JP2003231710A - Method for producing copolymer of olefin/polar vinyl monomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a copolymer obtained from an olefin/a polar vinyl monomer at a high activity. <P>SOLUTION: The method for producing the copolymer comprises copolymerizing (C) the olefin and (D) the polar vinyl monomer with the use of a catalyst consisting of (A) a layer compound and (B) a complex of a transition metal belonging to the table 4-10 of the periodic law. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an olefin / polar vinyl monomer copolymer, and more specifically, it is excellent in adhesiveness, printability, hydrophilicity and compatibility in polymer blends, and is a sheet material and extrusion molding. The present invention relates to a method for producing an olefin / polar vinyl monomer copolymer suitable as a material and an automobile material.

[0002]

2. Description of the Related Art Conventionally, using a metallocene complex catalyst,
As a method for copolymerizing an olefin and a polar vinyl monomer, JP-A-6-25320 (applicant: Mitsui Toatsu Chemical Co., Ltd.) and JP-A-6-172447 (applicant: Mitsubishi Petrochemical Co., Ltd.) , Special Table 2000-513
761 (Applicant: DSM), JP 2000-3
19332 (Applicant: Mitsui Chemicals, Inc.) and JP 2001-11103 (Applicant: Toyota Central Research Institute Co., Ltd.). Incidentally, JP-A-2000-319
Japanese Patent No. 332 also discloses a method using a nonmetallocene catalyst. Among these manufacturing methods, JP-A-6-
25320, JP 6-172447 A, JP 2000-513761 A, and JP 2001-1.
In the method for producing a copolymer of an olefin and a polar vinyl monomer described in Japanese Patent No. 1103, expensive methylaluminoxane or similarly expensive fluoroborate is used as a cocatalyst. It should be noted that these publications do not describe the use of the layered compound used in the present invention as a cocatalyst. Further, the copolymerization activity was not high. In addition, in Examples described in JP-A-6-25320 and JP-A-6-172447, in order to allow copolymerization of an olefin and a polar vinyl monomer, an olefin moiety and a functional group are used as a polar vinyl monomer. A 10-undecen-1-ol remote from the group (OH) is used. After that, special table 2000-
As described in the examples of Japanese Patent No. 513761,
It has been proposed to use polar vinyl monomers, such as 5-hexen-1-ol, in which the polar groups are closer to the olefinic moieties. However, the above-mentioned production method has a problem that the copolymerization of the olefin and the polar vinyl monomer in which the polar group is closer to the polar group does not proceed sufficiently. It should be noted that in the above-mentioned publications, allyl (CH
₂ = CHCH ₂₎ sites directly, embodiment using the polar vinyl monomer polar group is attached is not shown.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and relates to a production method for efficiently producing an olefin / polar vinyl monomer copolymer. Another object of the present invention is to provide a production method capable of sufficiently promoting the copolymerization of an olefin and a polar vinyl monomer in which the polar group is closer to the polar group.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by using a layered compound as a cocatalyst in a metallocene complex-based catalyst, MAO (methyl ether) as a cocatalyst can be obtained. Aluminoxane) or borate did not proceed sufficiently, the copolymerization of polar vinyl monomer and olefin in which the olefin moiety and the polar group are closer to each other proceeded sufficiently, and high activity,
It was found that an olefin / polar vinyl monomer copolymer can be obtained with high stereoregularity. The present invention has been completed based on such findings. That is, the present invention is
An olefin characterized in that (C) an olefin and (D) a polar vinyl monomer are copolymerized using a catalyst composed of (A) a layered compound and (B) a transition metal complex of Groups 4 to 10 of the periodic table. A method for producing a polar vinyl monomer copolymer is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of the layered compound (A) include clay, clay minerals and ion-exchangeable layered compounds. Clay is an aggregate of fine hydrated silicate minerals, which produces plasticity when kneaded with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. Clay minerals are hydrous silicates that are the main constituents of clay. For the preparation of the catalyst component used in the present invention, either clay or clay mineral may be used, and these may be naturally occurring or artificially synthesized. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like have weak binding forces to each other and have a parallel stacked structure, and the ions contained therein are exchangeable. Some clay minerals are ion-exchangeable layered compounds. Specific examples of these (A) components include, for example, phyllosilicates as clay minerals. Examples of the phyllosilicates include phyllosilicate and phyllosilicate. Phyllosilicates include montmorillonite, saponite, hectorite, illite, mica, and smectite / mica or mixed mica / vermiculite as a natural product. Can be mentioned. Moreover, as synthetic products, there may be mentioned fluorine tetrasilicon mica (manufactured by Coop Chemical Co., Ltd.), laponite (manufactured by Laport Kogyo Co., Ltd.), smecton (manufactured by Kunimine Kogyo Co., Ltd.) and the like. In addition, α-Zr (HPO ₄ ) ₂ and γ-Zr
(HPO ₄ ) ₂ , α-Ti (HPO ₄ ) ₂ and γ-Ti
An ionic crystalline compound having a layered crystal structure that is not a clay mineral such as (HPO ₄ ) ₂ can be used. Clays and clay minerals that do not belong to ion-exchangeable layered compounds include clay called bentonite because of its low montmorillonite content, kibushi clay, which contains many other components in montmorillonite, gyrrome clay, and sepiolite showing fibrous morphology. , Palygorskite, amorphous or low crystalline allophane, imogolite, etc.
In the present invention, the layer charge is 0.1 to 0.7 (preferably 0.2).
It is preferable to use a 2: 1 type lamellar compound having the formula (1) to (0.6), and among these, smectite group clay minerals belonging to the phyllosilicates and fluorine tetrasilicon mica (synthetic mica compound) having water swelling ability are particularly preferable.

Further, as the component (A), particles having a volume average particle diameter of 10 μm or less are preferable, and particles having a volume average particle diameter of 3 μm or less are more preferable. Generally, the particle shape of the particles has a particle size distribution, but as the component (A), the volume average particle diameter is 10 μm or less, and the content ratio of the volume average particle diameter of 3.0 μm or less is 10% by mass or more. It is preferable that the volume average particle diameter is 10 μm or less and the volume average particle diameter is 1.5 μm.
It is more preferable to have a particle size distribution in which the content ratio of m or less is 10 mass% or more. As a method of measuring the volume average particle diameter and the content ratio, for example, a device for measuring the particle diameter by light transmittance with a laser beam (GALAIProduct)
ion Ltd. A measurement method using CIS-1) manufactured by K.K.

The silane-treated product used in the present invention is a lamellar compound treated with a silane compound. The silane compound is represented by the general formula (2) R ⁴ _4-m SiX ² _m (2) (wherein R ⁴ represents a hydrocarbon-containing group. X ² is an element directly bonded to silicon, such as halogen, nitrogen or An organic silane compound represented by a functional group which is oxygen and m is an integer of 1 to 3 is preferable. In the general formula (2), examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, an aralkyl group and a cyclic saturated hydrocarbon group. In the present invention, an alkyl group, an alkenyl group and a cyclic saturated hydrocarbon group are preferred. In the case of an alkyl group,
The total number of carbon atoms in the alkyl group is preferably 2-12. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-hexyl group and an n-decyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, a cyclohexenyl group and the like, and those having 2 to 6 carbon atoms are preferable in the present invention.
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cyclic saturated hydrocarbon group include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group, and in the present invention, a cyclopentyl group and a cyclohexyl group are preferable. X ² is a halogen atom or a group in which the element directly bonded to silicon is nitrogen or oxygen. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and chlorine is preferred in the present invention. Examples of the group in which the element directly bonded to silicon is nitrogen include an amino group, an alkylamino group, a triazole group, and an imidazole group. Examples of the group in which the element directly bonded to silicon is oxygen include an alkoxy group and an aryloxy group. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a phenoxy group. In the present invention, a methoxy group and an ethoxy group are preferable.

Specific examples of the organic silane compound represented by the general formula (2) include trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, t-butyldimethylchlorosilane, t-butyldiphenylchlorosilane and phenethyldimethylchlorosilane. Chlorosilanes such as; dimethyldichlorosilane,
Diethyldichlorosilane, ethylmethyldichlorosilane, diisopropyldichlorosilane, isopropylmethyldichlorosilane, n-hexylmethyldichlorosilane, di-n-hexyldichlorosilane, dicyclohexyldichlorosilane, cyclohexylmethyldichlorosilane, docosylmethyldichlorosilane, vinylmethyl Dichlorosilanes such as dichlorosilane, divinyldichlorosilane, bis (phenethyl) dichlorosilane, methylphenethyldichlorosilane, diphenyldichlorosilane, dimesityldichlorosilane, ditolyldichlorosilane; methyltrichlorosilane, ethyltrichlorosilane, isopropyltrichlorosilane, t -Trichlorosilane such as butyltrichlorosilane, phenyltrichlorosilane, phenethyltrichlorosilane, etc. Halosilane in which the chlorine portion of the above compound is replaced by another halogen element; alkoxysilane such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and further dimethyldimethylaminosilane, bis (dimethyl) Amino) methylsilane, bis (dimethylamino) dimethylsilane, 1-trimethylsilyl-1,2,4-triazole, 1-trimethylsilylimidazole, hexamethyldisilazane, 1,1,
3,3,5,5-hexamethylcyclotrisilazane,
Examples include nitrogen-containing compounds such as 1,1,3,3,5,5,7,7-octamethylcyclotrisilazane.

In the present invention, among the organosilane compounds represented by the general formula (2), the general formula (2 ′) R ⁵ R ⁶ SiX ² ₂ (2 ′) (wherein R ⁵ and R ⁶ are (Indicates an alkyl group or an alkenyl group having a total carbon number of 2 to 12, and X ² is the same as the above.)
The organic silane compound represented by R ⁵ and R ⁶
Specific examples of the compound in which is a chain or cyclic alkyl group include dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldichlorosilane, diethyldimethoxysilane, diethyldiethoxysilane, ethylmethyldichlorosilane, and isopiro. Pyrmethyldichlorosilane, cyclohexylmethyldichlorosilane, dicyclohexyldichlorosilane, n-hexylmethyldichlorosilane, and di-n-hexyldichlorosilane may be mentioned. Examples of the compound in which R ⁵ and R ⁶ are alkenyl groups include divinyldichlorosilane and the like. Among these, more preferred are organosilane compounds in which the total number of carbon atoms in the alkyl group is 2 to 4.

In order to treat the layered compound of the component (A) with the organosilane compound, first, the layered compound is added in an amount of water sufficient to form an aqueous clay colloid solution, preferably 40 times or more the weight of the layered compound. An aqueous colloidal solution of the layered compound is prepared in addition to the amount of water. Next, the above-mentioned organic silane compound is added to the aqueous layered compound colloid solution thus prepared, and the layered compound is treated with the organic silane compound by heating and stirring. The temperature at which this treatment is carried out can be carried out at -30 to 100 ° C, but in order to shorten the catalyst preparation time, it is preferable to treat at a temperature near 100 ° C. And this processing time is
The time may be 30 minutes to 10 hours, although it is not uniform depending on the type of layered compound used and the treatment temperature.

The proportion of the organic silane compound used herein is 0.001 to 1000 in terms of the number of moles of silicon atoms per 1 kg of the layered compound of the component (A).
It is preferably 0.01 to 500. When the number of moles of this silane compound is 0.001 or less, the polymerization activity of the catalyst is low,
This is because if it exceeds 1000, the activity may decrease again. In this manner, when the layered compound colloidal aqueous solution is treated with the organic silane compound, the layered compound colloidal aqueous solution changes into a slurry suspension. Water is added to this slurry again to wash it, and then filtered with a filter,
The organic silane-treated layered compound can be obtained as a solid by drying. When a chelate complex or titanium complex of a metal of Groups 4 to 6 of the Periodic Table is used as the component (B) described below, the layered compound of the component (A) is subjected to silane treatment and is further treated with an organoaluminum compound (described later). The same catalytic activity can be obtained by treating the olefin with a polar vinyl monomer after contacting with a transition metal complex after the treatment with (). When a transition metal metallocene catalyst complex other than titanium is used, the silane treatment of the layered compound is more active, but pretreatment with organoaluminum is not always necessary.

In the present invention, (B) Periodic Table Nos. 4 to 1
The group 0 transition metal complex includes a metallocene complex containing a transition metal of groups 4 to 6 of the periodic table or a transition metal of groups 4 to 10, preferably 8 to 10 of the periodic table, and a ligand of a hetero atom. A chelate complex with is used. Of these,
The indenyl complex is preferable because it has a polymerization ability with respect to ethylene and propylene and has high activity. Further, a crosslinked half metallocene (including a constrained geometry type ligand complex and a CGC complex) having good copolymerization ability can also be used. As the metallocene complex of Group 4 to 6 of the periodic table, transition metal compounds represented by the following general formulas (3) to (5) can be mentioned as preferable ones from the viewpoint of activity, and also the periodic table 8
The chelate complex of group 10 to 10 has the following general formula (6)
The transition metal compounds represented by are preferred.

Q ¹ _a (C ₅ H _5-ab R ⁷ _b ) (C ₅ H _5-ac R ⁸ _c ) M ¹ X ³ _p Y ¹ _q (3) Q ² _a (C ₅ H _5-ad R ⁹ _d ) Z ¹ M ¹ X ³ _p Y ¹ _q (4) M ¹ X ⁴ _r (5) L ¹ L ² M ² X ⁴ _u Y ² _v (6)

[Wherein Q¹Is two conjugated five-membered ring ligands
(C_FiveH_5-abR⁷ _b) And (C_FiveH _5-acR⁸ _c)
Indicates a crosslinkable group, Q²Is a conjugated five-membered ring ligand
(C_FiveH _5-adR⁹ _d) And Z¹A linking group that bridges the group
Show. R⁷, R⁸And R⁹Are the hydrocarbon group and
Rogen atom, alkoxy group, silicon-containing hydrocarbon group, phosphorus
Hydrocarbon group containing, nitrogen containing hydrocarbon group or boron containing carbon
Represents a hydrogen group, and a is 0, 1 or 2. b, c and d
Are integers 0 to 5 when a = 0, and a = 1
Respectively an integer from 0 to 4 and 0 when a = 2
Indicates an integer of ˜3. (P + q) is (M¹Valence of -2)
Yes, r is M¹Indicates the valence of. M¹Is group 4-6 of the periodic table
Transition metal, M²Indicates a transition metal of Group 8 to 10 of the periodic table
And (u + v) is M²Indicates the valence of. Also, L¹, L²
Each represents a ligand having a coordinate bond, and X represents³, Y¹，
Z¹, X^Four, Y²Are covalent or ionic bonds, respectively.
It represents a compatible ligand. Note that L¹, L², X^FourOver
And Y²Are bonded to each other to form a ring structure.
May be. ]

Specific examples of Q ¹ and Q ² are:
(1) C1-C4 alkylene group such as methylene group, ethylene group, isopropylene group, methylphenylmethylene group, diphenylmethylene group, cyclohexylene group, cycloalkylene group or side chain lower alkyl or phenyl substitution product thereof, (2) silylene group, dimethylsilylene group, methylphenylsilylene group, diphenylsilylene group, disilylene group, tetramethyldisilylene group and other silylene groups, oligosilylene groups or their side chain lower alkyl or phenyl substituents, (3) ( CH ₃ ) ₂ Ge group,
(C ₆ H _{5) 2} Ge group, (CH ₃₎ P group, (C ₆ H ₅₎
P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (C
H ₃ ) B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group,
Hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum such as (C ₆ H ₅ ) Al group and (CH ₃ O) Al group [lower alkyl group, phenyl group, hydrocarbyloxy group (preferably lower alkoxy group) Etc.] and the like. Among these, an alkylene group and a silylene group are preferable from the viewpoint of activity.

Further, (C ₅ H _5-ab R ⁷ _b ), (C ₅ H
_5-ac R ⁸ _c ) and (C ₅ H _5-ad R ⁹ _d ) are conjugated five-membered ring ligands, and R ⁷ , R ⁸ and R ⁹ are a hydrocarbon group, a halogen atom and an alkoxy group, respectively. , A silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and a is 0, 1 or 2.
b, c, and d each represent an integer of 0 to 5 when a = 0, an integer of 0 to 4 when a = 1, and an integer of 0 to 3 when a = 2. Here, as the hydrocarbon group, those having 1 to 20 carbon atoms are preferable, and those having 1 to 12 carbon atoms are particularly preferable. This hydrocarbon group may be bonded as a monovalent group to a cyclopentadienyl group, which is a conjugated five-membered ring group, and when a plurality of them are present, the two are bonded to each other to form a cyclopentadienyl group. A ring structure may be formed together with part of the pentadienyl group. That is, a representative example of the conjugated five-membered ring ligand is a substituted or unsubstituted cyclopentadienyl group, indenyl group and fluorenyl group. The halogen atom includes chlorine, bromine, iodine and fluorine atoms, and the alkoxy group includes
Preferred are those having 1 to 12 carbon atoms. The silicon-containing hydrocarbon group, for example ^{-Si (R 10) (R 11} )
(R ¹² ) (R ¹⁰ , R ¹¹ and R ¹² are hydrocarbon groups having 1 to 24 carbon atoms) and the like, and as the phosphorus-containing hydrocarbon group, the nitrogen-containing hydrocarbon group and the boron-containing hydrocarbon group, respectively, ^{P- (R 13) (R 14} ), - N (R 13) (R 14) and -
^{B (R 13) (R 14} ) (R 13 and R ¹⁴ is a hydrocarbon group having 1 to 18 carbon atoms) and the like. When there are a plurality of R ⁷ , R ⁸ and R ⁹ , respectively, a plurality of R ⁷ , a plurality of R ⁸ and a plurality of R ⁹ may be the same or different in each. Further, in the general formula (3), the conjugated five-membered ring ligand (C ₅ H _5-ab R ⁷ _b ) and (C ₅ H _5-ac
R ⁸ _c ) may be the same or different. Examples of the hydrocarbon group having 1 to 24 carbon atoms or the hydrocarbon group having 1 to 18 carbon atoms include an alkyl group, an alkenyl group, an aryl group, and an alicyclic aliphatic hydrocarbon group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-hexyl group, and an n-decyl group, and in the present invention, Those having 1 to 20 carbon atoms are preferable. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-hexenyl group, a 1-octenyl group and a cyclohexenyl group, and those having 2 to 10 carbon atoms are preferable in the present invention. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and those having 6 to 14 carbon atoms are preferable in the present invention. Examples of the alicyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.

On the other hand, M ¹ represents a transition metal element of Groups 4 to 6 of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, vanadium, niobium, molybdenum and tungsten. In terms of activity, titanium, zirconium and hafnium are preferable. Z ¹ is a covalent bond ligand, and specifically, a halogen atom, oxygen (—O—), sulfur (—S—), carbon number 1
To 20, preferably 1 to 10 alkoxy group, carbon number 1
To 20, preferably 1 to 12 thioalkoxy group, 1 to 40 carbon atoms, preferably 1 to 18 nitrogen-containing hydrocarbon group (for example, t-butylamino group, t-butylimino group, etc.), 1 to carbon atoms 40, preferably 1-18 phosphorus-containing hydrocarbon radicals are represented. X ³ and Y ¹ are each a covalent ligand or a binding ligand, specifically, a hydrogen atom, a halogen atom, a carbon number of 1 to 20, and preferably 1 to
10 hydrocarbon groups, 1 to 20 carbon atoms, preferably 1 to 1
0 alkoxy group, amino group, 1 to 20 carbon atoms, preferably 1 to 12 phosphorus-containing hydrocarbon group (for example, diphenylphosphine group) or 1 to 20 carbon atoms, preferably 1 to 12 silicon-containing hydrocarbon A group (for example, a trimethylsilyl group), a carbon number of 1 to 20, preferably a carbon number of 1
12 shows a hydrocarbon group or a halogen-containing boron compound (for example, B (C ₆ H ₅ ) ₄ , BF ₄ ). Of these, a halogen atom and a hydrocarbon group are preferable. This X ³ and Y
¹ may be the same or different from each other. X ⁴ is a covalently bound ligand, specifically, a halogen atom, a hydrocarbylamino group or a hydrocarbyloxy group, preferably an alkoxy group.
In the present invention, the component (B) is preferably a transition metal compound represented by the general formula (3) or (4), and among these, a complex having a ligand having an indenyl, cyclopentadienyl or fluorenyl structure. Is particularly preferable.

(I) The following compounds may be mentioned as specific examples of the transition metal compound represented by the general formula (3) or (4). Bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) (Enyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl titanium dichloride, bis (indenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (cyclopentadienyl) Titanium chlorohydride,
Bis (cyclopentadienyl) methyltitanium chloride, bis (cyclopentadienyl) ethyltitanium chloride, bis (cyclopentadienyl) phenyltitanium chloride, bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) Diphenyltitanium, bis (cyclopentadienyl) dineopentyltitanium, bis (cyclopentadienyl) dihydrotitanium, (cyclopentadienyl) (indenyl) titanium dichloride, (cyclopentadienyl)
(Fluorenyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (Tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl zirconium dichloride, bis (indenyl) zirconium dichloride,
Bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium chlorohydride, bis (cyclopentadienyl) methyl zirconium chloride, bis (cyclopentadienyl) ethyl zirconium chloride, bis (cyclopentadienyl) phenyl zirconium chloride , Bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dineopentylzirconium, bis (cyclopentadienyl) dihydrozirconium, (cyclopentadienyl) ( Indenyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride, and other transition metals having two conjugated five-membered ring ligands without a bridging linking group Compounds,

Methylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, methylenebis (indenyl) titanium chlorohydride, ethylenebis (indenyl) methyltitanium chloride, ethylenebis (indenyl) methoxychlorotitanium, ethylenebis (indenyl) titanium Diethoxide, ethylenebis (indenyl) dimethyltitanium, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2-methylindenyl) titanium dichloride, ethylenebis (2,4-dimethyl) Indenyl) titanium dichloride, ethylenebis (2-methyl-4-trimethylsilylindenyl) titanium dichloride, ethylenebis (2,4-dimethyl) -5,6,7-Trihydroindenyl) titanium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride, ethylene (2-methyl-4) -T-butylcyclopentadienyl)
(3'-t-butyl-5'-methylcyclopentadienyl) titanium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) Titanium dichloride, isopropylidene bis (2-methylindenyl) titanium dichloride, isopropylidene bis (indenyl) titanium dichloride, isopropylidene bis (2,4-dimethylindenyl) titanium dichloride, isopropylidene (2,4-dimethylcyclopenta) Dienyl) (3'5'-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-
t-Butyl-5'-methylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl) (3,4
4-dimethylcyclopentadienyl) titanium chlorohydride, methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) dimethyltitanium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenyltitanium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) titanium dichloride, methylene ( Cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (2,3 , 4,5-Tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) titanium dichloride, isopropylidene (cyclopentadienyl) Fluorenyl) titanium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (2,5-dimethyl-cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) ) Titanium dichloride,
Ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenyl Methylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride,
Cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ',
4′-dimethylcyclopentadienyl) titanium dichloride, methylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, methylenebis (indenyl) zirconium chlorohydride, ethylenebis (indenyl) methylzirconium chloride, ethylenebis (indenyl) methoxy Chlorozirconium, ethylenebis (indenyl) zirconium diethoxide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylenebis (2,4-dimethylindenyl)
Zirconium dichloride, ethylene bis (2-methyl-
4-Trimethylsilylindenyl) zirconium dichloride, ethylenebis (2,4-dimethyl-5,6,7-
Trihydroindenyl) zirconium dichloride, ethylene (2,4-dimethylcyclopentadienyl)
(3 ', 5'-Dimethylcyclopentadienyl) zirconium dichloride, ethylene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'
-Methylcyclopentadienyl) zirconium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, isopropylidenebis (2-methyl) Indenyl) zirconium dichloride,
Isopropylidene bis (indenyl) zirconium dichloride, isopropylidene bis (2,4-dimethylindenyl) zirconium dichloride, isopropylidene (2,4-dimethylcyclopentadienyl) (3'5 '
-Dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-t-butyl-5'-methylcyclopentadienyl) zirconium dichloride,
Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium chlorohydride, methylene (cyclopentadienyl) (3,4-Dimethylcyclopentadienyl) dimethylzirconium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenylzirconium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium Dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (Cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopenta Dienyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl)
(3,5-Dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (2,5
5-dimethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,) hafnium diethoxide, ethylenebis (indenyl) dimethylhafnium 4-diethylcyclopenta Dienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (2,5 -Dimethylcyclopentadienyl) (3 ',
4'-dimethylcyclopentadienyl) zirconium dichloride, methylenebis (indenyl) hafnium dichloride, ethylenebis (indenyl) hafnium dichloride, methylenebis (indenyl) hafnium chlorohydride, ethylenebis (indenyl) methylhafnium chloride, ethylenebis (indenyl) methoxy Chlorohafnium, ethylenebis (indenyl) hafnium diethoxide, ethylenebis (indenyl) dimethylhafnium, ethylenebis (4,5,6,7-tetrahydroindenyl) hafnium dichloride, ethylenebis (2
-Methylindenyl) hafnium dichloride, ethylenebis (2,4-dimethylindenyl) hafnium dichloride, ethylenebis (2-methyl-4-trimethylsilylindenyl) hafnium dichloride, ethylenebis (2,4-dimethyl-5,6 , 7-Trihydroindenyl) hafnium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) hafnium dichloride, ethylene (2-methyl-4-t-butyl) Cyclopentadienyl)
(3'-t-butyl-5'-methylcyclopentadienyl) hafnium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) Hafnium dichloride, isopropylidene bis (2-methylindenyl) hafnium dichloride, isopropylidene bis (indenyl) hafnium dichloride, isopropylidene bis (2,4-dimethylindenyl) hafnium dichloride, isopropylidene (2,4-dimethylcyclopenta) Dienyl) (3'5'-dimethylcyclopentadienyl) hafnium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-
t-Butyl-5'-methylcyclopentadienyl) hafnium dichloride, methylene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) hafnium dichloride, methylene (cyclopentadienyl) (3,4
4-dimethylcyclopentadienyl) hafnium chlorohydrido, methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) dimethylhafnium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenylhafnium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) hafnium dichloride, methylene ( Cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) hafnium dichloride, isopropylidene (cyclopentadienyl) (2,3 , 4,5-Tetramethylcyclopentadienyl) hafnium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) hafnium dichloride, isopropylidene (cyclopentadienyl) Fluorenyl) hafnium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, isopropylidene (2,5-dimethyl-cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) hafnium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) ) Hafnium dichloride,
Ethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenyl Methylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ',
A transition metal compound having two conjugated five-membered ring ligands bridged with an alkylene group such as 4′-dimethylcyclopentadienyl) hafnium dichloride,

Dimethyl silylene bis (indenyl) titanium dichloride, dimethyl silylene bis (4,5,5
6,7-Tetrahydroindenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2,4-
Dimethylindenyl) titanium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoin Denyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-naphthylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) titanium dichloride, phenylmethylsilylenebis (indenyl) titanium dichloride, Phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, phenylmethylsilylenebis (2,4
-Dimethylindenyl) titanium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Titanium dichloride, phenylmethylsilylene (2,
3,5-trimethylcyclopentadienyl) (2 ',
4 ', 5'-trimethylcyclopentadienyl) titanium dichloride, phenylmethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride,
Diphenylsilylenebis (2,4-dimethylindenyl) titanium dichloride, diphenylsilylenebis (indenyl) titanium dichloride, diphenylsilylenebis (2-methylindenyl) titanium dichloride, tetramethyldisilylenebis (indenyl) titanium dichloride, tetramethyl Disilylene bis (cyclopentadienyl) titanium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene (cyclopentadienyl) ( Tramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) titanium dichloride, Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (2,
7-di-t-butylfluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethyl Silylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (2-
Ethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2 ', 7'-di -T-butylfluorenyl) titanium dichloride, dimethylsilylene (2,5
-Dimethylcyclopentadienyl) (2 ', 7'-di-
t-Butylfluorenyl) titanium dichloride, dimethylsilylene (2-ethylcyclopentadienyl)
(2 ', 7'-di-t-butylfluorenyl) titanium dichloride, dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl)
Titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl) titanium dichloride, dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylene (ethylcyclopentadienyl) (Octahydrofluorenyl) titanium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,6)
7-Tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,4
-Dimethylindenyl) zirconium dichloride, dimethylsilylene bis (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Zirconium dichloride, dimethyl silylene bis (2-
Methyl-4,5-benzoindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylene Bis (indenyl) zirconium dichloride, phenylmethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, phenylmethylsilylene bis (2,4-dimethylindenyl) zirconium dichloride, phenylmethylsilylene (2,4 -Dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5 '-Trimethylcyclopentadienyl) zirconium dichloride, phenylmethylsilylene bis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilylene bis (2,4
-Dimethylindenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, diphenylsilylenebis (2-methylindenyl) zirconium dichloride, tetramethyldisilylenebis (indenyl) zirconium dichloride, tetramethyldisilylenebis (cyclopentadiene) (Enyl) zirconium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) ( Tetraethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cycl Pentadienyl) (2,7-di -
t-Butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,2) 5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2
-Ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2 ', 7'- Di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (2,5-dimethylcyclopentadienyl) (2 ′,
7'-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl)
Zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl) zirconium dichloride, dimethylsilylene (Dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorene Nyl) zirconium dichloride, dimethylsilylenebis (indenyl) hafnium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) hafnium dichloride Dimethylsilylenebis (2-methylindenyl) hafnium dichloride, dimethylsilylenebis (2,4-dimethylindenyl) hafnium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethyl Cyclopentadienyl) hafnium dichloride, dimethylsilylenebis (2-methyl-4,5-benzoindenyl) hafnium dichloride, dimethylsilylenebis (2-methyl-)
4-naphthylindenyl) hafnium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) hafnium dichloride, phenylmethylsilylenebis (indenyl) hafnium dichloride, phenylmethylsilylenebis (4,5,6,7-tetrahydro) Indenyl) hafnium dichloride, phenylmethylsilylene bis (2,4-dimethylindenyl) hafnium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium Dichloride, phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dichloride, phenylmethylsilylene bis (tetramethylcyclo N-dienyl) hafnium dichloride, diphenylsilylenebis (2,4-dimethylindenyl) hafnium dichloride, diphenylsilylenebis (indenyl) hafnium dichloride, diphenylsilylenebis (2-methylindenyl) hafnium dichloride, tetramethyldisilylenebis (indenyl) Hafnium dichloride, tetramethyldisilylene bis (cyclopentadienyl) hafnium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-dimethyl) Cyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) hafnium dichloride, dimethy Lucilene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (triethyl) Cyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (2 , 7-Di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, dimethyl Len (2-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilylene (2,5-dimethyl-cyclopentadienyl)
(Fluorenyl) hafnium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilylene (2,5
-Diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (2,5- Dimethylcyclopentadienyl) (2 ',
7'-di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (2-ethylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (diethylcyclo) Pentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl)
Hafnium dichloride, dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) hafnium dichloride, dimethylsilylene (diethylcyclopentadienyl) A transition metal compound having two silylene group-bridged conjugated five-membered ring ligands such as (octahydrofluorenyl) hafnium dichloride,

Dimethylgermylene bis (indenyl)
Titanium dichloride, dimethylgermylene (cyclopentadienyl) (fluorenyl) titanium dichloride, methylaluminene bis (indenyl) titanium dichloride, phenylaluminene bis (indenyl) titanium dichloride, phenylphosphylene bis (indenyl) titanium dichloride, ethylborene bis ( Indenyl) titanium dichloride, phenylalumine bis (indenyl) titanium dichloride, phenylalumine (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylgermylene bis (indenyl) zirconium dichloride, dimethylgermylene (cyclopentadienyl) ( Fluorenyl) zirconium dichloride, methylaluminene bis (indenyl) zirconium dichloride, Phenylamylene bis (indenyl) zirconium dichloride, phenylphosphylene bis (indenyl) zirconium dichloride, ethylborene bis (indenyl) zirconium dichloride, phenylamylenebis (indenyl) zirconium dichloride, phenylamylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, dimethylgermylene bis (indenyl) hafnium dichloride, dimethylgermylene (cyclopentadienyl) (fluorenyl)
Hafnium dichloride, methylaluminene bis (indenyl) hafnium dichloride, phenylaluminene bis (indenyl) hafnium dichloride, phenylphosphylene bis (indenyl) hafnium dichloride, ethylborene bis (indenyl) hafnium dichloride, phenylamylene bis (indenyl) hafnium dichloride, Germanium such as phenylamylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
A transition metal compound having two conjugated five-membered ring ligands bridged by a hydrocarbon group containing aluminum, boron, phosphorus or nitrogen,

Pentamethylcyclopentadienyl (diphenylamino) titanium dichloride, indenyl (diphenylamino) titanium dichloride, pentamethylcyclopentadienyl-bis (trimethylsilyl)
Aminotitanium dichloride, pentamethylcyclopentadienylphenoxytitanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) t-butylaminotitanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylaminotitanium dichloride, dimethylsilylene (tetrahydro) Indenyl) decylaminotitanium dichloride, dimethylsilylene (tetrahydroindenyl) [bis (trimethylsilyl) amino] titanium dichloride, dimethylgermylene (tetramethylcyclopentadienyl)
Phenylaminotitanium dichloride, pentamethylcyclopentadienyltitanium trimethoxide, pentamethylcyclopentadienyltitanium trichloride,
Pentamethylcyclopentadienyl-bis (phenyl)
Aminozirconium dichloride, indenyl-bis (phenyl) aminozirconium dichloride, pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, pentamethylcyclopentadienylphenoxyzirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) t -Butylaminozirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylaminozirconium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminozirconium dichloride, dimethylsilylene (tetrahydroindenyl) [bis (trimethylsilyl) amino] zirconium dichloride, Dimethylgermylene (tetramethylcyclopentadienyl) phenyla Nozirconium dichloride, pentamethylcyclopentadienyl zirconium trimethoxide, pentamethylcyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl-bis (phenyl) aminohafnium dichloride, indenyl-bis (phenyl) aminohafnium dichloride, Pentamethylcyclopentadienyl-bis (trimethylsilyl) aminohafnium dichloride, pentamethylcyclopentadienylphenoxyhafnium dichloride, dimethylsilylene (tetramethylcyclopentadienyl)
t-Butylaminohafnium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylaminohafnium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminohafnium dichloride, dimethylsilylene (tetrahydroindenyl) [bis (trimethylsilyl) amino] hafnium dichloride , 1 dimethylgermylene (tetramethylcyclopentadienyl) phenylamino hafnium dichloride, pentamethyl cyclopentadienyl hafnium trimethoxide, pentamethyl cyclopentadienyl hafnium trichloride, etc. having one conjugated five-membered ring ligand Transition metal compounds,

(1,1'-dimethylsilylene) (2,
2'-isopropylidene) -bis (cyclopentadienyl) titanium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) -bis (cyclopentadienyl) titanium dichloride, (1,1) '-
Dimethylsilylene) (2,2'-isopropylidene)-
Bis (cyclopentadienyl) dimethyltitanium,
(1,1′-Dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) dibenzyltitanium, (1,1′-dimethylsilylene) (2,2
2'-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) titanium, (1,1 '
-Dimethylsilylene) (2,2'-isopropylidene)
-Bis (cyclopentadienyl) bis (trimethylsilylmethyl) titanium, (1,2'-dimethylsilylene) (2,1'-ethylene) -bis (indenyl) titanium dichloride, (1,1'-dimethylsilylene)
(2,2′-Ethylene) -bis (indenyl) titanium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) -bis (indenyl) titanium dichloride, (1,1′-dimethylsilylene) (2,2'-
Cyclohexylidene) -bis (indenyl) titanium dichloride, (1,1′-dimethylsilylene) (2,2
2'-isopropylidene) -bis (cyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride, (1,
1'-dimethylsilylene) (2,2'-isopropylidene) -bis (cyclopentadienyl) dimethylzirconium, (1,1'-dimethylsilylene) (2,2'-isopropylidene) -bis (cyclopentadiene) (Enyl) dibenzylzirconium, (1,1'-dimethylsilylene)
(2,2′-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) zirconium,
(1,1′-Dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilylmethyl) zirconium, (1,2′-dimethylsilylene) (2,1′-ethylene) -Bis (indenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-ethylene) -bis (indenyl) zirconium dichloride, (1,1'-ethylene)
(2,2'-Dimethylsilylene) -bis (indenyl)
Zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-cyclohexylidene) -bis (indenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (Cyclopentadienyl) hafnium dichloride, (1,
1′-Dimethylsilylene) (2,2′-dimethylsilylene) -bis (cyclopentadienyl) hafnium dichloride, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadiene) (Enyl) dimethylhafnium, (1,1'-dimethylsilylene)
(2,2'-isopropylidene) -bis (cyclopentadienyl) dibenzylhafnium, (1,1'-dimethylsilylene) (2,2'-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) ) Hafnium, (1,1'-dimethylsilylene) (2,2 '
-Isopropylidene) -bis (cyclopentadienyl)
Bis (trimethylsilylmethyl) hafnium, (1,
2'-Dimethylsilylene) (2,1'-ethylene) -bis (indenyl) hafnium dichloride, (1,1'-
Dimethylsilylene) (2,2'-ethylene) -bis (indenyl) hafnium dichloride, (1,1'-ethylene) (2,2'-dimethylsilylene) -bis (indenyl) hafnium dichloride, (1,1'- Transition metal compounds having two conjugated five-membered ring ligands in which ligands such as dimethylsilylene) (2,2′-cyclohexylidene) -bis (indenyl) hafnium dichloride are double-bridged, and In the compounds described in the above 1 to, the chlorine atom of these compounds is replaced by a bromine atom, an iodine atom, a hydrogen atom, a methyl group, a phenyl group, a benzyl group, a methoxy group,
The thing substituted by the dimethylamino group etc. can be mentioned.

Among the compounds described in 1 to 4, transition metal compounds having two silylene group-bridged conjugated five-membered ring ligands, wherein the transition metal is zirconium or titanium, are particularly preferably used. To be (II) The following compounds may be mentioned as specific examples of the transition metal compound represented by the general formula (5). Tetra
n-butoxytitanium, tetra-i-propoxytitanium, tetraphenoxytitanium, tetracrezoxytitanium, tetrachlorotitanium, tetrakis (diethylamino) titanium, tetrabromotitanium, and compounds in which titanium is replaced with zirconium or hafnium. You can Among these transition metal compounds, alkoxytitanium compounds, alkoxyzirconium compounds and alkoxyhafnium compounds are preferable.

(III) In the transition metal compound represented by the general formula (6), M ² represents a transition metal of Groups 8 to 10 of the periodic table, and specifically, iron, cobalt, nickel, palladium, platinum, etc. Among them, nickel, palladium and iron are preferable. L ¹ and L ² each represent a coordination-bonding organic ligand bonded to a transition metal via a nitrogen atom or a phosphorus atom, and X ⁴ and Y ² respectively represent a covalent bond or an ionic bond. Represents the ligand.
Here, as described above, for X ⁴ and Y ² , specifically, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, and 1 to 20 carbon atoms, preferably Is 1 to 10 alkoxy groups, imino groups, amino groups,
Phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 (for example, diphenylphosphine group) or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 (for example, trimethylsilyl group) , Carbon number 1-2
0, preferably 1 to 12 hydrocarbon groups, or halogen-containing boron compounds [eg B (C ₆ H ₅ ) ₄ , BF ₄ ].
Indicates. Among these, a halogen atom and a hydrocarbon group are preferable. X ⁴ and Y ² may be the same or different from each other. Furthermore, specific examples of L ¹ and L ² include triphenylphosphine; acetonitrile;
Benzonitrile; 1,2-bisdiphenylphosphinoethane; 1,3-bisdiphenylphosphinopropane;
1,1′-bisdiphenylphosphinoferrocene; cyclooctadiene; pyridine; quinoline; N-methylpyrrolidine; bistrimethylsilylaminobistrimethylsilyliminophosphorane. The above L ¹ , L ² , X ⁴ and Y ² may be bonded to each other to form a ring structure.

Specific examples of the transition metal compound represented by the general formula (6) are shown below: dibromobistriphenylphosphine nickel, dichlorobistriphenylphosphine nickel, dibromodiacetonitrile nickel, dibromodibenzonitrile nickel, dibromo (1 , 2-bisdiphenylphosphinoethane) nickel, dibromo (1,3-bisdiphenylphosphinopropane) nickel, dibromo (1,1′-diphenylbisphosphinoferrocene) nickel, dimethylbistriphenylphosphine nickel, dimethyl (1, 2-bisdiphenylphosphinoethane) nickel, methyl (1,2
-Bisdiphenylphosphinoethane) nickel tetrafluoroborate, (2-diphenylphosphino-1-phenylethyleneoxy) phenylpyridine nickel, dichlorobistriphenylphosphine palladium, dichlorodibenzonitrile palladium, dichlorodiacetonitrile palladium, dichloro (1,2) -Bisdiphenylphosphinoethane) palladium, bistriphenylphosphine palladium bistetrafluoroborate, bis (2,2'-bipyridine) methyliron tetrafluoroborate etherate and the compounds shown below.

[0027]

[Chemical 1]

[In the formula, Me represents a methyl group, and R represents a methyl group or an isopropyl group. Among these compounds, methyl (1,2-bisdiphenylphosphinoethane) nickel tetrafluoroborate, bistriphenylphosphine palladium bistetrafluoroborate, bis (2,2′-bipyridine) methyliron tetrafluoroborate etherate, etc. A cationic complex or a compound represented by the above formula is preferably used. In the catalyst of the present invention, the transition metal compound as the component (B) may be used alone or in combination of two or more.

Examples of the olefin as the component (C) include olefins, styrene and styrenes. The olefins are not particularly limited, but ethylene and α-olefins having 3 to 20 carbon atoms are preferable. Examples of the α-olefin include propylene, 1-butene, 1-
Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6-phenyl-1-hexene, 3-methyl-1-butene, 4-methyl- 1-butene, 3-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4, Linear or branched α-olefins such as 4-dimethyl-1-pentene and vinylcyclohexane, dienes such as 1,3-butadiene, 1,4-pentadiene and 1,5-hexadiene, hexafluoropropene, tetrafluoro Ethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene,
Halogen-substituted α-olefins such as 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 5-benzylnorbornene, etc. Cyclic olefins of As styrenes, p-methylstyrene, p-ethylstyrene, p-propylstyrene,
p-isopropylstyrene, p-butylstyrene, p-
t-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene,
m-ethyl styrene, m-isopropyl styrene, m-
Alkyl styrenes such as butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene and 3,5-dimethyl styrene, and alkoxy such as p-methoxy styrene, o-methoxy styrene and m-methoxy styrene. Styrenes, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o- Examples thereof include halogenated styrene such as methyl-p-fluorostyrene, trimethylsilylstyrene, vinyl benzoate, divinylbenzene and the like. In the present invention, the olefin as the component (C) may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be combined arbitrarily.

In the present invention, the above-mentioned olefins may be copolymerized with other monomers. Examples of other monomers used at this time include butadiene, isoprene and 1,4-pentadiene. , Chain diolefins such as 1,5-hexadiene, norbornene, 1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, polycyclic olefins such as 2-norbornene, norbornadiene, 5-ethylidene norbornene, 5-vinyl norbornene, dicyclopentadiene and the like. Examples thereof include cyclic diolefins. In the present invention, the olefin as the component (C) is preferably one selected from ethylene, propylene, 1-olefin having 4 to 12 carbon atoms, cyclic olefin and styrene. Among these, ethylene, propylene, 1-butene, 1-hexene, 1-octene and styrene are more preferable, and ethylene and propylene are particularly preferable. The olefin content in the copolymer is 70
It is preferably from 9 to 99.9% by mass, particularly preferably from 90 to 99.9% by mass. The production method of the present invention is a production method suitable for obtaining a copolymer using propylene as an olefin and having a propylene content of 70% by mass or more in the copolymer.

The polar vinyl monomer as the component (D) is not particularly limited, but is represented by the general formula (1) CH ₂ ═CR ¹ (CR ² ₂ ) _n X ¹ (1) [wherein R ¹ and R ² are hydrogen. Atom or carbon number 1-10
Hydrocarbon group of X ¹ is OH, OR ³ , NH ₂ , NHR
_{^{3, NR 3 2, COOH,}} COOR 3, SH, Cl, F,
I or Br (R ³ is a hydrocarbon group having 1 to 10 carbon atoms, or a functional group containing silicon or aluminum), and n is an integer of 0 to 20. ] What is represented by these is preferable.
Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, an alkenyl group and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert- group.
Examples thereof include a butyl group, an n-hexyl group, and an n-decyl group, and those having 1 to 20 carbon atoms are preferable in the present invention. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-hexenyl group, a 1-octenyl group and a cyclohexenyl group, and those having 2 to 10 carbon atoms are preferable in the present invention. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and those having 6 to 14 carbon atoms are preferable in the present invention. Examples of the functional group containing silicon include a trimethylsilyl group, a triethylsilyl group, a tri-t-butylsilyl group and a triisopropylsilyl group.
n is preferably 1-10. In the present invention, the polar vinyl monomer is represented by the general formula (1 ′) CH ₂ ═CHCH ₂ X ¹ (1 ′) [wherein X ¹ is OH, OR ³ , NH ₂ , NHR ³ , N].
R ³ _2, or SH (R ³ is a hydrocarbon group having 1 to 10 carbon atoms,
Or a functional group containing silicon or aluminum). ] Those represented by are particularly preferable.

Specific examples of the polar vinyl monomer include N
-Trimethylsilylallylamine, N-trimethylsilyl-3-butenylamine, N-trimethylsilyl-5-
Amines such as hexenylamine, allyl alcohol,
2-Methyl-3-buten-2-ol, 3-butene-1
-Ol, 2-methyl-3-buten-1-ol, 4-
Penten-1-ol, 5-hexen-1-ol, 6
-Hepten-1-ol, 7-octen-1-ol,
Alcohols such as 8-nonen-1-ol, 9-decen-1-ol and 10-undecen-1-ol,
There may be mentioned ethers such as allyl butyl ether, allyl ethyl ether, allyl benzyl ether, diallyl ether, 3-butenyl butyl ether, 3-butenyl ethyl ether and 3-butenyl benzyl ether. When a polar vinyl monomer having an active hydrogen such as an OH group or an NH group is used, protection with a functional group containing silicon or aluminum in advance can increase the polymerization activity.

The polymerization reaction is carried out using hydrocarbons such as butane, pentane, hexane, toluene and cyclohexane, and liquefied α
-It is performed in the presence of a solvent such as an olefin or under the condition of no solvent. The larger the amount of the (B) transition metal complex used with respect to the (A) layered compound, the higher the activity per catalyst mass, but in practice, the amount of the transition metal complex used is 0.1 to 100 micrograms per 1 g of the layered compound. It is a mole. The polymerization temperature is -50 ° C to 250 ° C, preferably room temperature to 150 ° C. The pressure is not particularly limited, but is preferably in the range of normal pressure to 200 MPa. Further, hydrogen may be present as a molecular weight modifier in the polymerization system. In the polymerization process, increase the internal temperature by 15 ° C due to heat generation in the polymerization reaction tank.
If either condition of suppressing to within (preferably within 10 ° C.) or preliminarily polymerizing the polymerization catalyst with olefin is satisfied, polymerization activity and selectivity of copolymerization can be secured. At the time of polymerization, the following organoaluminum compound can be added, if necessary. As the organic aluminum compound, the following general formula (7) is used.

R ¹⁵ _v AlQ ³ _3-v (7) (In the formula, R ¹⁵ is an alkyl group having 1 to 10 carbon atoms, Q ³ is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, and 6 to 2 carbon atoms.
0 represents an aryl group or a halogen atom, and v is an integer of 1 to 3. ) Compounds (excluding trimethylaluminum) are used. Specific examples of the compound represented by the general formula (7) include triethylaluminum,
Examples include triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more. Moreover, an aluminum oxy compound is mentioned as another organoaluminum compound. As the aluminum oxy compound, the following general formula (8) is used.

[0035]

[Chemical 2]

(Wherein R ¹⁶ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. Each R ¹⁶ may be the same or different. ) A chain aluminoxane represented by the following formula and the following general formula (9)

[0037]

[Chemical 3]

A cyclic aluminoxane represented by the formula (wherein R ¹⁶ and w are the same as those in the general formula (8)) can be mentioned. Specific examples of the aluminoxane include ethylaluminoxane and isobutylaluminoxane. In the present invention, as the organoaluminum compound, triethylaluminum, triisobutylaluminum, in the above general formula (8),
At least one alkyl group having 2 or more carbon atoms of R ^14, are preferred other R ¹⁴ is an alkyl group having 1 to 10 carbon atoms. If trimethylaluminum or methylaluminoxane is used, the addition polymer may be in the form of a lump, which may make the handling operation after polymerization difficult.

[0039]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
As will be appreciated, the invention is in no way limited by these examples.
Not something. [Example 1]Preparation of silane-treated layered compound 4 liters of distilled water in a 3-neck flask with an internal volume of 5 liters
, And while stirring, the layered compound (Corp Chemical Co., Ltd.
Manufactured by Na-Fluorotetrasilicon mica, product name Somasif ME-10
0, layer charge 0.6) 25 g was gradually added. Layer after addition
The compound suspension was stirred at room temperature for 1 hour. Then this melt
Diethyldichlorosilane [(C₂H _Five)₂SiCl
₂] Slowly add 5 ml to the layered compound suspension
It was After the addition, continue stirring at room temperature for 1 hour, then at 100 ° C.
The temperature was raised to 3, and the suspension was stirred at the same temperature for 3 hours. During this time
The suspension turned into a sedimentary hydrophobic slurry. This hydrophobic
Slurry pressurizer (air pressure 0.5MPa, membrane pore size 3μm
It was filtered while hot with a membrane filter). Required for filtration
It took 7 minutes. The filtered material obtained is dried at room temperature.
25 g of this filtered material is added to 250 ml of toluene.
Suspended in water.
Solution (1.0 mol / l) 160 ml
Add each of them, and after the addition, raise the temperature to 100 ° C and keep at the same temperature for 1 hour
It was stirred. The obtained aluminum-treated slurry was
After washing with water, the total amount of the solution is 500 millilitres with toluene.
And a silane-treated layered compound slurry was obtained.

Propylene using silane-treated layered compound
Copolymerization of N-trimethylsilylallylamine with 400 ml of dry toluene and 0.5 ml of triisobutylaluminum in a 1.6-liter three-necked flask.
Mmol, 20 ml of the silane-treated layered compound slurry prepared in the preceding paragraph (silane-treated layered compound 1.0 g)
And N-trimethylsilylallylamine [CH ₂ ═CH
CH ₂ NHSi (CH ₃ ) ₃ ] 0.5 ml was sequentially added and the temperature was raised to 70 ° C. Next, the pressure was increased while continuously supplying propylene gas, and the internal pressure was maintained at 0.7 MPa (gauge pressure). Then, a solution of dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride suspended in heptane (1 micromol / ml heptane) with the internal temperature kept at 70 ° C.
2 ml was added to the polymerization system. Polymerization pressure 0.7MP
a, Polymerization was carried out by continuing the supply of propylene while maintaining the polymerization temperature at 70 ° C. When 2 hours had passed from the start of the polymerization, methanol was added to the polymerization system to terminate the polymerization.
Next, the product was separated by filtration and dried at 90 ° C. under reduced pressure for 12 hours. As a result, 146 g of a dry mass of the copolymer was obtained. The content of the silane-treated layered compound in the copolymer was 0.68% by mass, and the polymerization activity was 802 kg / gZr.
Met.

Confirmation test of functional group introduction A solution of 23 mg of the copolymer obtained in the previous section and 10 ml of trichlorobenzene was heated to a temperature of 150 ° C., and the insoluble layered compound was filtered (mesh 5 μm).
It was filtered with. The filtrate was added to 300 ml of methanol with stirring to reprecipitate the dissolved polymer. Next, the precipitated copolymer was filtered using a filter having a mesh of 0.2 μm and dried in vacuum at 90 ° C. for 4 hours. Next, the presence of the primary amine contained in the copolymer was confirmed by a characteristic absorption spectrum using an infrared absorption spectrum device. FIG. 1 shows an infrared spectrum of polypropylene containing a primary amine. The antisymmetric stretching vibration and symmetric vibration of NH ₂ are 3414 cm ⁻¹ and 3347, respectively.
in cm ^-1, scissor vibration of NH ₂ from that appeared in 1642 cm ^-1, it was found that the copolymerization of allylamine and propylene is in progress. The N-trimethylsilyl group reacts with methanol when the copolymer is treated with methanol to release free amine.

Of allylamine units in the copolymer
Distribution Measurement 22 mg of the copolymer obtained in the preceding paragraph was dissolved in 10 ml of trichlorobenzene, and the insoluble layered compound was filtered with a filter (mesh 5 μm) while the temperature was raised to 150 ° C. Then, the filtrate is GPC-FTIR.
The instrument (gel permeation chromatography-Fourier transform infrared instrument) was run. As the GPC-FTIR, a GPC-body connected to the FTIR body using a transfer tube and a flow cell was used. The molecular weight distribution in the above copolymer and the composition distribution of the allylamine unit in the copolymer were measured according to the following methods. The measurement results are shown in FIG. In FIG. 2, A
Indicates the content of allylamine unit in the resin of each molecular weight, and B indicates the molecular weight distribution of the resin. From FIG. 2, it can be seen that the allylamine unit contained in the copolymer is distributed over each molecular weight, and the copolymerization of propylene and allylamine is progressing.

(A) Measuring instrument GPC main body: GL Science, high temperature GPC column oven FTIR: Nicolet OMNIC E. S. P and Nicolet SPEC-FTIR Ver. 2.
10.2 (b) Measurement conditions Solvent: 1,2,4-trichlorobenzene, measurement temperature: 1
45 ° C, flow rate: 1.0 ml / min, sample concentration:
0.3 (w / v), sample injection volume: 1,000 ml,
GPC column: Shodex UT806MLT 2 (C) FTIR measurement conditions Detector type: MCT detector, IR spectrum resolution: 4 cm ^-1 , 1 data (IR spectrum) scan count: 13 scans, 1 data (IR spectrum) ) Acquisition time: 1 data acquisition every 10.8 seconds (d) Molecular weight distribution curve, Mw (weight average molecular weight) and M
Measurement of n (number average molecular weight) A chromatogram was obtained by the above GPC-FTIR, and data analysis software for GPC-FTIR (Nicolet OMNICSEC- ) was obtained for this chromatogram.
FTIR Ver. 2.10.2), the molecular weight distribution curve [log ₁₀ M to d (w) / d
(Log ₁₀ M)], the weight average molecular weight Mw and the molecular weight distribution Mw / Mn were determined. The molecular weight was calculated by using a standard calibration curve prepared by using standard polystyrene manufactured by Tosoh Corporation. In addition, all molecular weights were calculated as polypropylene equivalents based on the Q value method. (E) Measurement of allylamine composition curve Using the data analysis software for GPC-FTIR, the amount of allylamine copolymerized with propylene (measured by the strength ratio of the methyl group and the methylene group in the copolymer) was calculated, and the calculated value was calculated. The composition curve of the allylamine unit was prepared from

Comparative Example 1 Propylene and N-tris using methylaluminoxane
Methylsilylallylamine Copolymerization In Example 1, instead of using 1.0 g of the silane-treated layered compound, MAO (manufactured by Tosoh Akzo, toluene-diluted methylaluminoxane: 2.0 mmol / ml in terms of Al atom) 0.5 Copolymerization of propylene and N-trimethylsilylallylamine was carried out in exactly the same manner as in Example 1 except for using milliliter. The polymerization proceeded slowly and 30 g of a dry mass of polymer was obtained. Distribution Measurement of Allylamine Unit in Polymer As in Example 1, the polymer was dissolved, filtered, and the obtained filtrate was dispersed in methanol to reprecipitate the polymer.
Next, the dried polymer is applied to a GPC-FTIR apparatus,
When the content of amine in the polymer was examined, the content of allylamine unit was zero at each molecular weight. That is, when MAO was used instead of the layered compound, the copolymerization of propylene and N-trimethylsilylamine did not proceed.

[Example 2] Copolymerization of propylene and allyl alcohol In Example 1, 0.5 ml of N-trimethylsilylallylamine was changed to 0.5 ml of allyl alcohol, and the amount of triisobutylaluminum used was changed.
Example 1 except 0.5 mM to 2 mM
Copolymerization of propylene and allyl alcohol was carried out in the same manner as in. The polymerization proceeded slowly, with a dry mass of 9.7.
g of copolymer was obtained. The content of the silane-treated layered compound in the copolymer was 10.3% by mass, and the polymerization activity was 55.
It was kg / g Zr. Distribution Measurement of Allyl Alcohol Unit in Copolymer The same treatment as in Example 1 was carried out, and the filtrate was applied to a GPC-FTIR apparatus. The result is shown in FIG. In FIG. 3, A
Indicates the content of allyl alcohol unit in the resin of each molecular weight, and B indicates the molecular weight distribution of the resin. From FIG. 3, it can be seen that the amount of allyl alcohol contained in the copolymer is small but distributed over each molecular weight, and the copolymerization of propylene and allyl alcohol is progressing.

COMPARATIVE EXAMPLE 2 Instead of using 1.0 g of the silane-treated layered compound in Example 2, MAO (manufactured by Tosoh Akzo Co., toluene-diluted methylaluminoxane: A) was used.
0.5 milliliter) was used in the same manner as in Example 2, except that 1 milliliter converted to 2.0 millimol / ml.
Copolymerization of propylene and allyl alcohol was performed. However, absorption of propylene did not occur even after 2 hours. Also, the liquid after the polymerization operation treatment was dispersed in a large amount of methanol, but no polymer formation was observed.

[0047]

According to the production method of the present invention, copolymerization of an olefin and a polar vinyl monomer can be carried out with high activity.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of polypropylene containing a primary amine in Example 1.

FIG. 2 is a diagram showing a molecular weight distribution of a polymer and a composition distribution of an allylamine unit in the polymer in Example 1.

FIG. 3 is a diagram showing a molecular weight distribution of a polymer and a composition distribution of an allyl alcohol unit in the polymer in Example 2.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J028 AA01A AA02A AB00A AB01A                       AB02A AC01A AC05A AC07A                       AC08A AC10A AC24A AC25A                       AC26A AC28A AC45A AC46A                       AC47A AC48A BA00A BA01B                       BA02B BA03B BB00A BB00B                       BB01B BB02B BC15B BC25B                       BC33B BC34B BC39B CA30B                       EA01 EB02 EB04 EB05 EB07                       EB09 EB12 EB13 EB14 EB17                       EB18 EB21 EB22 EB23 EB24                       EB25 EB26                 4J100 AA02P AA03P AA04P AA07P                       AA09P AA15P AA16P AA18P                       AA19P AA20P AB01P AB04P                       AB07P AB08P AB09P AB10P                       AB16P AC02P AC22P AC23P                       AC24P AC25P AC26P AC27P                       AD01Q AD03Q AE13Q AE18Q                       AE21Q AE64Q AG08P AN02Q                       AN05Q AR04P AR05P AR11P                       AR21P AR22P AS02P AS03P                       AS04P AS11P AS15P AU21P                       BA05P BA72P BA72Q BC43P                       BC43Q CA00 CA04 JA03

Claims (9)

[Claims] 1. A layered compound (A) and a periodic table (B) No. 4
A method for producing an olefin / polar vinyl monomer copolymer, which comprises copolymerizing (C) an olefin and (D) a polar vinyl monomer using a catalyst composed of a Group 10 to 10 transition metal complex. 2. The polar vinyl monomer (D) has the general formula (1) CH ₂ ═CR ¹ (CR ² ₂ ) _n X ¹ (1) [wherein R ¹ and R ² are hydrogen atoms or carbon atoms. 1-10
Hydrocarbon group of X ¹ is OH, OR ³ , NH ₂ , NHR
_{^{3, NR 3 2, COOH,}} COOR 3, SH, Cl, F,
I or Br (R ³ is a hydrocarbon group having 1 to 10 carbon atoms, a functional group containing silicon or aluminum), and n is 0 to
It is an integer of 20. ] The manufacturing method of Claim 1 which is a polar vinyl monomer represented by these. 3. The method according to claim 1, wherein the component (A) is a 2: 1 type layered compound having a layer charge of 0.1 to 0.7. 4. The component (A) comprises the compound represented by the general formula (2) R ⁴ _4-m SiX ² _m (2) (wherein R ⁴ represents a hydrocarbon-containing group. X ² is directly bonded to silicon). The element is a halogen, nitrogen or oxygen functional group, and m is an integer of 1 to 3.) is a layered compound treated with an organosilane compound represented by any one of claims 1 to 3. The manufacturing method described. 5. The production method according to claim 1, wherein the component (B) is a metal complex having a ligand having a conjugated 5-membered ring or a chelate ligand of a hetero atom. 6. The production method according to claim 1, wherein the component (B) is a metal complex having a ligand having a conjugated 5-membered ring, and the transition metal is zirconium or titanium. 7. The component (C) is ethylene, propylene,
The manufacturing method according to any one of claims 1 to 6, which is selected from 1-olefins having 4 to 12 carbon atoms and cyclic olefins. 8. The component (C) is propylene, and the propylene content in the copolymer is 70% by mass or more.
The manufacturing method described in. 9. The component (D) is represented by the general formula (1 ′) CH ₂ ═CHCH ₂ X ¹ (1 ′) [wherein, X ¹ is OH, OR ³ , NH ₂ , NHR ³ , N].
R ³ ₂ or SH (R ³ are functional groups containing a hydrocarbon group, a silicon or aluminum to 10 carbon atoms). ] The manufacturing method in any one of Claims 2-8 which is a polar vinyl monomer represented by these.