolymer, Copolymers containing polyene in a propylene-based polymer such as a propylene / p-phenylstyrene copolymer and a low stereoregular isotactic polypropylene / α-olefin copolymer such as ethylene are exemplified.
Specific examples of the polymer (c) include polybutene, butene / ethylene copolymer, butene / propylene copolymer, butene / decene copolymer, butene / eicosene copolymer, butene / styrene copolymer, butene / Copolymers containing a polyene in an α-olefin-based polymer such as a norbornene copolymer, poly-4-methyl-pentene-1, and a copolymer in which butene is changed to 4-methyl-pentene-1 are exemplified.
Specific examples of the polymer (d) include isotactic polystyrene, atactic polystyrene, styrene / ethylene copolymer, styrene / propylene copolymer, styrene / octene copolymer, styrene / decene copolymer, styrene / Styrene-based polymers such as eicosene copolymers, styrene / norbornene copolymers, and styrene / p-methylstyrene copolymers include polyene-containing copolymers.
Specific examples of the polymer (e) include norbornene / polyene copolymer, norbornene / ethylene / polyene copolymer, norbornene / propylene / polyene copolymer, norbornene / butene / polyene copolymer, norbornene / octene / polyene Copolymer, norbornene / styrene / polyene copolymer, norbornene / ethylene / propylene / polyene copolymer, norbornene / ethylene / styrene / polyene copolymer, norbornene / ethylidene norbornene / polyene copolymer, and the like.
In the present invention, polyethylene / polyene copolymer, ethylene / propylene / polyene copolymer, ethylene / butene / polyene copolymer, ethylene / hexene / polyene copolymer, ethylene / octene / polyene copolymer, isotactic Tic polypropylene / polyene copolymer, isotactic polypropylene / ethylene / polyene copolymer, isotactic polypropylene / octene / polyene copolymer, butene / polyene copolymer, 4-methyl-1-pentene / polyene copolymer Copolymer, 3-methyl-1-butene / polyene copolymer, 4-methyl-1-pentene / ethylene / polyene copolymer, and 4-methyl-1-pentene / propylene / polyene copolymer are preferred.
The stereoregularity of the polymer is an atactic structure, a syndiotactic structure or an isotactic structure, and preferably has an isotactic structure. [Mmmm] = 40 to 99.9% in the case of an isotactic structure, and [rrrr] = 35 to 99.9% in the case of a syndiotactic structure.

The polymerization in the polymerization step [I] may be any of a slurry polymerization method, a bulk polymerization method and a gas phase polymerization method, and the reactor may be any of a batch type and a continuous type. When the polymerization is performed in a solvent, examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and kerosene. Examples of the aliphatic hydrocarbon include propane, butane, pentane, hexane, heptane, octane, decane, and the like. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, and mixed isomers of xylene. Examples of the alicyclic hydrocarbon include cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and the like. Also, a mixed solvent of these solvents such as heptane / toluene can be used.
The polymerization is carried out under the conditions of a temperature of -100 to 300 ° C, preferably 0 to 200 ° C, a pressure of 0.001 to 10 MPa, preferably 0.05 to 3 MPa, and a polymerization time of 10 seconds to 10 hours, preferably 1 minute to 5 hours. Is preferred. The molecular weight of the polymer produced in the polymerization step [I] can be controlled by the amount of hydrogenation, polymerization temperature, monomer concentration, polymerization pressure and the like. The composition of the polymer can be changed by changing the charged amount of the monomer, and the content of the polyene in the polymer can be increased or decreased by changing the charged amount of the polyene.
In the polymer produced in the polymerization step [I], the molecular weight represented by the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is usually 0.05 to 20 deciliters / g, preferably 0.2 to 20 deciliters / g. It is 18 deciliter / g, more preferably 0.3 to 16 deciliter / g, and most preferably 0.4 to 13 deciliter / g. When the intrinsic viscosity [η] is less than 0.05 deciliter / g, physical properties such as rigidity and impact resistance are reduced, and when the intrinsic viscosity is more than 20 deciliter / g, moldability may be reduced.
In the polymer produced in the polymerization step [I], the molecular weight distribution is not particularly limited, and may be in a usual range. Preferably, the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC (gel permeation chromatography) is in the range of 1.8 to 60, and 3.5 to 3.5. 15 is more preferred. Usually, the molecular weight distribution is almost determined by the catalyst used. To expand the molecular weight distribution, in the polymerization step [I], conditions for changing the molecular weight such as, for example, hydrogen concentration, polymerization pressure and polymerization temperature are used. You can change it.
In the polymer produced in the polymerization step [I], the polyene content is usually more than 0 and 30 mol% or less, preferably more than 0 and 25 mol% or less, more preferably more than 0 and 20 mol% or less. More preferably, it is more than 0 to 15 mol%, still more preferably, more than 0 to 10 mol%, still more preferably 0.001 to 5 mol%, more preferably 0.001 to 2.5 mol%, and most preferably. Is 0.001 to 2 mol%. When the polyene content is 0, the effect of the present invention as a resin compatibilizer and the effect of improving the melt fluidity are poor, and when the polyene content exceeds 30 mol%, the melt fluidity is inferior. .

The polymer produced in the polymerization step [I] may partially have a long-chain branch formed by a polyene. The structure of the long-chain branch has a branch length of 10 carbon atoms to a molecular weight similar to that of the main chain, and the number of branches is 0.0001 to 10 per 1000 carbon atoms. The structure of the long-chain branch can be controlled by increasing the amount of the polyene used in the polymerization step [I].
The following methods (a) and (b) are available as methods for detecting long-chain branching.
(A) Evaluation method based on shear rate dependence of melt viscosity A polyolefin having a long chain branch even in a trace amount detects a long chain branched structure by utilizing that the shear rate dependence of the melt viscosity is different from a polyolefin containing no branches. How to That is, when long-chain branching is present, the dependency of the melt viscosity on the shear rate is greater than in a system without long-chain branching. Therefore, the presence of long-chain branches can be detected by comparing the linear polymer having no long-chain branches with the graft polymer.
This method is known to be affected by the molecular weight distribution. In this case, the molecular weight distribution obtained by GPC (gel permeation chromatography) is almost the same, That is, a comparison is made with a polyolefin linear polymer having the same monomer species and substantially the same composition ratio. Further, as another method, a polyolefin having apparently no branching and having the same monomer species and substantially the same composition ratio is used, and the shear rate dependence of the melt viscosity on the molecular weight distribution is determined in advance, and the polymerization step [I] is performed. The presence of long-chain branching can be detected by comparing the same molecular weight distribution region as that of the above polymer. A specific measurement method given as an example is as follows.

(1) Measuring method Apparatus: Melt viscosity measuring apparatus RMS800 (Rheometrics)
<Measurement conditions>
Temperature: at least the highest melting point or the highest glass transition temperature of the polymer in the polymerization step [I]
Usually a temperature 10 to 60 ° C. higher than the highest melting point of the polymer in the polymerization step [I].
Usually, a temperature higher by 10 to 200 ° C. than the maximum glass transition temperature of the polymer in the polymerization step [I]. Strain: 15%
Angular velocity: 0.01 to 300 rad / s
Sample shape: cone plate

The melt viscosity with respect to the shear rate (that is, the angular velocity ω) is measured with the above apparatus and conditions.
<Data processing>
The angular velocity at which the melt viscosity is 10 Pa · s is ω ₁ , and the angular velocity at which the melt viscosity is 10 ³ Pa · s is ω _2, and the value of ω ₂ / 10ω ₁ is calculated.
<Comparative sample>
A polyolefin containing no branch and having the same monomer species and the same composition ratio as the polymer in the polymerization step [I] is used.
(2) Detection of long-chain branching Case 1: The ratio of the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer in the polymerization step [I] to the molecular weight distribution of the comparative sample is 0.8 to the value of ω ₂ / 10ω ₁ of the polymer when polymerization process [I] in the range 1.8 times the N ^1, when the value of ω ₂ / 10ω ₁ of the comparative sample was as N ^0, the following equation ( 5)
1.01 ≦ N ¹ / N ⁰ ≦ 80 (5)
The case where it is satisfied is evaluated as a long chain branched structure.
Case 2: When the ratio between the molecular weight distribution of the polymer in the polymerization step [I] and the molecular weight distribution of the comparative sample is out of the range of Case 1, the value of N ⁰ with respect to the molecular weight distribution is previously determined by comparing a plurality of comparative samples having different molecular weight distributions. Is determined using That is, N ⁰ (the value of ω ₂ / 10ω ₁ of the comparative sample) is plotted against the molecular weight distribution (Mw / Mn) obtained from the GPC of the comparative sample, and a monotonically increasing function N ⁰ = f (Mw / Mn) is obtained from this relationship. ) Is determined by the least squares method.
In this relation, the case where N ¹ obtained from the value of the molecular weight distribution (Mw / Mn) of the polymer in the polymerization step [I] satisfies the above formula (5) is evaluated as a graft structure.

In the above equation (5),
1.02 ≦ N ¹ / N ⁰ ≦ 70 is preferred,
1.03 ≦ N ¹ / N ⁰ ≦ 65 is more preferable,
1.04 ≦ N ¹ / N ⁰ ≦ 60 is more preferable,
Most preferably, 1.05 ≦ N ¹ / N ⁰ ≦ 55.
When N ¹ / N ⁰ is less than 1.01, long-chain branching is small, and the effect of the present invention may not be exhibited. If N ¹ / N ⁰ exceeds 80, gel or the like may be generated, and the moldability may be reduced.
(B) Evaluation method by GPC-light scattering
(1) Determination method of branch parameter (α) GPC / MALLS (multi-angle light scattering) measurement of a sample was performed, and at each elution position, <R ² > ^1/2 (radius 2) Square root of the square mean), the weight average molecular weight Mw was obtained from the intercept of the scattered light intensity, the logarithm of <R ² > ^1/2 and Mw was plotted, and the slope α was calculated by the least squares method.
The GPC / MALLS measurement of the sample was performed under the following conditions.
Solvent: 1,2,4-trichlorobenzene Concentration: 0.3% (w / v)
Melting temperature: 135 ° C
Measuring device: Waters 150-C (GPC)
DAWN EOS ^TM manufactured by Wyatt Technology
(Multi-angle light scattering)
Column: Showa Denko Corporation ShodexUT806MLT
(7.8mmφ × 50cm)
Injection volume: 300 microliters Flow rate: 1.0 milliliter / min
Concentration increment of refractive index (dn / dc): -0.095

(2) Evaluation of long-chain branching The above measurement was carried out using the same polymer species as the polymer in the polymerization step [I] and the polymer in the polymerization step [I], and similar copolymer compositions (error of about ± 10%). ) Perform on both linear polymers and determine the α value. When the ratio of the α values [(α) ^L / (α) ^B ] exceeds 1, it is evaluated that a long-chain branch exists. Here, (α) ^L indicates the α value of the linear polymer, and (α) ^B indicates the α value of the polymer in the polymerization step [I].
(Α) ^L / (α) ^B is
1.0 <(α) ^L / (α) ^B ≦ 10 is preferred,
1.0 <(α) ^L / (α) ^B ≦ 8 is more preferable,
1.0 <(α) ^L / (α) ^B ≦ 6 is more preferable,
1.0 <(α) ^L / (α) ^B ≦ 4 is still more preferable,
1.0 <(α) ^L / (α) ^B ≦ 2 is still more preferable,
1.0 <(α) ^L / (α) ^B ≦ 1.5 is more preferable,
Most preferably, 1.0 <(α) ^L / (α) ^B ≦ 1.3.
When there is no long-chain branch, (α) ^L / (α) ^B is 1. If (α) ^L / (α) ^B exceeds 10, gels may be generated and moldability may be reduced.

The concentration (titanium atom concentration) of the main catalyst component of the catalyst used in the polymerization step [I] is usually 3 × 10 ^{−7 to} 5 × 10 ⁻² mol / l, preferably 1 × 10 ^{−7 to} 3 × 10 ^{7. -2} mol / l, more preferably 1 × 10 ⁻⁶ to 2 × 10 ⁻² mol / l.
The ratio of the main catalyst component and the total monomers used in the polymerization process [I] is the main catalyst component 1 × 10 ^-7 mol, in total monomers ^10-3 to ² mole (mole ratio 1 : 10 ⁴ to 10 ⁹ ), more preferably 2 × 10 ⁻³ to 1 mol (molar ratio 1: 2 × 10 ⁴ to 10 ⁻⁷ ). The use ratio of the main catalyst component and the polyene is preferably 10 ⁻⁵ to 1 mol (molar ratio of 1 × 10 ² to 10 ⁷ ) with respect to 1 × 10 ⁻⁷ mol of the main catalyst component, and 2 × 10 ⁻ More preferably, it is ^{5 to} 0.8 mol (molar ratio 1: 2 × 10 ² to 8 × 10 ⁶ ).
When a prepolymerized catalyst is used, the following implementation method can be used.

(1) The catalyst charge ratio (the aluminum / titanium atomic ratio of the organoaluminum compound is 1 to 1000, preferably 10 to 500, and the electron donating compound / organoaluminum compound molar ratio is 0, based on the titanium atom concentration of the prepolymerized catalyst). 0.00001 to 5.0, preferably 0.01 to 2.0, and more preferably 0.05 to 1.0. (The electron donating compound and the organoaluminum compound used here are prepolymerized.) May be the same as or different from those used in (1)).
(2) A method in which the electron-donating compound is used without using an electron-donating compound in performing the above-described catalyst charging ratio based on the titanium atom concentration of the pre-polymerization catalyst (the organoaluminum compound used in the pre-polymerization was used). May be the same or different.)
(3) A method of conducting without using an organoaluminum compound in carrying out the above catalyst charge ratio based on the titanium atom concentration of the prepolymerized catalyst (the electron donating compound used here was used in the prepolymerization. May be the same or different.)

The polyene has the same polymerization reaction site and has the same polymerization reactivity. For example, the above-mentioned general formula (i), general formula (iii-2), general formula (iii-3) and general formula (iii-3) In the case of the polyene represented by ii), specifically, p-divinylbenzene, the amount of the polyene to be used is generally 5.0 × 10 ⁻⁷ to 1 × 1 g per 1 g of the polymer produced in the polymerization step [I]. 2.0 × 10 ⁻² mol, preferably 7.0 × 10 ^{−7 to} 7.0 × 10 ⁻³ mol, more preferably 1.0 × 10 ^{−6 to} 6.0 × 10 ⁻³ mol, furthermore Preferably it is 1.5 * 10 < ^-6 > -5.0 * 10 < ^-3 > mol, Most preferably, it is 2.0 * 10 < ^-6 > -4.0 * 10 < ^-3 > mol.
The polyene has a structure in which the polymerization reaction sites are not the same and the polymerization reactivity is non-equivalent. For example, the above-mentioned general formula (iii-1), general formula (IV), general formula (v-1), general formula (v-1) v-2), polyenes represented by the general formula (vi-1), the general formula (vi-2) and the general formula (ii), specifically, o-divinylbenzene, m-divinylbenzene and a nuclear-substituted product thereof , Which has a p-divinylbenzene skeleton and is a nucleus-substituted product, such as 1-substituted substituted p-divinylbenzene and 3-substituted substituted p-divinylbenzene, the amount of the polyene used in the polymerization step [I] Is usually 2.2 × 10 ^{−6 to} 5.0 × 10 ⁻² mol, preferably 3.5 × 10 ^{−6 to} 3.5 × 10 ⁻² mol, more preferably 1 g of the polymer produced in the above. 5.0 × 10 ^-6 ~3.0 × 10 ^-2 mol, more preferably 7.5 × 10 ^-6 to 2.5 10 ^-2 mol, most preferably 1.0 × 10 ^-5 to 2.0 × 10 ^-2 mol.
If the amount of the polyene is too small, the concentration of the polyene at the starting point of the grafting reaction in the polymerization step [II] will be low. In the present invention, those of the general formulas (i), (ii) and (iv) are preferred.

The polymer produced in the polymerization step [I] is washed in the washing step. Washing refers to all operations for removing unreacted polyene contained in the reaction mixture in the polymerization step [I] to the outside of the reaction system. Specific washing methods include (1) using a solvent in the polymerization step. There are a method of removing unreacted polyene from the reaction mixture generated in [I] by washing, and (2) a method of removing unreacted polyene component by drying. In both of the cleaning methods (1) and (2), it is preferable to use an inert gas such as nitrogen or argon and to remove the polyene under an inert atmosphere. As the solvent used in the washing method (1), the same solvents as those exemplified in the polymerization step [I] can be used, and it is preferable to use the same solvent as used in the polymerization step [I].
Regarding a specific method of the washing method (1), a case where the polymerization method in the polymerization step [I] is slurry polymerization, bulk polymerization, or gas phase polymerization will be described. In the case of slurry polymerization, the cleaning method includes at least the following steps 1 to 3.

Step 1 is a step of separating the solid component from the polymerization solvent and the components dissolved in the solvent after the completion of the polymerization. This separation method is a method in which stirring is stopped and the mixture is allowed to stand, a solid component is precipitated in the lower layer, and then the solvent component in the upper layer is extracted.The reaction mixture is put into a centrifugal separator to separate the solvent component and the solid component. There are ways to do that. Separation is performed at a temperature of -30 to 80 ° C. Upon separation, it is desirable to reduce the liquid content of the solid component as much as possible.
Step 2 is a step of washing the solid components with the above-mentioned solvent. Washing can be performed by stirring, and washing is performed at a washing temperature of −30 to 80 ° C. for a washing time of 10 seconds to 5 hours with stirring. The amount of the solvent to be used is 100 to 2000 ml per 100 g of the solid component, and the solvent is represented by the general formula R _v AlQ _3-v
(Wherein, R represents an alkyl group having 1 to 10 carbon atoms, Q represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group or a halogen atom having 6 to 20 carbon atoms, and v is an integer of 1 to 3) Is)
It is preferable that the alkylaluminum compound represented by the following formula is contained at a concentration of 0.0005 to 0.1% by mass (5 to 1000% by mass), more preferably 0.0008 to 0.05% by mass (8 to 500% by mass). , Most preferably 0.0015 to 0.03 mass% (15 to 300 massppm). As the alkylaluminum compound, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormal hexylaluminum, diethylaluminum chloride, ethylaluminum dichloride, and ethylaluminum sesquichloride are preferable.
Step 3 is a step of recovering the washing solvent, and can be performed in the same manner as in step 1 described above. When the cleaning is repeated, steps 2 and 3 may be repeated.
When the polymerization method in the polymerization step [I] is bulk polymerization, it differs depending on whether the liquid phase is a gas or a liquid at normal temperature and normal pressure. When the liquid phase is a gas under normal temperature and normal pressure, Step 1 is a step of removing the liquid phase by depressurization. When the liquid phase is liquid at normal temperature and normal pressure, Step 1 is the same process as Step 1 in the slurry polymerization. Steps 2 and 3 are the same as steps 2 and 3 in the slurry polymerization.
When the polymerization method in the polymerization step [I] is gas phase polymerization, washing is performed in steps 2 and 3 in slurry polymerization.

The washing method (2) (a method of removing unreacted polyene components by drying) includes two methods, and one is a method of using one or both of heating and reduced pressure. Washing by this method is usually performed at a temperature of 50 ° C. to a temperature lower than the melting point of the polymer in the polymerization step [I], and under a reduced pressure of 1.33 × 10 ^{−2 to} 1.33 × 10 ⁴ Pa. Another method of the cleaning method (2) is a method of removing unreacted polyene components under a stream of an inert gas such as nitrogen gas. In the cleaning by this method, the inert gas is heated to a temperature of 50 to 200 ° C., and the polymer of the polymerization step [I] is stirred in the inert gas or the polymer of the polymerization step [I] in a fluid state is heated. Through an inert gas heated to a temperature of 50 to 200 ° C. and drying.
The recovery rate of the polyene removed by the washing method (1) can be determined as follows. Assuming that the recovered solvent amount is B _n (unit: liter) of the total solvent amount _An (unit: liter) in a certain washing step n, the polyene recovery rate is represented by B _n / A _n , The recovery is represented by [1- ( _Bn / _An )]. In the washing step (n + 1) subsequent to the washing step n, the recovery rate of the polyene is B _{n + 1} / A _{n + 1} , and the recovery rate of the polyene in the cleaning step (n + 1) is [1- (B _n / A _n ). ] × (B _{n + 1} / A _{n + 1} ). When the cleaning step is repeated a plurality of times, the sum of the recovery rates of polyene in each of these cleaning steps is the total recovery rate of polyene. Here, n = 0 corresponds to the operation of extracting and recovering unreacted polyene that is performed first after the end of the polymerization step [I], and is usually n = 0 to 5.
The recovery rate of the polyene removed by the washing method (2) is obtained as a ratio of the weight of the polyene recovered as a condensate and the weight of the polyene not participating in the copolymerization.
In the present invention, the recovery of polyene is preferably 70% by mass or more, more preferably 75% by mass or more, further preferably 78% by mass or more, and most preferably 80% by mass or more. If the recovery rate of the polyene is less than 70% by mass, gel components frequently occur in the polymerization step [II], and the physical properties and processing performance of the produced graft copolymer may be reduced.

The polymerization step [II] is a polymerization step for performing graft polymerization on the polymer containing a polyene residue obtained in the polymerization step [I]. The monomer used in the polymerization step [II] is at least one monomer selected from ethylene, α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrenes as in the polymerization step [I]. The same kind of monomer as the polymerization step [I] or a different kind of monomer may be used.
The polymerization chains produced in the polymerization step [II] include the following polymerization chains (a) to (e). In the present invention, (a), (b) and (c) are preferred.
(A) an ethylene homopolymer or a polymerization chain containing 50 mol% or more of ethylene units (b) a propylene homopolymer or a polymerization chain containing 50 mol% or more of propylene units (c) an α-olefin having 4 to 20 carbon atoms Or a polymerization chain containing 50 mol% or more of an α-olefin having 4 to 20 carbon atoms (d) A homopolymerization chain or a copolymerization chain of styrenes [a copolymerization chain comprising a plurality of types of styrenes, styrenes] (≧ 50 mol%) and another monomer)
(E) Homopolymerization chain or copolymerization chain of cyclic olefins [copolymerization chain consisting of plural types of cyclic olefins, copolymerization chain consisting of cyclic olefins (≧ 50 mol%) and other monomers]

Specific examples of the polymerization chain (a) include HDPE (high-density polyethylene) chain, ethylene / propylene copolymer chain, ethylene / butene copolymer chain, ethylene / hexene copolymer chain, ethylene / octene copolymer chain, ethylene / decene Examples include a copolymer chain, an ethylene / eicosene copolymer chain, an ethylene / styrene copolymer chain, an ethylene / p-methylstyrene copolymer chain, an ethylene / p-phenylstyrene copolymer chain, and an ethylene / norbornene copolymer chain.
Specific examples of the polymerization chain (b) include an isotactic polypropylene chain, a syndiotactic polypropylene chain, an atactic polypropylene chain, a low stereoregular isotactic polypropylene chain, a propylene / ethylene copolymer chain, and a propylene / butene copolymer. Chain, propylene / hexene copolymer chain, propylene / octene copolymer chain, propylene / decene copolymer chain, propylene / eicosene copolymer chain, propylene / norbornene copolymer chain, propylene / styrene copolymer chain, propylene / p-methylstyrene Copolymer chains, propylene / p-phenylstyrene copolymer chains and low stereoregular isotactic / polypropylene / α-olefin chains such as ethylene.
Specific examples of the polymerization chain (c) include polybutene chain, butene / ethylene copolymer chain, butene / propylene copolymer chain, butene / decene copolymer chain, butene / eicosene copolymer chain, butene / styrene copolymer chain, and butene chain. / Norbornene copolymer chain, poly-4-methyl-pentene-1 and copolymer chain obtained by changing butene to 4-methyl-pentene-1.
Specific examples of the polymerization chain (d) include an isotactic polystyrene chain, an atactic polystyrene chain, a styrene / ethylene copolymer chain, a styrene / propylene copolymer chain, a styrene / octene copolymer chain, a styrene / decene copolymer chain, Examples include a styrene / eicosene copolymer chain, a styrene / norbornene copolymer chain, and a styrene / p-methylstyrene copolymer chain.
Specific examples of the polymerization chain (e) include a norbornene polymerization chain, a norbornene / ethylene copolymer chain, a norbornene / propylene copolymer chain, a norbornene / butene copolymer chain, a norbornene / octene copolymer chain, a norbornene / styrene copolymer chain, Examples include a norbornene / ethylene / propylene copolymer chain, a norbornene / ethylene / styrene copolymer chain, and a norbornene / ethylidene norbornene copolymer chain.

Examples of the graft polymer obtained through the polymerization step [I], the washing step and the polymerization step [II] include those shown in Table 1, and preferred examples of the polymer produced in the polymerization step [I] are also described. I do.

The polymerization in the polymerization step [II] may be any of a slurry polymerization method, a bulk polymerization method, and a gas phase polymerization method, and the reactor may be any of a batch type and a continuous type. When the polymerization is carried out in a solvent, examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and kerosene. Examples of the aliphatic hydrocarbon include propane, butane, pentane, hexane, heptane, octane, decane, and the like. Examples of the aromatic hydrocarbon include benzene, toluene, xylene, and mixed isomers of xylene. Examples of the alicyclic hydrocarbon include cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and the like. Also, a mixed solvent of these solvents such as heptane / toluene can be used.
The polymerization is performed at a temperature of -100 to 300 ° C, preferably 0 to 200 ° C, a pressure of 0.001 to 10 MPa, preferably 0.05 to 3 MPa, a polymerization time of 10 seconds to 10 hours, preferably 1 minute to 5 hours. The polymerization amount relative to [I] (the value of the ratio of the mass of the polymer generated in the polymerization step [II] to the weight of the polymer generated in the polymerization step [I] expressed as a percentage) is 5 to 600%, preferably 6 to 500%, More preferably, it is performed under the conditions of 7 to 450%, further preferably 8 to 400%, more preferably 9 to 350%, and most preferably 10 to 300%. The molecular weight of the polymer produced in the polymerization step [II] can be controlled by the amount of hydrogenation, polymerization temperature, monomer concentration, polymerization pressure and the like. The composition of the polymer can be adjusted by changing the amount of the charged monomer. Also, a small amount of polyene can be added as long as the effects of the present invention are not impaired.

In the polymer produced in the polymerization step [II], the molecular weight represented by the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is usually 0.05 to 20 deciliters / g, preferably 0.2 to 20 deciliters / g. It is 18 deciliter / g, more preferably 0.3 to 16 deciliter / g, and most preferably 0.4 to 13 deciliter / g. When the intrinsic viscosity [η] is less than 0.05 deciliter / g, physical properties such as rigidity and impact resistance are reduced, and when the intrinsic viscosity is more than 20 deciliter / g, moldability may be reduced.
When the molecular weight of the polymer produced in the polymerization step [II] is defined by a melt index (MI) which is an index of the molecular weight in a molten state, it is preferably in the range of 0.01 to 500 g / 10 minutes. The measurement conditions for each polymer are as follows. In addition, this MI was measured based on JISK7210.
(1) Polymer containing 50 mol% or more of ethylene: 190 ° C, 21.18N load
(2) Polymer containing 50 mol% or more of propylene: 230 ° C, 21.18N load
(3) Polymer containing 50 mol% or more of α-olefin having 4 to 20 carbon atoms: 230 ° C., 21.18 N load

In the polymer produced in the polymerization step [II], the molecular weight distribution is not particularly limited, and may be in a usual range. Preferably, the ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC (gel permeation chromatography) is in the range of 2.7 to 70, and 3.8 to 70. 25 is more preferred. Usually, the molecular weight distribution is almost determined by the catalyst to be used. However, in order to expand the molecular weight distribution, in the polymerization step [II], for example, the temperature, pressure, and the amount of polymer produced in the polymerization step [II] may be increased. What is necessary is just to change the conditions which change a molecular weight.
In the polymer produced in the polymerization step [II], the polyene content is generally more than 0 and 25 mol% or less, preferably more than 0 and 23 mol% or less, more preferably more than 0 and 18 mol% or less. More preferably, more than 0 and 14 mol% or less, even more preferably more than 0 and 9 mol%, still more preferably 0.001 to 4.8 mol%, more preferably 0.001 to 2.3 mol%, Most preferably, it is 0.001 to 1.8 mol%. When the polyene content is 0, the effect as a desired resin compatibilizer and the effect of improving the melt fluidity in the present invention are poor, and when the polyene content exceeds 25 mol%, the melt fluidity is inferior. .

The polymer produced in the polymerization step [II] has a long chain branch generated by graft-polymerizing the monomer used in the polymerization step [II] to the polyene residue of the polymer in the polymerization step [I]. The polymer produced in the polymerization step [II] may be one having a long-chain branch formed by the polyene produced in the polymerization step [I].
As a method for detecting long-chain branching, there are (a) an evaluation method based on the dependency of the melt viscosity on the shear rate, and (b) an evaluation method based on GPC-light scattering. Details of these methods are as described in the polymerization step [I].
In the evaluation method based on the dependence of the melt viscosity on the shear rate, the following formula (5): 1.05 ≦ N ¹ / N ⁰ ≦ 80 (5)
The case where it is satisfied is evaluated as a long chain branched structure.
In the above equation (5),
1.07 ≦ N ¹ / N ⁰ ≦ 70 is preferred,
1.08 ≦ N ¹ / N ⁰ ≦ 65 is more preferable,
1.09 ≦ N ¹ / N ⁰ ≦ 60 is more preferable,
1.10 ≦ N ¹ / N ⁰ ≦ 55 is most preferable.
If N ¹ / N ⁰ is less than 1.05, the number and length of long-chain branches are insufficient, so that the effect of improving moldability and compatibilizing function may be reduced. If N ¹ / N ⁰ exceeds 80, gel or the like may be generated, and the moldability may be reduced.

In the evaluation method using GPC-light scattering, when the ratio of α values [(α) ^L / (α) ^B ] is 1 or more, it is evaluated that a long chain branch exists. Here, (α) ^L indicates the α value of the linear polymer, and (α) ^B indicates the α value of the polymer in the polymerization step [III].
(Α) ^L / (α) ^B is
1.05 ≦ (α) ^L / (α) ^B ≦ 80 is preferred,
1.06 ≦ (α) ^L / (α) ^B ≦ 70 is more preferable,
1.07 ≦ (α) ^L / (α) ^B ≦ 60 is more preferable,
1.08 ≦ (α) ^L / (α) ^B ≦ 50 is still more preferable,
1.09 ≦ (α) ^L / (α) ^B ≦ 40 is still more preferable,
1.10 ≦ (α) ^L / (α) ^B ≦ 30 is more preferable,
1.11 ≦ (α) ^L / (α) ^B ≦ 20 is most preferable.
If (α) ^L / (α) ^B is less than 1.05, the number and length of long-chain branches are insufficient, and the effect of improving moldability and compatibilizing function may be reduced. If (α) ^L / (α) ^B exceeds 80, a gel or the like may be generated and the moldability may be reduced.
In the present invention, the gel component is a heat-paraxylene-insoluble portion, and the measuring method thereof will be described later. In the polymer obtained in the polymerization step [II], the content of the gel component is usually 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. , Most preferably 12% by mass or less.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The olefin graft copolymer and the like were evaluated by the following methods.
(1) Polyene recovery rate It was determined by the method described in the text of the specification. That is, assuming that the recovered solvent amount is B _n (unit: liter) of the total solvent amount _An (unit: liter) in a certain washing step n, the polyene recovery rate is represented by B _n / _An , Is represented by [1- ( _Bn / _An )]. In the washing step (n + 1) subsequent to the washing step n, the recovery rate of the polyene is B _{n + 1} / A _{n + 1} , and the recovery rate of the polyene in the cleaning step (n + 1) is [1- (B _n / A _n ). ] × (B _{n + 1} / A _{n + 1} ). When the cleaning step is repeated a plurality of times, the sum of the recovery rates of polyene in each of these cleaning steps is the total recovery rate of polyene. In the first embodiment, n is 3.
(2) Polymerization ratio of polymerization step [I] and polymerization step [II] The polymerization step [I] / polymerization step [II] was calculated from the amount of propylene absorbed in the polymerization steps [I] and [II]. The propylene absorption was determined by a mass flow sensor.
(3) Measurement of intrinsic viscosity [η] It was measured at 135 ° C in a decalin solvent using a VMR-053 automatic viscometer manufactured by Rigo Co., Ltd.
(4) Molecular weight distribution (Mw / Mn)
It was expressed as the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC (gel permeation chromatography).
(5) Gel fraction In a glass separable flask equipped with a stirrer, placed in a basket made of stainless steel 400 mesh (wire diameter 0.03 μm, opening 0.034 mm, space ratio 27.8%), a polymerization step was performed. 50 mg of the polymer obtained in [II] was charged and fixed to a stirring blade. 700 ml of para-xylene containing 1 g of an antioxidant (BHT: 2,6-di-t-butyl-4-methylphenol) was added, and the mixture was stirred at a temperature of 140 ° C. for 2 hours to form an olefin-based graft copolymer. Dissolved. The basket containing the para-xylene-insoluble portion was collected, dried sufficiently, and weighed to obtain the para-xylene-insoluble portion. The gel fraction (% by mass) defined as the hot paraxylene insoluble part was calculated by the following equation.
Gel fraction = [remaining amount in mesh (g) / prepared sample amount (g)] × 100

Example 1
(1) equipped with a stirrer round-bottom flask having a content volume of 200 ml was replaced with the preparation nitrogen catalyst component, and a suspension was charged a 80 ml diethoxy magnesium 10g and toluene and then TiCl ₄ 20 to the suspension Milliliter was added, the temperature was raised to 90 ° C., 27 ml of n-butyl phthalate was added, the temperature was further raised to 115 ° C., and the mixture was reacted for 2 hours with stirring. After the completion of the reaction, the resultant was washed twice with 100 ml of toluene at 90 ° C., 20 ml of TiCl ₄ and 80 ml of toluene were newly added, and reacted at 115 ° C. for 2 hours while stirring. After the reaction was completed, the reaction product was washed 10 times with 200 mm of n-heptane at 40 ° C. When the titanium content of the obtained solid catalyst component was measured, it was 2.61% by mass.
(2) Production of Graft Copolymer After sufficiently drying a stainless steel pressure-resistant autoclave with a stirrer having an internal volume of 15 liters, 7 liters of heptane, 25 mmol of triisobutylaluminum, dicyclopentyldimethoxysilane under a nitrogen stream. 5 mmol and 147 ml of 1,7-octadiene were charged and stirred for 5 minutes.
0.25 mmol of the titanium-containing solid catalyst component prepared in the above (1) was added thereto in terms of titanium atom, hydrogen was introduced at 0.11 MPa · G, and the temperature was raised to 80 ° C. Propylene was introduced into the mixture while adjusting the pressure to 0.7 MPa · G, and polymerization was carried out for 2 hours [polymerization step [I]].
After completion of the reaction, the system was cooled, depressurized, and stopped stirring. After the polymer had settled, 5.2 liters of a liquid portion was recovered using a dip tube. Next, 5 liters of a 0.009% by mass (90% by mass) heptane solution of triisobutylaluminum was added, and the mixture was washed with stirring at 40 ° C. for 5 minutes. After the repetition, 5.2 liters of the same heptane solution as above was added to complete the washing step, and the liquid level at the end of the polymerization step [I] was obtained. The polyene recovery rate measured by the above method was 95.2% [washing step].
Next, 2.5 mmol of dicyclopentyldimethoxysilane was introduced, hydrogen was introduced at 0.01 MPa · G, and propylene and ethylene were introduced at a flow rate ratio of propylene / ethylene = 10/5, and the pressure was increased to 0. Polymerization was performed at 57 ° C. for 90 minutes while adjusting to 75 MPa [polymerization step [II]].
After the polymerization was completed, 50 ml of ethyl alcohol was added to inactivate the mixture. The reaction mixture was filtered through a # 400 mesh, and the copolymer remaining on the mesh was washed three times with 5 l of heptane. This was recovered and dried to obtain 2930 g of a graft copolymer. The catalytic activity was 245 kg / g · Ti. Table 2 shows the results of evaluating the physical properties of the graft copolymer by the above evaluation methods.
In addition, the crystalline polypropylene portion was separated by crystallization fractionation, and when ¹³ C-NMR analysis was performed on this portion, the presence of ethylene units was observed, and the obtained copolymer was a graft copolymer. It was confirmed.

Comparative Example 1
In Example 1- (2), 3010 g of a graft copolymer was produced in the same manner as in Example 1 except that the washing step was omitted. Table 2 shows the physical property evaluation results.

Example 2
A graft copolymer was produced in the same manner as in Example 1- (4) except that triisobutylaluminum was not added to the heptane solvent used in the washing step in Example 1- (2). The recovery of polyene in the washing step was 96.0%. The catalyst activity was 123 kg / g · Ti. Table 2 shows the physical property evaluation results.
In addition, the crystalline polypropylene portion was separated by crystallization fractionation, and when ¹³ C-NMR analysis was performed on this portion, the presence of ethylene units was observed, and the obtained copolymer was a graft copolymer. It was confirmed.

Example 3
(1) Preparation of catalyst component 60 ml of dehydrated octane and 16 g of diethoxymagnesium were added to a 500 ml three-necked flask equipped with a stirrer and purged with nitrogen. After heating to 40 ° C., 2.4 ml of silicon tetrachloride was added and stirred for 20 minutes, and 1.6 ml of dibutyl phthalate was added. The temperature of the solution was raised to 80 ° C., followed by dropwise addition of 77 ml of titanium tetrachloride, followed by stirring at an internal temperature of 125 ° C. for 2 hours to perform a contact operation. Thereafter, the stirring was stopped to settle the solid, and the supernatant was extracted.
Next, 100 ml of dehydrated octane was added to the solid, the temperature was raised to 125 ° C. with stirring, and the temperature was maintained for 1 minute. After that, the stirring operation was stopped, the solid was settled, and the supernatant was withdrawn. The washing operation was repeated seven times. . Further, 122 ml of titanium tetrachloride was added, and the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to perform a second contact operation. Thereafter, the same washing operation as described above with dehydrated octane was repeated six times to obtain a solid catalyst component.
(2) Production of Graft Copolymer After sufficiently drying a 1.6-liter stainless steel pressure-resistant autoclave equipped with a stirrer, 400 ml of dehydrated octane and 2 mmol of triethylaluminum were introduced under a nitrogen stream, and 5 Stirred at room temperature for minutes. To this, 0.1 mmol of dicyclopentyldimethoxysilane was added and stirred for 2 minutes. Further, 10 ml of 1,7-octadiene was added, and the mixture was stirred for 5 minutes.
0.005 mmol of the titanium-containing solid catalyst component prepared in the above (1) was added thereto in terms of titanium atom, hydrogen was introduced at 0.05 MPa · G, and the temperature was raised to 80 ° C. To this, propylene was introduced while adjusting the pressure so as to be 0.8 MPa · G, and polymerization was carried out for 45 minutes [polymerization step [I]].
After completion of the reaction, the system was cooled, depressurized, and stopped stirring. After the polymer had settled, 240 ml of the liquid part was recovered with a dip tube. Next, 250 ml of a 0.009% by mass (90% by mass) heptane solution of triethylaluminum is added, and the mixture is washed with stirring at 40 ° C. for 5 minutes. Then, the washing is stopped three times, and the washing is stopped. After that, 230 ml of the same heptane solution as above was added to complete the washing step, and the liquid level at the end of the polymerization step [I] was obtained. The recovery rate of polyene measured by the above method was 94.8% [washing step].
Next, 0.1 mmol of dicyclopentyldimethoxysilane was introduced, hydrogen was introduced at 0.01 MPa · G, and propylene and ethylene were introduced at a flow rate ratio of propylene / ethylene = 10/5. Polymerization was carried out at 57 ° C. for 30 minutes while adjusting to 75 MPa [polymerization step [II]].
After the polymerization was completed, 5 ml of ethyl alcohol was added to inactivate the mixture, the reaction mixture was filtered through a # 400 mesh, and the copolymer remaining on the mesh was washed three times with 700 ml of heptane. This was recovered and dried to obtain 185 g of a graft copolymer. The catalyst activity was 772 kg / g · Ti. Table 2 shows the results of evaluating the physical properties of the graft copolymer by the above evaluation methods.
In addition, the crystalline polypropylene portion was separated by crystallization fractionation, and when ¹³ C-NMR analysis was performed on this portion, the presence of ethylene units was observed, and the obtained copolymer was a graft copolymer. It was confirmed.

Example 4
(1) Preparation of solid product 16 g (0.14 mol) of diethoxymagnesium was charged into a three-necked flask equipped with a stirrer having an internal volume of 500 ml and purged with nitrogen, and 60 ml of dehydrated heptane was added. The mixture was heated to 40 ° C., 2.45 ml (22.5 mmol) of silicon tetrachloride was added, and the mixture was stirred for 20 minutes, and 12.7 mmol of di-n-butyl phthalate was added. The temperature of this solution was raised to 80 ° C., and 77 ml (0.70 mol) of titanium tetrachloride was subsequently added dropwise using a dropping funnel. The internal temperature was set to 110 ° C., and the mixture was stirred for 2 hours to perform a loading operation. Thereafter, washing was sufficiently performed using dehydrated heptane. Further, 122 ml (1.12 mol) of titanium tetrachloride was added, the internal temperature was set to 110 ° C., and the mixture was stirred for 2 hours to perform a second loading operation. Thereafter, the product was sufficiently washed with dehydrated heptane to obtain a solid product.
(2) Preparation of solid catalyst component (contact of solid product with organoaluminum and organosilane components)
10 g (3.3 mmol-Ti) of the solid product was placed in a three-necked flask equipped with a stirrer having an inner volume of 500 ml and purged with nitrogen, and 60 ml of dehydrated heptane was added. After heating to 40 ° C., 46.2 mmol of triethylaluminum and 82.5 mmol of dicyclopentyldimethoxysilane were added, stirred for 12 hours, and sufficiently washed with dehydrated heptane. The obtained solid component was used as a solid catalyst component.
(3) Production of graft copolymer In Example 3- (2), 400 ml of dehydrated heptane was used as a solvent, 0.25 mmol of dicyclopentyldimethoxysilane used in the polymerization step [I] and the polymerization step [II], and the polymerization step The same operation as in Example 3- (2) was conducted except that the hydrogen of [I] was 0.1 MPa · G, and the titanium-containing solid catalyst component prepared in the above (2) was 0.005 mmol in terms of titanium atoms. . The recovery of polyene in the washing step was 92.5%. The amount of the obtained graft copolymer was 140 g. Table 2 shows the measurement results.
In addition, the crystalline polypropylene portion was separated by crystallization fractionation, and when ¹³ C-NMR analysis was performed on this portion, the presence of ethylene units was observed, and the obtained copolymer was a graft copolymer. It was confirmed.

Reference Example 1
The graft copolymers obtained in Example 1 and Comparative Example 1 were added to a composition of block polypropylene (block PP) and a high molecular weight rubber, and the performance as a compatibilizer was compared by the following evaluation method. It shows in Table 3 with the evaluation result about the composition which does not add a graft copolymer.
As the block PP, commercially available block PP (melt flow rate (MFR) = 60 g / 10 min, amorphous part content = 7 mass%, intrinsic viscosity of amorphous part [η] = 6 deciliter / g, crystal part Of intrinsic viscosity [η] = 1 deciliter / g, ethylene was used as a comonomer), and EP57P (ethylene propylene rubber) manufactured by JSR Corporation was used as a high molecular weight rubber. The production of the kneaded sample was performed using a co-rotating twin-screw extruder with L / D (length / diameter) = 33, at a cylinder set temperature of 180 ° C., at 200 rpm, and at 10 kg / h.

(6) Flexural modulus According to ASTM D790, the flexural modulus at 23 ° C. was measured.
(7) Izod impact strength Notched Izod impact strength at 23 ° C. was measured according to ASTM D256.
(8) Low-temperature surface impact A flat plate having a size of 75 mm x 75 mm x 3 mm was prepared by injection molding, placed on a pedestal provided with a hole having a diameter of 50 mm at -20 ° C, and a striker having a diameter of 13 mm was moved at a speed of 5 m / The energy required from the time of s collision with the center of the plate to the time of penetration was determined and evaluated.

Claims (5)

In the method for producing an olefin-based graft copolymer comprising a polyene and one or more monomers selected from ethylene, α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrenes, at least the following polymerization step [I] A method for producing an olefin-based graft copolymer, comprising a washing step and a polymerization step [II].
Polymerization Step [I]: Using a catalyst comprising (A) a titanium trichloride compound or a catalyst component containing titanium, magnesium and a halogen element as essential components and (B) an organoaluminum compound, ethylene, a C3-20 a step of producing an olefin polymer by copolymerizing at least one monomer selected from α-olefins, cyclic olefins and styrenes with a polyene.
Washing step: a step of removing the polyene from the reaction mixture of the olefin polymer obtained in the polymerization step [I].
Polymerization step [II]: one or more monomers selected from ethylene, α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrenes in the presence of an olefin polymer having undergone a washing step, A step of polymerizing monomers of the same or different type as those used in step [I]. The method according to claim 1, wherein the monomer used in the polymerization step [I] and the polymerization step [II] is at least one selected from ethylene and a C3-20α-olefin. One or more of the monomer species used in the polymerization step [I] and the polymerization step [II] are different, or the monomer species used in the polymerization step [I] and the polymerization step [II] are the same, The production method according to claim 1, wherein one or more of a monomer composition ratio, a stereoregularity, and a molecular weight of a produced polymer are different. A polyene having two or more polymerizable carbon-carbon double bonds in the molecule, a polyene having an α-olefin skeleton / α-olefin skeleton in the molecule, a polyene having a styrene skeleton / styrene skeleton in the molecule, A cyclic olefin skeleton / polyene having a cyclic olefin skeleton in the molecule, a styrene skeleton / polyene having an α-olefin skeleton in the molecule, a polyene having a cyclic olefin skeleton / α-olefin skeleton in the molecule, and a styrene skeleton / cyclic olefin skeleton The production method according to any one of claims 1 to 3, wherein the production method is at least one selected from polyenes contained in a molecule. オ レ フ ィ ン An olefin-based graft copolymer obtained by the production method according to claim 1.