JP2003206308A - Polymerization catalyst for vinyl compound, polymer of vinyl compound and its manufacturing method, and composite resin comprising the polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer of a vinyl compound considerably enhanced in melt viscoelasticity or mechanical characteristics and a composite resin comprising the polymer of a vinyl compound excellent in various mechanical characteristics. <P>SOLUTION: The polymer of a vinyl compound is obtained using a catalyst composed of an alkenylsilane-treated product (component A) obtained by treating a layered compound with an alkenylsilane and a metal complex (component B) of a group 4-6 or group 8-10 transition metal in the periodic table. The composite resin is manufactured using the polymer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a alkenylsilane-treated product (component A) obtained by treating a layered compound with alkenylsilane and a transition metal complex of Group 4 to 6 or 8 to 10 of the periodic table (component B). And a catalyst for vinyl compound polymerization, which comprises a) and a method for polymerizing a vinyl compound using the catalyst. The present invention also relates to a polymer of a vinyl compound obtained by using the catalyst and a composite resin comprising the polymer of the vinyl compound and a thermoplastic resin. The present invention further relates to a composite resin composition comprising a copolymer of alkenylsilane and propylene and a layered compound, wherein the layered compound is dispersed in the copolymer as very fine particles. It is a thing.

[0002]

BACKGROUND OF THE INVENTION Copolymerization of alkenylsilanes and olefins is known, but addition polymers having a preferable melt viscoelasticity, particularly addition polymers having a high non-Newtonian property cannot be obtained. In order to obtain an addition polymer having excellent melt viscoelasticity, crosslinking by radiation (Japanese Patent No. 3169385) or transition metal complex treatment (Japanese Patent No. 3169386) was necessary.
That is, in these techniques, the intended purpose cannot be achieved unless the copolymer of alkenylsilane and olefin is produced and more operations are performed. As a method for polymerizing an olefin using a layered silicate and a metallocene complex, for example, WO99 / 14247 and WO99 /
48930, WO00 / 11044 and W
O00 / 32642 and the like are known, but addition polymers having high melt viscoelasticity and excellent mechanical properties have not been obtained. A description of a polymerization catalyst comprising an alkenylsilane-treated product (component A) obtained by treating a layered compound with alkenylsilane and a transition metal complex of Group 4 to 6 or 8 to 10 of the periodic table (component B) There is no.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is an alkenylsilane-treated product (component A) obtained by treating a layered compound with alkenylsilane and Periodic Tables 4 to 6. Or Group 8-10 transition metal complex (component B)
An object of the present invention is to provide a vinyl compound polymerization catalyst consisting of and a method for polymerizing a vinyl compound using the catalyst. Another object of the present invention is to provide a polymer of a vinyl compound obtained by using the catalyst and a composite resin composed of a polymer of the vinyl compound and a thermoplastic resin. The present invention further relates to a composite resin composition comprising a copolymer of alkenylsilane and propylene and a layered compound, wherein the layered compound is dispersed in the copolymer as very fine particles. It is a thing.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an alkenylsilane-treated product (component A) obtained by treating a layered compound with alkenylsilane Use of a polymerization catalyst composed of a transition metal complex of Group 4 to 6 or Group 8 to 10 (B component) of the Periodic Table enhances the non-Newtonian property of the vinyl compound polymer or significantly increases mechanical properties such as tensile properties. It was found to improve. Furthermore, they have found that a composite resin composed of a polymer of a vinyl compound and a thermoplastic resin is excellent in various mechanical properties, and completed the present invention. That is, the present invention is as follows.
Alkenylsilane-treated product (component A) obtained by treating a layered compound with alkenylsilane and Periodic Table Nos. 4 to 6 or 8
1. A vinyl compound polymerization catalyst comprising a group-10 transition metal complex (component B); The layered compound has a layer charge of 0.1 to 0.
2. The catalyst for polymerization of vinyl compound according to 1 above, which is a 2: 1 type layered compound having 7. The alkenylsilane is represented by the general formula R ⁹ _4-n SiX _n (wherein, R ⁹ is a hydrocarbon-containing group and at least one is a group having a carbon-carbon double bond, and X is an element directly bonded to silicon. Is a functional group of halogen, nitrogen or oxygen, and n is an integer of 1 to 3. However, when R ⁹ is plural, each R ⁹ may be the same or different. 3. The catalyst for polymerization of vinyl compound according to 1 or 2 above, Alkenyl silane of the general formula _{H 2 C = CH- (CH 2} ) k -SiH m R 3-m ( wherein, R is an alkyl group having 1 to 5 carbon atoms, k is 1
The above integer, m is an integer of 1 to 3. ). 4. The vinyl compound polymerization catalyst according to 1 or 2, which is a silane compound containing a hydride represented by 5. The component (B) is a catalyst for vinyl compound polymerization according to any one of 1 to 4 above, which is a metal complex having a ligand having a 5-membered carbon ring or a chelate ligand of a hetero atom. 6. A method for producing a catalyst for vinyl compound polymerization, which comprises contacting a layered compound with an alkenylsilane, and then contacting the resulting component (A) with component (B). Upon contacting the layered compound and the alkenylsilane, the layered compound is contacted with the organosilane compound treatment excluding the alkenylsilane compound in advance, or is contacted with the organosilane compound excluding the alkenylsilane compound at the same time as or after the alkenylsilane compound,
7. The method for producing the vinyl compound polymerization catalyst according to 6 above, which comprises preparing the component (A); Per unit weight g of the component (A),
8. The method for producing a vinyl compound polymerization catalyst according to any one of 6 to 7 above, wherein the component (B) is contacted in an amount of 0.01 to 100 µmol. A method for polymerizing a vinyl compound (component C), which uses the polymerization catalyst according to any one of 1 to 5 above or the polymerization catalyst produced by the method according to any one of 6 to 8 above,
10. Component (C) is ethylene, propylene, butene,
10. The method for polymerizing a vinyl compound described in 9 above, which is one or more olefins selected from butadiene, cyclic olefins having 5 to 20 carbon atoms, and styrene. 12. A polymer of a vinyl compound (C component) obtained by using the polymerization catalyst according to any one of 1 to 5 above or the polymerization catalyst produced by the method according to any one of 6 to 8 above. 13. A composite resin comprising the polymer of the vinyl compound (component C) according to 11 above and a thermoplastic resin; The present invention relates to a composite resin composition comprising a copolymer of alkenylsilane and propylene and a layered compound, wherein the layered compound is dispersed in the copolymer as particles of 1 μm or less.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The layered compound of the present invention is a clay, a clay mineral, or an ion-exchangeable layered compound. Clay is an aggregate of fine hydrous silicate minerals, which produces plasticity when kneaded with an appropriate amount of water, shows rigidity when dried, and sinters when baked at high temperatures. Clay minerals are hydrous silicates that are the main components of clay. To prepare the A component,
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 the layered compound include phyllosilicates as clay minerals. Examples of the phyllosilicates include phyllosilicate and phyllosilicate. Phyllosilicates include, as natural products, montmorillonites, saponites, hectorites, hectorites, illites, mica, and smectites and mica, or mixed-layer minerals of mica and vermiculite. Can be mentioned. Further, as synthetic products, tetrafluorosilicon mica, laponite, smecton and the like can be mentioned. Besides this, α
_{-Zr (HPO 4) 2, γ} -Zr (HPO 4) 2, α-Ti
Ionic crystalline compounds having a layered crystal structure that is not a clay mineral, such as (HPO ₄ ) ₂ and γ-Ti (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 a lot of other components in montmorillonite, gyrrome clay, and sepiolite showing fibrous morphology. , Palygorskite, or amorphous or low crystalline allophane,
There are imogo lights etc. Further, the layered compound is preferably particles having a volume average particle diameter of 10 μm or less, and more preferably particles having a volume average particle diameter of 3 μm or less. In general, the particle shape of the particles has a particle size distribution, but as the layered compound, 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.
It is preferable to have a particle size distribution of at least 10% by weight, a volume average particle size of not more than 10 μm, and a particle size distribution of 10% by weight or more with a volume average particle size of not more than 1.5 μm. Is more preferable. 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 (GALAI P
production Ltd. A measurement method using CIS-1) manufactured by K.K. Among these layered compounds,
A compound having a high ability to form an intercalation compound (also referred to as intercalation) by adsorbing or reacting an amine compound or a Bronsted acid adduct thereof with clay or the like is preferable. For example, clay or clay minerals are preferable, specifically, phyllosilicates are preferable, and smectite is more preferable.
Particularly preferred is montmorillonite. Particularly preferred layered compounds are 2: having a layer charge of 0.1 to 0.7:
Among them, it is a type 1 layered compound, and among them, smectite group clay minerals and fluorine tetrasilicon mica group having water swelling ability are preferable.

The alkenylsilane of the present invention has the general formula R ⁹ _4-n SiX _n (wherein R ⁹ is a hydrocarbon-containing group, and at least one is a group having a carbon-carbon double bond, and X is The element directly bonded to silicon is a functional group of halogen, nitrogen or oxygen, and n is an integer of 1 to 3. However, when R ⁹ is plural, each R ⁹ may be the same or different. ) Is a silane compound. Specific examples thereof include vinyltrichlorosilane, vinylmethyldichlorosilane, vinylethyldichlorosilane, vinyloctyldichlorosilane, vinyldiphenylchlorosilane, allyltrichlorosilane, allylmethyldichlorosilane, allylethyldichlorosilane, allyl (2-cyclohexenyl- 2-
Ethyl) dichlorosilane, allyldimethylchlorosilane, allylhexyldichlorosilane, allylphenyldichlorosilane, 5- (bicycloheptenyl) methyldichlorosilane, 5- (bicycloheptenyl) trichlorosilane, (2- (3-cyclohexenyl) ethyl ) Dimethylchlorosilane, (2- (3-cyclohexenyl) ethyl) methyldichlorosilane, and (2- (3-cyclohexenyl) ethyl) trichlorosilane. In addition, a silane compound in which the halide of the above compound is changed to an alkoxy group, an amino group, or an amide group, and a group of vinyl silicones (vinyl-terminated silicone oil) called reactive silicones can also be mentioned. Furthermore,
Alkenylsilane of the present invention have the general formula _{H 2 C = CH- (CH 2} ) k -SiH m R 3-m ( wherein, R is an alkyl group having 1 to 5 carbon atoms, k is 1
The above integer, m is an integer of 1 to 3. ). A silane compound containing a hydride represented by, for example, allyldimethylsilane.

As the component (B) used in the present invention, a transition metal complex of Groups 4 to 6 or 8 to 10 of the periodic table is used. Among them, the transition metal complexes of Groups 4 to 6 of the Periodic Table are represented by the following general formulas (I-3) to (I-
Those represented by 5) can be mentioned as preferable ones, and as the transition metal complex of Group 8 to 10 of the periodic table, those represented by the following general formula (I-6) are preferable. Can be mentioned. ^{_{Q 1 a (C 5 H 5}} -ab R 1 b) (C 5 H 5-ac R 2 c) M 1 X 1 P Y 1 q ··· (I-3) Q 2 a (C 5 H 5- _ad R ³ _d ) Z ¹ M ¹ X ¹ _P Y ¹ _q ... (I-4) M ¹ X ² _r ... (I-5) L ¹ L ² M ² X ² _u Y ² _v ... · (I-6) [in formula (I), Q ¹ is two conjugated five-membered ring ligand (C ₅ H
_5-ab R ¹ _b ) and (C ₅ H _5-ac R ² _c ) are linked to each other, and Q ² is a conjugated five-membered ring ligand (C ₅ H _5-ad R ³ _d ). Z ¹
The bonding group which bridge | crosslinks a group is shown. R ¹ , R ² and R ³ each represent a hydrocarbon group, a halogen atom, an alkoxy group, 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
Is. b, c, and d are 0 when a = 0
5, an integer of 0 to 4 when a = 1, a =
When 2, it is an integer of 0 to 3. (P + q) is (valence of M ¹ −2), and r is the valence of M ¹ . M ¹
Is a transition metal of Groups 4 to 6 of the Periodic Table, M ² is a Periodic Table 8 to 1
It represents a Group 0 transition metal, and (u + v) represents the valence of M ² . L ¹ and L ² each represent a ligand having a coordinate bond, and X ¹ , Y ¹ , Z ¹ , X ² and Y ² each represent a covalent bond or an ionic bond. Represents. In addition, L ¹ ,
L ² , X ² and Y ² may be bonded to each other to form a ring structure. Specific examples of Q ¹ and Q ² include (1) methylene group, ethylene group, isopropylene group, methylphenylmethylene group, diphenylmethylene group, cyclohexylene group, and other alkylene groups having 1 to 4 carbon atoms; Alkylene group or side chain lower alkyl or phenyl substitution product thereof, (2) silylene group, dimethylsilylene group, methylphenylsilylene group, diphenylsilylene group, disilylene group, silylene group such as tetramethyldisilylene group, oligosilylene group or the like Side chain lower alkyl or phenyl substitution product, (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, (CH ₃ ) B
Group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group, (C ₆ H ₅ ) Al
Group, a hydrocarbon group containing germanium such as (CH ₃ O) Al group, phosphorus, nitrogen, boron or aluminum [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. In addition, (C ₅ H _5-ab R ¹ _b ), (C ₅ H
_5-ac R ² _c ) and (C ₅ H _5-ad R ³ _d ) are conjugated five-membered ring ligands, and R ¹ , R ² and R ³ 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
Are integers of 0 to 5 when a = 0, integers of 0 to 4 when a = 1, and 0 when a = 2.
Indicates an integer of ˜3. 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 preferably has 1 to 12 carbon atoms. Examples of the silicon-containing hydrocarbon group include —Si (R ⁴ ) (R ⁵ ) (R ⁶ ) (R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups having 1 to 24 carbon atoms), and the like. The hydrocarbon group, the nitrogen-containing hydrocarbon group and the boron-containing hydrocarbon group are each P- (R ⁷ )
^{(R 5), - N (} R 7) (R 8) and ^{-B (R 7) (R 8} )
(R ⁷ and R ⁸ are hydrocarbon groups having 1 to 18 carbon atoms) and the like. When there are a plurality of R ¹ , R ² and R ³ , respectively, a plurality of R ¹ , a plurality of R ² and a plurality of R ³ may be the same or different in each. In addition, in the general formula (I-3), a conjugated five-membered ring ligand (C ₅ H
_5-ab R ¹ _b ) and (C ₅ H _5-ac R ² _c ) may be the same or different. 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,
Tungsten and the like can be mentioned, but among these, titanium, zirconium and hafnium are preferable from the viewpoint of activity. Z ¹ is a covalent ligand, and specifically, a halogen atom, oxygen (—O—), sulfur (—S)
-), An alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and a nitrogen-containing hydrocarbon having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms Group (for example, t-butylamino group, t-butylimino group, etc.), having 1 to 40 carbon atoms, preferably 1 to
18 shows a phosphorus-containing hydrocarbon group. X ¹ and Y ¹ are each a covalent ligand or a binding ligand, specifically, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. , 1 to 20 carbon atoms, preferably 1 to 10 alkoxy groups, amino groups, 1 to 1 carbon atoms
20, preferably 1 to 12 phosphorus-containing hydrocarbon group (for example, diphenylphosphine group) or 1 to 2 carbon atoms
0, preferably 1 to 12 silicon-containing hydrocarbon groups (eg, trimethylsilyl group), 1 to 20 carbon atoms, preferably 1 to 12 hydrocarbon groups, or halogen-containing boron compounds (eg, B (C ₆ H ₅ )). ₄ , BF ₄ ). Of these, a halogen atom and a hydrocarbon group are preferable. This X ¹
And Y ¹ may be the same or different from each other. X ² is a covalently bound ligand, specifically a halogen atom, a hydrocarbylamino group or a hydrocarbyloxy group, preferably an alkoxy group.

(I) The above general formulas (I-3) and (I-
As a specific example of the transition metal complex represented by 4),
We can mention compound. Bis (cyclopentadienyl) titanium dichloride
De, bis (methylcyclopentadienyl) titanium di
Chloride, bis (dimethylcyclopentadienyl) tita
Bis (trimethylcyclopentadiene)
Nyl) titanium dichloride, bis (tetramethylcyclo)
Lopentadienyl) titanium dichloride, bis (pen
Tamethylcyclopentadienyl) titanium dichloride
De, bis (n-butylcyclopentadienyltitanium
Dichloride, bis (indenyl) titanium dichloride
De, bis (fluorenyl) titanium dichloride, bis
(Cyclopentadienyl) titanium chlorohydride,
Bis (cyclopentadienyl) methyl titanium chloride
De, bis (cyclopentadienyl) ethyl titanium
Lolid, bis (cyclopentadienyl) phenyl titani
Umchloride, bis (cyclopentadienyl) dimethyl
Titanium, bis (cyclopentadienyl) diphenyl
Titanium, bis (cyclopentadienyl) dineopen
Till titanium, bis (cyclopentadienyl) dihydride
Rotitanium, (cyclopentadienyl) (indeni
Ru) titanium dichloride, (cyclopentadienyl)
(Fluorenyl) titanium dichloride, bis (cyclo
Pentadienyl) zirconium dichloride, bis (meth)
Rucyclopentadienyl) zirconium dichloride, bi
Sus (dimethylcyclopentadienyl) zirconium dioxide
Lolid, bis (trimethylcyclopentadienyl) zyl
Conium dichloride, bis (tetramethylcyclopenta
Dienyl) zirconium dichloride, bis (pentamethyi)
Rucyclopentadienyl) zirconium dichloride, bi
Sus (n-butylcyclopentadienyl zirconium dioxide
Lolid, bis (indenyl) zirconium dichloride,
Bis (fluorenyl) zirconium dichloride, bis
(Cyclopentadienyl) zirconium chlorohydrido
De, bis (cyclopentadienyl) methyl zirconium
Chloride, bis (cyclopentadienyl) ethyl zirco
Nium chloride, bis (cyclopentadienyl) phenyl
Ruzirconium chloride, bis (cyclopentadiene
) Dimethylzirconium, bis (cyclopentadiene)
Le) diphenyl zirconium, bis (cyclopentadiene)
Nyl) dineopentyl zirconium, bis (cyclopen
Tadienyl) dihydrozirconium, (cyclopentadi
(Enyl) (indenyl) zirconium dichloride, (si
Clopentadienyl) (fluorenyl) zirconium di
Conjugated five-membered ring coordination without having a bridging linking group such as chloride
A transition metal complex having two molecules, methylenebis (indenyl) titanium dichloride,
Ethylenebis (indenyl) titanium dichloride,
Tylene bis (indenyl) titanium chlorohydride,
Ethylene bis (indenyl) methyl titanium chloride
De, ethylene bis (indenyl) methoxychlorotitani
Um, ethylene bis (indenyl) titanium diet
Cid, ethylene bis (indenyl) dimethyl titaniu
, Ethylene bis (4,5,6,7-tetrahydroin
Denyl) titanium dichloride, ethylene bis (2-me
Tylindenyl) titanium dichloride, ethylene bis
(2,4-Dimethylindenyl) titanium dichloride
De, ethylenebis (2-methyl-4-trimethylsilyl)
Indenyl) titanium dichloride, ethylene bis
(2,4-dimethyl-5,6,7-trihydroindeni
Ru) Titanium dichloride, ethylene (2,4-dimethyl)
(Lucyclopentadienyl) (3 ', 5'-dimethylcyclo)
Lopentadienyl) titanium dichloride, ethylene
(2-Methyl-4-t-butylcyclopentadienyl)
(3'-t-butyl-5'-methylcyclopentadiene
Ru) Titanium dichloride, ethylene (2,3,5-to
Limethylcyclopentadienyl) (2 ', 4', 5'-to
Limethylcyclopentadienyl) titanium dichloride
De, isopropylidene bis (2-methylindenyl) thi
Tanium dichloride, isopropylidene bis (indeni
Ru) Titanium dichloride, isopropylidene bis
(2,4-Dimethylindenyl) titanium dichloride
Desopropylidene (2,4-dimethylcyclopenta
Dienyl) (3'5'-dimethylcyclopentadienyl
Ru) Titanium dichloride, isopropylidene (2-me
Tyl-4-t-butylcyclopentadienyl) (3′-
t-butyl-5'-methylcyclopentadienyl) tita
Aluminum dichloride, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) titanium
Dichloride, methylene (cyclopentadienyl) (3,
4-dimethylcyclopentadienyl) titanium chloro
Hydride, methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) dimethyl titanium
Methylene (cyclopentadienyl) (3,4-dimme
Cyclopentadienyl) diphenyltitanium,
Tylene (Cyclopentadienyl) (Trimethylcyclope
Titanium dichloride, titanium dichloride, methylene
Ropentadienyl) (tetramethylcyclopentadienyl)
) Titanium dichloride, isopropylidene (cyclo
Pentadienyl) (3,4-dimethylcyclopentadiene
Nyl) titanium dichloride, isopropylidene (shik
Ropentadienyl) (2,3,4,5-tetramethylcyclo
Clopentadienyl) titanium dichloride, isopro
Pyridene (cyclopentadienyl) (3-methylindene
Nyl) titanium dichloride, isopropylidene (shik
Lopentadienyl) (fluorenyl) titanium dichloride
Lido, isopropylidene (2-methylcyclopentadiene
Nyl) (fluorenyl) titanium dichloride, isop
Ropylidene (2,5-dimethylcyclopentadienyl)
(3,4-dimethylcyclopentadienyl) titanium
Dichloride, isopropylidene (2,5-dimethyl
Lopentadienyl) (fluorenyl) titanium dichloride
Lido, ethylene (cyclopentadienyl) (3,5-di
Methylcyclopentadienyl) titanium dichloride,
Ethylene (cyclopentadienyl) (fluorenyl) ti
Tanium dichloride, ethylene (2,5-dimethyl
Lopentadienyl) (fluorenyl) titanium dichloride
Lido, ethylene (2,5-diethylcyclopentadiene
Le) (fluorenyl) titanium dichloride, dipheni
Lumethylene (cyclopentadienyl) (3,4-diethyl
Cyclopentadienyl) titanium dichloride, dif
Phenylmethylene (cyclopentadienyl) (3,4-di
Ethylcyclopentadienyl) titanium dichloride,
Cyclohexylidene (cyclopentadienyl) (fluor
(Renyl) titanium dichloride, cyclohexylidene
(2,5-dimethylcyclopentadienyl) (3 ',
4'-dimethylcyclopentadienyl) titanium di
Lolid, methylenebis (indenyl) zirconium dioxide
Lolid, ethylene bis (indenyl) zirconium dioxide
Lolid, methylenebis (indenyl) zirconium chloride
Rohydride, ethylenebis (indenyl) methylzirco
Nium chloride, ethylenebis (indenyl) methoxy
Chloro zirconium, ethylene bis (indenyl) dil
Conium diethoxide, ethylenebis (indenyl) di
Methyl zirconium, ethylene bis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride, d
Tylene bis (2-methylindenyl) zirconium dioxide
Lolid, ethylene bis (2,4-dimethylindenyl)
Zirconium dichloride, ethylene bis (2-methyl-
4-Trimethylsilylindenyl) zirconium dichloride
Lido, ethylene bis (2,4-dimethyl-5,6,7-
Trihydroindenyl) zirconium dichloride, ethyl
Ren (2,4-dimethylcyclopentadienyl)
(3 ', 5'-Dimethylcyclopentadienyl) zirco
Aluminum dichloride, ethylene (2-methyl-4-t-bu)
Tylcyclopentadienyl) (3′-t-butyl-5 ′)
-Methylcyclopentadienyl) zirconium dichloride
De, ethylene (2,3,5-trimethylcyclopentadiene
Nyl) (2 ', 4', 5'-trimethylcyclopentadi
(Enyl) zirconium dichloride, isopropylidene bi
Bis (2-methylindenyl) zirconium dichloride,
Isopropylidene bis (indenyl) zirconium dioxide
Lolid, isopropylidene bis (2,4-dimethylin
Denyl) zirconium dichloride, isopropylidene
(2,4-dimethylcyclopentadienyl) (3'5 '
-Dimethylcyclopentadienyl) zirconium dichloride
Lido, isopropylidene (2-methyl-4-t-butyl)
Cyclopentadienyl) (3'-t-butyl-5'-me
Tylcyclopentadienyl) zirconium dichloride,
Methylene (cyclopentadienyl) (3,4-dimethyl
Cyclopentadienyl) zirconium dichloride, methyl
Ren (cyclopentadienyl) (3,4-dimethyl
Lopentadienyl) zirconium chlorohydride, methyl
Ren (cyclopentadienyl) (3,4-dimethyl
Lopentadienyl) dimethyl zirconium, methylene
(Cyclopentadienyl) (3,4-dimethylcyclope
Ntadienyl) diphenylzirconium, methylene
Clopentadienyl) (trimethylcyclopentadienyl)
Ru) zirconium dichloride, methylene (cyclopenta
Dienyl) (tetramethylcyclopentadienyl) dil
Conium dichloride, isopropylidene (cyclopenta
Dienyl) (3,4-dimethylcyclopentadienyl)
Zirconium dichloride, isopropylidene (cyclope
Ntadienyl) (2,3,4,5-tetramethylcyclo
Pentadienyl) zirconium dichloride, isopropyl
Ridene (cyclopentadienyl) (3-methylindeni
Z) Zirconium dichloride, isopropylidene
Lopentadienyl) (fluorenyl) zirconium di
Lolid, isopropylidene (2-methylcyclopentadiene
(Enyl) (fluorenyl) zirconium dichloride, a
Sopropylidene (2,5-dimethylcyclopentadiene
) (3,4-Dimethylcyclopentadienyl) zirco
Nium dichloride, isopropylidene (2,5-dimethyl
Rucyclopentadienyl) (fluorenyl) zirconium
Mudic chloride, ethylene (cyclopentadienyl)
(3,5-Dimethylcyclopentadienyl) zirconium
Mudic chloride, ethylene (cyclopentadienyl)
Ruorenyl) zirconium dichloride, ethylene (2,
5-dimethylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, ethylene (2,5-diethyl
Cyclopentadienyl) (fluorenyl) zirconium
Dichloride, diphenylmethylene (cyclopentadiene
) (3,4-Diethylcyclopentadienyl) zirco
Nium dichloride, cyclohexylidene (cyclopenta
Dienyl) (fluorenyl) zirconium dichloride,
Cyclohexylidene (2,5-dimethylcyclopentadiene
(Enyl) (3 ', 4'-dimethylcyclopentadienyl
Z) Zirconium dichloride, methylene bis (indeni
Le) hafnium dichloride, ethylene bis (indeni
Le) hafnium dichloride, methylene bis (indeni
Hafnium chlorohydride, ethylene bis (indene)
Nyl) methyl hafnium chloride, ethylene bis (yne
Denyl) methoxychlorohafnium, ethylene bis (a)
Ndenyl) hafnium diethoxide, ethylene bis (a)
Ndenyl) dimethyl hafnium, ethylene bis (4,
5,6,7-Tetrahydroindenyl) hafnium dich
Lolid, ethylenebis (2-methylindenyl) hafni
Umdichloride, ethylenebis (2,4-dimethylin)
Denyl) hafnium dichloride, ethylene bis (2-me
Cyl-4-trimethylsilylindenyl) hafnium di
Chloride, ethylene bis (2,4-dimethyl-5,6,6
7-trihydroindenyl) hafnium dichloride, d
Tylene (2,4-dimethylcyclopentadienyl)
(3 ', 5'-Dimethylcyclopentadienyl) hafni
Umdichloride, ethylene (2-methyl-4-t-butyl)
L-cyclopentadienyl) (3'-t-butyl-5'-
Methylcyclopentadienyl) hafnium dichloride,
Ethylene (2,3,5-trimethylcyclopentadiene
Ru) (2 ', 4', 5'-trimethylcyclopentadiene
Nil) hafnium dichloride, isopropylidene bis
(2-Methylindenyl) hafnium dichloride, iso
Propylidene bis (indenyl) hafnium dichloride
And isopropylidene bis (2,4-dimethylindene
Le) hafnium dichloride, isopropylidene (2,4
-Dimethylcyclopentadienyl) (3'5'-dimethyl
(Lucyclopentadienyl) hafnium dichloride, iso
Propylidene (2-methyl-4-t-butylcyclopen
Tadienyl) (3'-t-butyl-5'-methylcyclo
Pentadienyl) hafnium dichloride, methylene (si
Clopentadienyl) (3,4-dimethylcyclopenta
Dienyl) hafnium dichloride, methylene (cyclope
(3,4-dimethylcyclopentadienyl)
Hafnium chlorohydride, methylene (cyclopen
Tadienyl) (3,4-dimethylcyclopentadienyl
Le) dimethyl hafnium, methylene (cyclopentadiene
Nil) (3,4-dimethylcyclopentadienyl) dif
Phenyl hafnium, methylene (cyclopentadienyl)
(Trimethylcyclopentadienyl) hafnium dichlor
Lido, methylene (cyclopentadienyl) (tetramethyl
(Lucyclopentadienyl) hafnium dichloride, iso
Propylidene (cyclopentadienyl) (3,4-dimme
Cylcyclopentadienyl) hafnium dichloride, a
Sopropylidene (cyclopentadienyl) (2,3,
4,5-Tetramethylcyclopentadienyl) hafuniu
Mudichloride, isopropylidene (cyclopentadiene
(3-methylindenyl) hafnium dichloride,
Isopropylidene (cyclopentadienyl) (fluorescein
Nyl) hafnium dichloride, isopropylidene (2-
Methylcyclopentadienyl) (fluorenyl) hafni
Umdichloride, isopropylidene (2,5-dimethyl
Cyclopentadienyl) (3,4-dimethylcyclopen
Tadienyl) hafnium dichloride, isopropylidene
(2,5-dimethylcyclopentadienyl) (fluorescein
Nyl) hafnium dichloride, ethylene (cyclopenta
Dienyl) (3,5-dimethylcyclopentadienyl)
Hafnium dichloride, ethylene (cyclopentadiene
Ru) (fluorenyl) hafnium dichloride, ethylene
(2,5-dimethylcyclopentadienyl) (fluorescein
Nyl) hafnium dichloride, ethylene (2,5-die
Cylcyclopentadienyl) (fluorenyl) hafuniu
Mudichloride, diphenylmethylene (cyclopentadiene
Nil) (3,4-diethylcyclopentadienyl) huff
Nium dichloride, diphenylmethylene (cyclopenta
Dienyl) (3,4-diethylcyclopentadienyl)
Hafnium dichloride, cyclohexylidene (cyclope
(Dienyl) (fluorenyl) hafnium dichloride
De, cyclohexylidene (2,5-dimethylcyclopen
Tadienyl) (3 ', 4'-dimethylcyclopentadiene
Nyl) hafnium dichloride and other alkylene groups
, A transition metal complex having two conjugated five-membered ring ligands, dimethylsilylenebis (indenyl) titanium dichloride
Lolid, dimethyl silylene bis (4,5,6,7-teto
Lahydroindenyl) titanium dichloride, dimethyl
Silylene bis (2-methylindenyl) titanium dioxide
Lolid, dimethylsilylene bis (2,4-dimethylin
Denyl) titanium dichloride, dimethylsilylene bis
(2,4-dimethylcyclopentadienyl) (3 ′,
5'-dimethylcyclopentadienyl) titanium di
Lolid, dimethylsilylene bis (2-methyl-4,5-
Benzoindenyl) titanium dichloride, dimethyl
Rylene bis (2-methyl-4-naphthylindenyl) ti
Tanium dichloride, dimethyl silylene bis (2-methyl
Lu-4-phenylindenyl) titanium dichloride,
Phenylmethylsilylene bis (indenyl) titanium
Dichloride, phenylmethylsilylene bis (4,5,
6,7-Tetrahydroindenyl) titanium dichloride
Phenylmethylsilylene bis (2,4-dimethyl
Ndenyl) titanium dichloride, phenylmethylsilyl
Ren (2,4-dimethylcyclopentadienyl)
(3 ', 5'-Dimethylcyclopentadienyl) titani
Ummdichloride, phenylmethylsilylene (2,3,5
-Trimethylcyclopentadienyl) (2 ', 4',
5'-trimethylcyclopentadienyl) titanium di
Chloride, phenylmethylsilylene bis (tetramethyl
Cyclopentadienyl) titanium dichloride, diphe
Nylsilylene bis (2,4-dimethylindenyl) tita
Indium dichloride, diphenyl silylene bis (indeni
Ru) Titanium dichloride, diphenylsilylene bis
(2-Methylindenyl) titanium dichloride, tet
Lamethyldisilylene bis (indenyl) titanium dik
Lolid, tetramethyldisilylene bis (cyclopentadiene
(Enyl) titanium dichloride, tetramethyldisilire
(3-methylcyclopentadienyl) (indenyl)
Titanium dichloride, dimethyl silylene (cyclopen
Tadienyl) (3,4-dimethylcyclopentadienyl
) Titanium dichloride, dimethylsilylene (cyclo
Pentadienyl) (trimethylcyclopentadienyl)
Titanium dichloride, dimethyl silylene (cyclopen
Tadienyl) (tetramethylcyclopentadienyl) thi
Tanium dichloride, dimethyl silylene (cyclopenta
Dienyl) (3,4-diethylcyclopentadienyl)
Titanium dichloride, dimethyl silylene (cyclopen
Tadienyl) (triethylcyclopentadienyl) tita
Nium dichloride, dimethyl silylene (cyclopentadiene
(Enyl) (tetraethylcyclopentadienyl) titani
Um dichloride, dimethyl silylene (cyclopentadiene
Nyl) (fluorenyl) titanium dichloride, dimethy
Lucillene (cyclopentadienyl) (2,7-di-t
-Butylfluorenyl) titanium dichloride, dimethy
Lucillene (cyclopentadienyl) (octahydrofuran
Fluorenyl) titanium dichloride, dimethylsilylene
(2-methylcyclopentadienyl) (fluorenyl)
Titanium dichloride, dimethyl silylene (2,5-di
Methylcyclopentadienyl) (fluorenyl) titani
Umdichloride, dimethylsilylene (2-ethylcyclo
Pentadienyl) (fluorenyl) titanium dichloride
Demethyldimethylene (2,5-diethylcyclopenta
Dienyl) (fluorenyl) titanium dichloride, di
Ethylsilylene (2-methylcyclopentadienyl)
(2 ', 7'-di-t-butylfluorenyl) titaniu
Mudic chloride, dimethyl silylene (2,5-dimethyl
Clopentadienyl) (2 ', 7'-di-t-butylphen
Fluorenyl) titanium dichloride, dimethylsilylene
(2-ethylcyclopentadienyl) (2 ', 7'-di
-T-butylfluorenyl) titanium dichloride, di
Methylsilylene (diethylcyclopentadienyl)
(2,7-di-t-butylfluorenyl) titanium di
Chloride, dimethylsilylene (methylcyclopentadiene
Nyl) (octahydrfluorenyl) titanium dichloride
De, dimethyl silylene (dimethyl cyclopentadiene
(Octahydrofluorenyl) titanium dichloride
De, dimethylsilylene (ethylcyclopentadienyl)
(Octahydrofluorenyl) titanium dichloride,
Dimethylsilylene (diethylcyclopentadienyl)
(Octahydrofluorenyl) titanium dichloride,
Dimethyl silylene bis (indenyl) zirconium dioxide
Lolid, dimethyl silylene bis (4,5,6,7-teto
Lahydroindenyl) zirconium dichloride, dimethy
Rusilylene bis (2-methylindenyl) zirconium
Dichloride, dimethylsilylene bis (2,4-dimethyl
Indenyl) zirconium dichloride, dimethyl silyl
Bis (2,4-dimethylcyclopentadienyl)
(3 ', 5'-Dimethylcyclopentadienyl) zirco
Nium dichloride, dimethyl silylene bis (2-methyl
-4,5-Benzoindenyl) zirconium dichloride
Dimethyl silylene bis (2-methyl-4-naphthyl)
Indenyl) zirconium dichloride, dimethyl silyl
Bis (2-methyl-4-phenylindenyl) zirco
Indium dichloride, phenylmethylsilylene bis (yne
Denyl) zirconium dichloride, phenylmethylsilyl
Renbis (4,5,6,7-tetrahydroindenyl)
Zirconium dichloride, phenylmethyl silylene bis
(2,4-Dimethylindenyl) zirconium dichloride
, Phenylmethylsilylene (2,4-dimethylcyclo
Pentadienyl) (3 ', 5'-dimethylcyclopenta
Dienyl) zirconium dichloride, phenylmethylsilane
Rylene (2,3,5-trimethylcyclopentadiene
Ru) (2 ', 4', 5'-trimethylcyclopentadiene
Nyl) zirconium dichloride, phenylmethylsilyl
Bis (tetramethylcyclopentadienyl) zirconi
Ummdichloride, diphenylsilylene bis (2,4-di
Methylindenyl) zirconium dichloride, dipheni
Rusilylene bis (indenyl) zirconium dichloride
De, diphenylsilylene bis (2-methylindenyl)
Zirconium dichloride, tetramethyldisilylene bis
(Indenyl) zirconium dichloride, tetramethyl
Disilylene bis (cyclopentadienyl) zirconium
Dichloride, tetramethyldisilylene (3-methylcyclo)
Ropentadienyl) (indenyl) zirconium dichloride
Lido, dimethylsilylene (cyclopentadienyl)
(3,4-Dimethylcyclopentadienyl) zirconium
Mudic chloride, dimethylsilylene (cyclopentadiene
) (Trimethylcyclopentadienyl) zirconium
Dichloride, dimethylsilylene (cyclopentadiene
) (Tetramethylcyclopentadienyl) zirconium
Mudic chloride, dimethylsilylene (cyclopentadiene
) (3,4-Diethylcyclopentadienyl) zirco
Nium dichloride, dimethyl silylene (cyclopentadiene
(Enyl) (triethylcyclopentadienyl) zirconi
Um dichloride, dimethyl silylene (cyclopentadiene
Nyl) (tetraethylcyclopentadienyl) zirconi
Um dichloride, dimethyl silylene (cyclopentadiene
Nyl) (fluorenyl) zirconium dichloride, dime
Tylsilylene (cyclopentadienyl) (2,7-di-
t-Butylfluorenyl) zirconium dichloride, di
Methylsilylene (cyclopentadienyl) (octahydr
Lofluorenyl) zirconium dichloride, dimethyl
Rylene (2-methylcyclopentadienyl) (fluore
Nyl) zirconium dichloride, dimethyl silylene
(2,5-dimethylcyclopentadienyl) (fluorescein
Nyl) zirconium dichloride, dimethylsilylene (2
-Ethylcyclopentadienyl) (fluorenyl) zyl
Conium dichloride, dimethyl silylene (2,5-die
Tylcyclopentadienyl) (fluorenyl) zirconi
Umdichloride, diethylsilylene (2-methylcyclo
Pentadienyl) (2 ', 7'-di-t-butylfluor
Renyl) zirconium dichloride, dimethylsilylene
(2,5-dimethylcyclopentadienyl) (2 ',
7'-di-t-butylfluorenyl) zirconium di
Lolid, dimethylsilylene (2-ethylcyclopentadiene
(Enyl) (2 ', 7'-di-t-butylfluorenyl)
Zirconium dichloride, dimethyl silylene (diethyl
Cyclopentadienyl) (2,7-di-t-butylfur
Orenyl) zirconium dichloride, dimethyl silylene
(Methylcyclopentadienyl) (octahydrfluore
Nyl) zirconium dichloride, dimethylsilylene (di)
Methylcyclopentadienyl) (octahydrofluore
Nyl) zirconium dichloride, dimethylsilylene (d
Cylcyclopentadienyl) (octahydrofluoreni
Z) Zirconium dichloride, dimethyl silylene (die
Cylcyclopentadienyl) (octahydrofluoreni
Z) Zirconium dichloride, dimethylsilylene bis
(Indenyl) hafnium dichloride, dimethyl silyle
Bis (4,5,6,7-tetrahydroindenyl) ha
Funium dichloride, dimethyl silylene bis (2-methyl
Ruindenyl) hafnium dichloride, dimethyl silyle
Bis (2,4-dimethylindenyl) hafnium dich
Lolid, dimethyl silylene bis (2,4-dimethyl
Ropentadienyl) (3 ', 5'-dimethylcyclopen
Tadienyl) hafnium dichloride, dimethylsilylene
Bis (2-methyl-4,5-benzoindenyl) hafni
Umdichloride, dimethylsilylene bis (2-methyl-
4-naphthylindenyl) hafnium dichloride, dime
Tylsilylene bis (2-methyl-4-phenylindeni
Le) hafnium dichloride, phenylmethyl silylene bi
Su (indenyl) hafnium dichloride, phenylmethy
Lucillene bis (4,5,6,7-tetrahydroindene
Nyl) hafnium dichloride, phenylmethylsilylene
Bis (2,4-dimethylindenyl) hafnium dichlor
Lido, phenylmethylsilylene (2,4-dimethyl
Ropentadienyl) (3 ', 5'-dimethylcyclopen
Tadienyl) hafnium dichloride, phenylmethylsilane
Rylene (2,3,5-trimethylcyclopentadiene
Ru) (2 ', 4', 5'-trimethylcyclopentadiene
Nyl) hafnium dichloride, phenylmethylsilylene
Bis (tetramethylcyclopentadienyl) hafnium
Dichloride, diphenylsilylene bis (2,4-dimethyl
Ruindenyl) hafnium dichloride, diphenylsilyl
Lenbis (indenyl) hafnium dichloride, diphe
Nylsilylenebis (2-methylindenyl) hafnium
Dichloride, tetramethyldisilylene bis (indeni
Le) Hafnium dichloride, Tetramethyldisilirenbi
Su (cyclopentadienyl) hafnium dichloride, te
Tramethyldisilylene (3-methylcyclopentadiene
Le) (indenyl) hafnium dichloride, dimethyl
Rylene (cyclopentadienyl) (3,4-dimethyl
Clopentadienyl) hafnium dichloride, dimethyl
Silylene (cyclopentadienyl) (trimethylcyclo
Pentadienyl) hafnium dichloride, dimethylsilyl
Ren (cyclopentadienyl) (tetramethylcyclope
Hafnium dichloride, dimethyl silylate
(Cyclopentadienyl) (3,4-diethylcyclo
Pentadienyl) hafnium dichloride, dimethylsilyl
Ren (cyclopentadienyl) (triethylcyclopen
Tadienyl) hafnium dichloride, dimethylsilylene
(Cyclopentadienyl) (Tetraethylcyclopenta
Dienyl) hafnium dichloride, dimethylsilylene
(Cyclopentadienyl) (fluorenyl) hafnium
Dichloride, dimethylsilylene (cyclopentadiene
) (2,7-Di-t-butylfluorenyl) hafuniu
Mudic chloride, dimethylsilylene (cyclopentadiene
Ha) (octahydrofluorenyl) hafnium dichloride
Demethyldimethylene (2-methylcyclopentadiene
Ru) (fluorenyl) hafnium dichloride, dimethyl
Silylene (2,5-dimethylcyclopentadienyl)
(Fluorenyl) hafnium dichloride, dimethylsilyl
Ren (2-ethylcyclopentadienyl) (fluorenyl
Hafnium dichloride, dimethylsilylene (2,5)
-Diethylcyclopentadienyl) (fluorenyl) ha
Funnium dichloride, diethyl silylene (2-methylsilane
Clopentadienyl) (2 ', 7'-di-t-butylphen
Fluorenyl) hafnium dichloride, dimethylsilylene
(2,5-dimethylcyclopentadienyl) (2 ',
7'-di-t-butylfluorenyl) hafnium dichlor
Lido, dimethylsilylene (2-ethylcyclopentadiene
Nil) (2 ', 7'-di-t-butylfluorenyl) ha
Funnium dichloride, dimethyl silylene (diethyl
Ropentadienyl) (2,7-di-t-butylfluore
Nyl) hafnium dichloride, dimethyl silylene (methyl
(Lucyclopentadienyl) (octahydrfluorenyl)
Hafnium dichloride, dimethyl silylene (dimethyl
Clopentadienyl) (octahydrofluorenyl)
Funium dichloride, dimethyl silylene (ethylcyclo
Pentadienyl) (octahydrofluorenyl) hafni
Umdichloride, dimethylsilylene (diethylcyclope
Ntadienyl) (octahydrofluorenyl) hafuniu
A silylene group-bridged conjugated five-membered ring ligand such as mudichloride
Transition metal complex having two, dimethylgermylene bis (indenyl) titanium di
Chloride, dimethylgermylene (cyclopentadiene
L) (fluorenyl) titanium dichloride, methyla
Lumilenbis (indenyl) titanium dichloride, f
Phenylaluminene bis (indenyl) titanium dichloride
Lido, phenylphosphylene bis (indenyl) titani
Umdichloride, ethylborene bis (indenyl) tita
Indium dichloride, phenylamylene bis (indeni
Ru) Titanium dichloride, Phenylaluminene
Lopentadienyl) (fluorenyl) titanium dichloride
Lido, dimethylgermylene bis (indenyl) zirconi
Umdichloride, dimethylgermylene (cyclopentadiene
(Enyl) (fluorenyl) zirconium dichloride,
Cylaluminene bis (indenyl) zirconium dichloride
Lido, phenylamylene bis (indenyl) zirconium
Mudic chloride, phenylphosphylene bis (indeni
Z) Zirconium dichloride, ethylborene bis (yne
Denyl) zirconium dichloride, phenylamilenbi
Su (indenyl) zirconium dichloride, phenyla
Mylene (cyclopentadienyl) (fluorenyl) dil
Conium dichloride, dimethylgermylene bis (indene
Nyl) hafnium dichloride, dimethylgermylene
Clopentadienyl) (fluorenyl) hafnium dich
Lolid, methylaluminene bis (indenyl) hafuniu
Mudic chloride, phenylamylene bis (indenyl) ha
Funnium dichloride, phenylphosphylene bis (yne
Denyl) hafnium dichloride, ethyl boren bis (a)
Ndenyl) hafnium dichloride, phenylamilenbi
Su (indenyl) hafnium dichloride, phenylami
Len (cyclopentadienyl) (fluorenyl) hafni
Germanium such as umdichloride, aluminum, boron
Conjugates crosslinked with hydrocarbon radicals containing elemental, phosphorus or nitrogen
A transition metal complex having two membered ring ligands, pentamethylcyclopentadienyl (diphenylamido)
No) titanium dichloride, indenyl (diphenyl
Mino) titanium dichloride, pentamethylcyclopen
Tadienyl-bis (trimethylsilyl) aminotitaniu
Mudic chloride, pentamethylcyclopentadienylfe
Noxitanium dichloride, dimethyl silylene (teto
Lamethylcyclopentadienyl) t-butylamino tita
Aluminum dichloride, dimethylsilylene (tetramethylsilane
Clopentadienyl) phenylaminotitanium dichloride
Lido, dimethylsilylene (tetrahydroindenyl) de
Sylaminotitanium dichloride, dimethylsilylene
(Tetrahydroindenyl) [bis (trimethylsilyl)
Le) Amino] titanium dichloride, dimethylgermile
(Tetramethylcyclopentadienyl) phenylami
Notitanium dichloride, pentamethylcyclopentadi
Ethenyl titanium trimethoxide, pentamethylcyclo
Pentadienyl titanium trichloride, pentamethyl
Cyclopentadienyl-bis (phenyl) aminozirco
Indium dichloride, indenyl-bis (phenyl) ami
Nozirconium dichloride, pentamethylcyclopenta
Dienyl-bis (trimethylsilyl) amino zirconium
Mudic chloride, pentamethylcyclopentadienylfe
Noxyzirconium dichloride, dimethyl silylene (the
Tramethylcyclopentadienyl) t-butylaminodi
Ruconium dichloride, Dimethylsilylene (Tetramethy
Lucyclopentadienyl) phenylaminozirconium
Dichloride, dimethylsilylene (tetrahydroindeni
Le) decylaminozirconium dichloride, dimethyl
Rylene (tetrahydroindenyl) [bis (trimethyl
(Silyl) amino] zirconium dichloride, dimethyl ester
Lumylene (tetramethylcyclopentadienyl) phenyl
Ruaminozirconium dichloride, pentamethylcyclo
Pentadienylzirconium trimethoxide, pentameth
Tylcyclopentadienylzirconium trichloride,
Pentamethylcyclopentadienyl-bis (phenyl)
Aminohafnium dichloride, indenyl-bis (phen
Nyl) aminohafnium dichloride, pentamethylsik
Lopentadienyl-bis (trimethylsilyl) aminoha
Funnium dichloride, pentamethylcyclopentadiene
Ruphenoxy hafnium dichloride, dimethyl silylene
(Tetramethylcyclopentadienyl) t-butylami
Nohafnium dichloride, dimethylsilylene (tetrame
Cylcyclopentadienyl) phenylamino hafnium
Dichloride, dimethylsilylene (tetrahydroindeni
Le) Decylaminohafnium dichloride, dimethylsilyl
Ren (tetrahydroindenyl) [bis (trimethylsilane
Ryl) amino] hafnium dichloride, dimethylgermi
Len (tetramethylcyclopentadienyl) phenyla
Minohafnium dichloride, pentamethylcyclopenta
Dienyl hafnium trimethoxide, pentamethylsik
Conjugates such as lopentadienyl hafnium trichloride
Transition metal complex having one membered ring ligand, (1,1'-dimethylsilylene) (2,2'-isop
Ropylidene) -bis (cyclopentadienyl) titaniu
Mudichloride, (1,1'-dimethylsilylene) (2,
2'-Dimethylsilylene) -bis (cyclopentadiene)
Le) titanium dichloride, (1,1'-dimethylsili
Ren) (2,2'-isopropylidene) -bis (cyclo
Pentadienyl) dimethyltitanium, (1,1'-di
Methylsilylene) (2,2'-isopropylidene) -bi
Sus (cyclopentadienyl) dibenzyltitanium,
(1,1'-dimethylsilylene) (2,2'-isopro
Pyridene) -bis (cyclopentadienyl) bis (tri
Methylsilyl) titanium, (1,1'-dimethylsilyl)
Ren) (2,2'-isopropylidene) -bis (cyclo
Pentadienyl) bis (trimethylsilylmethyl) tita
Nium, (1,2'-dimethylsilylene) (2,1'-
Ethylene) -bis (indenyl) titanium dichloride
De, (1,1'-dimethylsilylene) (2,2'-ethyl
Len) -bis (indenyl) titanium dichloride,
(1,1'-ethylene) (2,2'-dimethyl silylate
) -Bis (indenyl) titanium dichloride,
(1,1'-dimethylsilylene) (2,2'-cyclohexyl
Xylidene) -bis (indenyl) titanium dichloride
De, (1,1'-dimethylsilylene) (2,2'-iso
Propylidene) -bis (cyclopentadienyl) zirco
Nium dichloride, (1,1'-dimethylsilylene)
(2,2'-Dimethylsilylene) -bis (cyclopenta
Dienyl) zirconium dichloride, (1,1'-dimethyl
Tylsilylene) (2,2'-isopropylidene) -bis
(Cyclopentadienyl) dimethyl zirconium,
(1,1'-dimethylsilylene) (2,2'-isopro
Pyridene) -bis (cyclopentadienyl) dibenzyl
Zirconium, (1,1'-dimethylsilylene) (2,
2'-isopropylidene) -bis (cyclopentadienyl)
Ru) bis (trimethylsilyl) zirconium, (1,
1'-dimethylsilylene) (2,2'-isopropylidene
) -Bis (cyclopentadienyl) bis (trimethyl
Silylmethyl) zirconium, (1,2'-dimethylsi
Rylene) (2,1'-ethylene) -bis (indenyl)
Zirconium dichloride, (1,1'-dimethyl silylate
) (2,2'-Ethylene) -bis (indenyl) zyl
Conium dichloride, (1,1'-ethylene) (2,
2'-Dimethylsilylene) -bis (indenyl) zirco
Nium dichloride, (1,1'-dimethylsilylene)
(2,2'-Cyclohexylidene) -bis (indeni
Le) zirconium dichloride, (1,1'-dimethyl
Rylene) (2,2'-isopropylidene) -bis (shik
Lopentadienyl) hafnium dichloride, (1,1 '
-Dimethylsilylene) (2,2'-dimethylsilylene)
-Bis (cyclopentadienyl) hafnium dichloride
De, (1,1'-dimethylsilylene) (2,2'-iso
Propylidene) -bis (cyclopentadienyl) dimethyl
Ruhafnium, (1,1'-dimethylsilylene) (2,
2'-isopropylidene) -bis (cyclopentadienyl)
Le) dibenzylhafnium, (1,1'-dimethylsilyl
Ren) (2,2'-isopropylidene) -bis (cyclo
Pentadienyl) bis (trimethylsilyl) hafuniu
, (1,1'-Dimethylsilylene) (2,2'-iso
Propylidene) -bis (cyclopentadienyl) bis
(Trimethylsilylmethyl) hafnium, (1,2'-
Dimethylsilylene) (2,1'-ethylene) -bis (ii)
Ndenyl) hafnium dichloride, (1,1'-dimethyl)
Lucillene) (2,2'-ethylene) -bis (indeni
Le) hafnium dichloride, (1,1'-ethylene)
(2,2'-Dimethylsilylene) -bis (indenyl)
Hafnium dichloride, (1,1'-dimethyl silylate
) (2,2'-Cyclohexylidene) -bis (indene
Nyl) Hafnium dichloride and other ligands
A transition metal complex having two bridged conjugated five-membered ring ligands, and further in the compounds described in the above
Chlorine atom of these compounds is replaced by bromine atom, iodine atom, hydrogen source
Child, methyl group, phenyl group, benzyl group, methoxy group,
Something that has been replaced with a dimethylamino group, etc.
it can. Of the compounds described in 1 to 3, a silylene group of
A transition metal complex having two bridged conjugated five-membered ring ligands
A transition metal complex having one 5-membered ring ligand is vinylated.
It is particularly preferably used in the production of a compound polymer. (II) Specific examples of the transition metal complex represented by the general formula (I-5)
The following compounds can be mentioned as examples. Tet
La-n-butoxytitanium, tetra-i-propoxy
Titanium, tetraphenoxytitanium, tetracre
Zoxytitanium, tetrachlorotitanium, tetraki
S (diethylamino) titanium, tetrabromotitanium
Replaced um and titanium with zirconium and hafnium
The compounds obtained may be mentioned. These transition money
Among the metal complexes, alkoxytitanium compounds, alkoxy compounds
Sizirconium compound and alkoxy hafnium compound
Is preferred.

(III) Transition represented by general formula (I-6)
In the metal complex, M²Is the transitional gold of Groups 8-10 of the Periodic Table
Genus, but specifically iron, cobalt, nickel, para
Examples of such metals include platinum and platinum. Among them, nickel,
Palladium and iron are preferred. Also, L¹, L²Is that
Bound to a transition metal via a nitrogen atom or phosphorus atom
Represents a coordinate-bonding organic ligand, X², Y²Are each
It represents a covalent bond or an ionic bond.
Where X², Y²For details, as described above,
Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20, preferably
1 to 10 hydrocarbon groups, 1 to 20 carbon atoms, preferred
1-10 alkoxy, imino, amino, charcoal
Phosphorus-containing hydrocarbon having a prime number of 1 to 20, preferably 1 to 12
Group (for example, diphenylphosphine group) or carbon number
1-20, preferably 1-12 silicon-containing hydrocarbon radicals
(Eg, trimethylsilyl group, etc.), carbon number 1-2
0, preferably 1 to 12 hydrocarbon groups, or halogen
Boron-containing boron compound [eg B (C ₆H_Five)_Four, BF_Four]
You Of these, halogen atoms and hydrocarbon groups are preferred.
Good This X²And Y²Are the same, but different
It may be. Furthermore, L¹, L²As a concrete example of
Is triphenylphosphine; acetonitrile; benzo
Nitrile; 1,2-bisdiphenylphosphinoethane;
1,3-bisdiphenylphosphinopropane; 1,1 '
-Bisdiphenylphosphinoferrocene; cycloocta
Diene; pyridine; quinoline; N-methylpyrrolidine;
Bistrimethylsilylamino bistrimethylsilylimi
Nophosphorane and the like can be mentioned. The above L
¹, L², X²And Y²Are connected to each other and
The structure may be formed. This is represented by the general formula (I-6).
Examples of the transition metal complex
Lomobistriphenylphosphine nickel, dichlorobi
Striphenylphosphine nickel, dibromodiacetate
Nitrile nickel, dibromodibenzonitrile nickel
Le, dibromo (1,2-bisdiphenylphosphinoeta
Nickel), dibromo (1,3-bisdiphenylphosphine
Finopropane) nickel, dibromo (1,1'-diff
Phenylbisphosphinoferrocene) nickel, dimethyl
Bistriphenylphosphine nickel, dimethyl (1,
2-bisdiphenylphosphinoethane) nickel, methyl
Ru (1,2-bisdiphenylphosphinoethane) nickel
Rutetrafluoroborate, (2-diphenylphosphine
No-1-phenylethyleneoxy) phenylpyridine
Axel, dichlorobistriphenylphosphine paradiu
System, dichlorodibenzonitrile palladium, dichlorodiene
Acetonitrile Palladium, dichloro (1,2-bisdi
Phenylphosphinoethane) palladium, bistrife
Nylphosphine Palladium bis tetrafluoro volley
Bis (2,2'-bipyridine) methyl iron tetraflu
Oroborate etherate and compounds shown below
Is mentioned.

[0010]

[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-
A cationic complex such as bisdiphenylphosphinoethane) nickel tetrafluoroborate, bistriphenylphosphine palladium bistetrafluoroborate, bis (2,2'-bipyridine) methyliron tetrafluoroborate etherate, or a compound represented by the above formula is preferable. Used. In the catalyst of the present invention, the transition metal complex as the component (B) may be used alone or in combination of two or more. Particularly preferable complexes are transition metal complexes represented by the general formulas (I-3) and (I-4), and a complex having a ligand having an indenyl, cyclopentadienyl or fluorenyl structure is preferable.

Examples of the organic silane compound include R ¹⁰ _4-n SiX _n (wherein R ¹⁰ is a hydrocarbon group having no carbon-carbon double bond, and X is a halogen atom which is directly bonded to silicon). , A functional group of nitrogen or oxygen, and n is an integer of 1 to 3.). Specific examples of the organic silane compound include, for example, trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, t-butyldimethylsilyl chloride, t-butyldiphenylsilyl chloride,
Trialkylsilyl chlorides such as phenethyl dimethyl silyl chloride, dimethyl silyl dichloride, diethyl silyl dichloride, diisopropyl silyl dichloride,
Di-n-hexylsilyl dichloride, dicyclohexyl silyl dichloride, docosylmethyl silyl dichloride,
Dialkylsilyl dichlorides such as bis (phenethyl) silyl dichloride, methylphenethyl silyl dichloride, diphenyl silyl dichloride, dimesityl silyl dichloride, ditolyl silyl dichloride, methyl silyl trichloride, ethyl silyl trichloride, isopropyl silyl trichloride, t- Examples thereof include alkylsilyl trichlorides such as butylsilyl trichloride, phenylsilyl trichloride, phenethylsilyl trichloride, and silyl halides in which the chloride part in the above compound is replaced with another halogen element. And silanes having a hydride such as dimethylchlorosilane, (N, N-dimethylamino) dimethylsilane, diisobutylchlorosilane, trimethylsilyl hydroxide, triethylsilyl hydroxide, triisopropylsilyl hydroxide, t-butyldimethylsilyl hydroxide, Examples thereof include alkylsilyl hydroxides such as phenethyl dimethyl silyl hydroxide, dicyclohexyl silyl dihydroxide and diphenyl silyl dihydroxide, and polysilanols commonly known as peralkyl polysiloxy polyols. Further, the above-mentioned organic silane compound further includes a general formula R ¹⁰ _t X _3-t Si (CH ₂ ) _s SiX _3-t R ¹⁰ _t (wherein R ¹⁰ is a carbon-carbon double bond-free Is a hydrogen group, X is a functional group in which the element directly bonded to silicon is halogen, nitrogen or oxygen, s is 1 to 10 and t is 1 to 3
Is an integer. ) And bissilyl compounds, polynuclear polysiloxanes, polysilazanes, and the like. As the bissilyl compound, bis (methyldichlorosilyl) methane,
Examples thereof include bissilyl compounds such as 1,2-bis (methyldichlorosilyl) ethane, bis (methyldichlorosilyl) octane, and bis (triethoxysilyl) ethane. As the polynuclear polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5 , 7-Tetraphenylcyclotetrasiloxane and other cyclic polysiloxanes and 1,1,
Examples include linear polysiloxanes such as 5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane. Examples of polysilazanes include bis (trimethylsilyl) amide, bis (triethylsilyl) amide, bis (triisopropylsilyl) amide, bis (dimethylethylsilyl) amide, bis (diethylmethylsilyl) amide, bis (dimethylphenylsilyl) amide and bis Examples thereof include disilazanes such as (dimethyltolylsilyl) amide and bis (dimethylmenthylsilyl) amide.
In the organosilane compound used in combination with the alkenylsilane, the substituent R ¹⁰ preferably has no nitrogen atom or sulfur atom, and more preferably a hydrocarbon group.

In the present invention, the component (A) is replaced by the component (B)
It is preferred to contact the organoaluminum compound prior to contacting the components. Examples of such an organoaluminum compound include the following general formula R ¹¹ _x AlP _3-x (wherein R ¹¹ is an alkyl group having 1 to 10 carbon atoms, P is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, carbon Number 6 to 20
Is an aryl group or a halogen atom, and x is an integer of 1 to 3). Specific examples of the compound represented by the above formula include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride. , Diethylaluminum hydride, ethylaluminum sesquichloride and the like. 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 an aluminum oxy compound,
The following general formula

[0014]

[Chemical 2]

(Wherein R ¹² 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. In addition, each R ¹² may be the same or different. ) A chain aluminoxane represented by, or the following general formula

[0016]

[Chemical 3]

(Wherein R ¹² 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. In addition, each R ¹² may be the same or different. ) The cyclic aluminoxane shown by these can be mentioned. Specific examples of the aluminoxane include ethylaluminoxane and isobutylaluminoxane. Examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum or the general formula (R ¹³ , R ¹⁴ ) ₂ Al (OAlR ¹⁵ ) _y R ¹⁶ (in the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are carbon atoms, respectively). It has an alkyl group of 1 to 10 and at least a part of which is an alkyl group having 2 or more carbon atoms, and y is an integer of 1 to 3.). The aluminum oxy compound represented by If trimethylaluminum or methylalumoxane is used, the polymer may become lumpy, and the handling operation after polymerization may be difficult.

In the method for producing the vinyl compound polymerization catalyst of the present invention, the catalyst components are contacted in the following order. Operations after the treatment of the layered compound with alkenylsilane are preferably carried out in an inert gas atmosphere. First, the layered compound is added to a sufficient amount of water to form a colloidal aqueous solution, preferably 40 times or more the weight of the layered compound, to prepare an aqueous colloidal solution. Next, alkenylsilane is added to the aqueous colloid solution thus prepared, and the mixture is heated and stirred to treat the layered compound with alkenylsilane. The temperature when performing this process is
It can be carried out at -30 to 100 ° C, but in order to shorten the catalyst preparation time, it is preferable to carry out the treatment at a temperature near 100 ° C. The treatment time is not uniform depending on the type of the layered compound used and the treatment temperature, but is 30
The time may be from 10 minutes to 10 minutes. The alkenylsilane used here is used in an amount of 0.001 to 100 in terms of the number of moles of silicon atoms per 1 kg of the layered compound.
It is 0, preferably 0.01 to 100. When the number of moles of this alkenylsilane is 0.001 or less, the non-Newtonian property of the polymer of the vinyl compound is not improved, mechanical properties such as tensile properties are deteriorated, and when it exceeds 1000, the polymerization activity is decreased. Because there are things. In this way, when the aqueous colloid solution is treated with alkenylsilane, the aqueous colloid solution changes into a slurry suspension.
This slurry can be obtained as a solid by adding water again, washing, filtering with a filter, and drying. Further, the alkenylsilane may be brought into contact with the layered compound alone, but it is preferably used in combination with the organic silane compound and brought into contact with the layered compound. When the organic silane compound is used in combination, it is preferable to use the same molar amount or more as the alkenylsilane. For contact with layered compounds,
The alkenylsilane and the organic silane may be treated simultaneously or sequentially. This treatment is preferably carried out in water, but a vapor phase treatment can be carried out.

When an organoaluminum compound is added to an alkenylsilane-treated product obtained by treating a layered compound with alkenylsilane, the aluminum of the organoaluminum compound is added per 1 kg of the alkenylsilane-treated product (component A). 0.1 to 10 in number of moles of atoms
00, preferably 1 to 100. This is because if the addition ratio is less than 0.1, the effect of improving the polymerization activity is not sufficient, and even if the amount ratio exceeds 1000, the activity improvement commensurate with the effect cannot be obtained. Also,
The contact treatment is preferably carried out by a method of suspending or dissolving both of these components in an organic solvent such as pentane, hexane, heptane, toluenexylene and mixing them. Next, when the transition metal complex is brought into contact with the alkenylsilane-treated product (component A) thus obtained, the moles of metal atoms in the transition metal complex are added per 1 kg of the alkenylsilane-treated product (component A). In numbers,
0.0001-0.5, preferably 0.001-0.2
Is desirable. The addition ratio of this transition metal complex is
This is because if it is less than 0.0001, the effect of improving the polymerization activity is not sufficient, and if it exceeds 0.5, the polymerization activity per transition metal decreases.

Examples of vinyl compounds include olefins, styrene, styrenes, acrylic acid derivatives, fatty acid vinyls and the like. 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,
Linear or branched α-olefins such as 4,4-dimethyl-1-pentene and vinylcyclohexane, dienes such as 1,3-butadiene, 1,4-pentadiene and 1,5-hexadiene, hexafluoropropene, Halogen-substituted α-olefins such as tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene And cyclic olefins having 5 to 20 carbon atoms such as 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, and 5-benzylnorbornene. As styrenes, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-
Isopropyl styrene, p-butyl styrene, pt-
Butyl styrene, p-phenyl styrene, o-methyl styrene, o-ethyl styrene, o-propyl styrene,
o-isopropylstyrene, m-methylstyrene, m-
Alkyl styrenes such as ethyl styrene, m-isopropyl styrene, m-butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,5-dimethyl styrene, p-methoxy styrene, o- Alkoxystyrenes such as methoxystyrene and m-methoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-. Examples thereof include halogenated styrenes such as fluorostyrene, o-fluorostyrene and o-methyl-p-fluorostyrene, and further trimethylsilylstyrene, vinyl benzoate, divinylbenzene and the like. Examples of the acrylic acid derivative include ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and the like. Examples of the fatty acid vinyls include vinyl acetate, isopropenyl acetate, vinyl acrylate and the like. In the present invention, the vinyl compounds may be used alone or in combination of two or more. When copolymerizing two or more kinds of vinyl compounds, the above olefins can be arbitrarily combined. Further, in the present invention, the above olefins may be copolymerized with other monomers, and as the other monomer used at this time, for example, butadiene, isoprene, 1,4-pentadiene,
Chain diolefins such as 1,5-hexadiene, norbornene, 1,4,5,8-dimethano-1,2,3,3
4,4a, 5,8,8a-octahydronaphthalene, 2
And polycyclic olefins such as norbornene, cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinyl norbornene and dicyclopentadiene, unsaturated esters such as ethyl acrylate and methyl methacrylate, and the like. . The vinyl compound is preferably any of ethylene, propylene, 1-butene, 1-hexene, 1-octene and styrene, and among them, ethylene and propylene are particularly preferable.

The polymerization reaction is carried out by 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 temperature is room temperature to 200 ° C., and the pressure is not particularly limited, but preferably atmospheric pressure to 200 MPa.
It is the range of G. Further, hydrogen may be present as a molecular weight modifier in the polymerization system. When obtaining an olefin polymer, it is preferable to select the polymerization conditions in a proportion of 0.001 to 20% by weight of the layered compound. When the content of the layered compound is further increased, the physical properties of the addition polymer composition are deteriorated and the dispersibility of the layered compound is deteriorated. For example, when the polymer powder is press-molded into a film having a thickness of 1 mm, a lump of the layered compound is visually observed in the film. When the polymerization temperature is 200 ° C. or higher, the dispersibility of the silane-treated layered compound deteriorates, which is not preferable. Therefore,
The polymerization is preferably performed at room temperature to 200 ° C.
The larger the amount of the transition metal complex used with respect to the layered compound, the better the dispersibility, but practically, the amount of the transition metal complex is 0.01 to 100 μmol per unit weight g of the layered compound.

The alkenylsilane-treated product (component A) is uniformly dispersed in the vinyl compound polymer and the composite resin of the vinyl compound polymer and the thermoplastic resin of the present invention. The particle size of the silane-treated layered compound is particularly preferably 1 μm or less. As the thermoplastic resin of the present invention,
Examples thereof include polyolefin resins, styrene resins and acrylic acid resins. Examples of the polyolefin resin include various polyethylene, various polypropylene, polybutadiene, polyisobutylene, polyisoprene, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer. Examples thereof include polymers, ethylene / vinyl alcohol copolymers and ethylene / vinyl acetate / vinyl alcohol terpolymers. Examples of the styrene resin include various polystyrenes, styrene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene terpolymers, and the like. Examples of acrylic acid-based resins include polymethyl acrylate and polyethyl acrylate.

The composite resin comprising the vinyl compound polymer and the thermoplastic resin of the present invention may optionally contain the following additive components. Examples thereof include antioxidants, flame retardants, ultraviolet absorbers, colorants, reinforcing agents such as fillers and glass, plasticizers, antistatic agents and lubricants. The blending amount of these components is not particularly limited as long as the properties of the composite resin of the present invention are maintained. Next, a method for producing the composite resin of the present invention will be described. The composite resin of the present invention is obtained by blending a polymer of a vinyl compound and a thermoplastic resin, further blending the above-mentioned additional components, which are used as necessary, in a predetermined ratio and kneading. Compounding and kneading at this time, a commonly used equipment, for example, a ribbon blender, a drum tumbler or the like is premixed, Banbury mixer, single screw extruder, twin screw extruder, multi-screw extruder and It can be performed by a method using a co-kneader or the like. The heating temperature during kneading is
Usually, it is appropriately selected within the range of 150 to 300 ° C. As this melt-kneading molding, it is preferable to use an extrusion molding machine, especially a vent type extrusion molding machine.

[0024]

EXAMPLES Next, the present invention will be described in more detail by way of examples.
However, the present invention is in no way limited by these examples.
Not a thing. [Example 1] Preparation of vinylsilane-treated layered compound Pour 4 L of distilled water into a 3 L flask with a volume of 5 L and stir.
However, the 2: 1 type layered compound [Na-fluorine tetrasilicon mica,
Layer charge 0.6, manufactured by Coop Chemical Co., ME-100] 2
5 g was added slowly. After the addition, add the layered compound suspension to the chamber.
Stir at temperature for 1 hour. Next, diethyldichlorosilane
[(C₂H_Five)₂SiCl₂] 5 ml to layered compound suspension
It was dripped slowly. After dropping, continue to vinyltrichloro
Silane [(CH₂= CH) SiCl₃] 2.5 ml suspension
The mixture was added dropwise to the liquid, and stirring was continued for 1 hour at room temperature. Change
Then, the temperature was raised to 100 ° C, and the suspension was stirred at the same temperature for 3 hours.
It was During this time, the suspension changed to a sedimentary hydrophobic slurry.
It was Press this hydrophobic slurry with a pressurizer (air pressure 5 kg / cm²
・ G, use a membrane filter with 3μ membrane hole)
I had The time required for filtration was 7 minutes. Dry at room temperature
25 g of the filtered product was suspended in 250 ml of toluene and
A toluene solution of triisobutylaluminum
(1.0 mol / L) 160 ml was gradually added, and after addition
It heated up at 100 degreeC and stirred at the same temperature for 1 hour. Obtained a
Luminium treated slurry is washed with toluene and then
Adjust the amount to 500 ml with toluene and treat with vinyl silane.
This was designated as compound slurry A. Dimethyl silylene bis (4-phenyl-2-methyl group
Propylene with Ndenyl) zirconyl dichloride complex
Len polymerization 2.0 L of dry toluene in an autoclave with an internal volume of 5 L,
Prepared with 3.0 mmol of triisobutylaluminum
100 ml of silane-treated layered compound slurry A
5.0g) of layered compounds were added in sequence and the temperature was raised to 60 ° C.
Warmed. Then, while continuously supplying propylene gas,
Press the inner pressure to 7kg / cm²・ Kept to G. Furthermore, 60
Dimethyl silylate suspended in heptane while maintaining at ℃
Bis (2-methyl-4-phenylindenyl) zirco
Solution of dinium chloride (1 micromol / ml hepta
30 ml of a heptane solution containing 3 ml of
Was added to. Polymerization pressure 7kg / cm²・ G, polymerization temperature 6
Polymerization was carried out by continuously supplying propylene while maintaining the temperature at 0 ° C.
It was When 2 hours have passed from the start of polymerization, addition of methanol
Polymerization was stopped by addition. Then, use the filter paper to pull the polymer
It was separated by filtration and dried under reduced pressure at 90 ° C. for 12 hours. That conclusion
As a result, 116 g of an addition polymer was obtained. Polymer silane
The treated layered compound content was 4.3 wt%. Haute
Polymer immediately after removal from the rabe (toluene-methanol
(Wet state of the mixed liquid), white polymer powder
The spots of the silane-treated layered compound (yellow) are visually
Was not detected. Distribution measurement of vinylsilane in polymer The polymer obtained in (Silane-treated layered compound-containing polymerization
Body) 22 mg and trichlorobenzene 10 ml solution warm
After heating to 150 ℃, fill the insoluble layered compound.
Filter (mesh 5 μm) to remove. The filtrate is G
It was run on a PC-FTIR instrument. GPC-FTIR is G
Use the transfer tube and flow cell from the PC body.
Used in combination with the FTIR body. Polymerization above
Molecular weight distribution and vinylsilane composition distribution in polymers
The measurement was performed according to the following method. (A) Measuring equipment GPC body; high temperature GPC column made by GL Sciences
Even FTIR; Nicolet MAGNA-IR 560
SPECTROMETER Data analysis software; 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 amount: 1.000 ml, GPC color
Mu: Two Shodex UT806MLT (C) FTIR measurement conditions Detector type: MCT detector IR spectrum resolution: 4 cm^-1 Number of scans of 1 data (IR spectrum): 13 scans
Chan Acquisition time of 1 data (IR spectrum): 10.8
1 data acquisition per second (D) Measurement of molecular weight distribution curve, Mw and Mn A chromatogram was obtained by the above GPC-FTIR,
For this chromatogram, the data for GPC-FTIR
Data analysis software (Nicolet OMNIC SE
C-FTIR Ver. 2.10.2), data analysis
The molecular weight distribution curve [log_Ten M (side
Axis) -d (w) / d (log_Ten M) (vertical axis)], weight
The average molecular weight Mw and the molecular weight distribution Mw / Mn were determined.
For the calculation of molecular weight, use standard polystyrene manufactured by Tosoh Corporation.
The standard calibration curve prepared above was used. Also, the molecular weight
Are all polypropylene equivalent molecular weights based on the Q value method.
I asked. (E) Measurement of vinylsilane composition curve Using the data analysis software for GPC-FTIR,
Amount of vinylsilane copolymerized with propylene (wt%)
(Measured by the strength ratio of the methyl group and methylene group in the coalescence)
Calculation is performed, and then the vinylsilane composition curve [log
_Ten M (horizontal axis) -vinylsilane amount (vertical axis)]
It was The results are shown in FIG. From Figure 1, the polymer
Vinyl silane contained is distributed over each molecular weight,
Progress of copolymerization of propylene and vinylsilane
There was found. Observation by optical microscope A part of the polymer powder obtained in
14 mm wide and 200 μm thick)
Shape (molding temperature 200 ° C, molding pressure 50 kg / cm ²)
It was Next, an optical microscope (Olympus Optical Co., Ltd.
Made by BH-2), observe the heat press sheet (eyepiece)
Lens: 10x, Objective lens: 40x)
Of yellow (silane-treated layered compound) with a diameter larger than 1μ
No particles were found.

[Embodiment 2] Preparation of allylsilane-treated layered compound The vinyltrichlorosilane [(CH₂= C
H) SiCl₃] To allylmethyldichlorosilane [(C
H₂= CHCH₂) CH₃SiCl₂], Except that
Silane treatment was performed in the same manner as in Example 1 to obtain hydrophobicity.
A slurry was obtained. Next, powder 2 obtained by filtering and drying
5 g of organoaluminum was treated in exactly the same manner as in Example 1.
Then, allylsilane-treated compound slurry B was obtained. Dimethyl silylene bis (4-phenyl-2-methyl group
Propylene with Ndenyl) zirconyl dichloride complex
Len polymerization 2.0 L of toluene of Example 1 was mixed with 2.0 L of heptane and
Allylsilane treatment of 100 ml of orchid-treated compound slurry A
Physical compound slurry B 100 ml and MMAO (Tosoh
Made by Einchem; modified methylalumoxane) 1.0 mm
ol (Al atom conversion) mixture, polymerization temperature 60 ℃ 70
Propylene as in Example 1 except that the temperature was changed to ° C.
Polymerization was carried out. 30 minutes after the start of polymerization, the polymerization is stopped
It was The dry weight of the obtained polymer was 136 g.
The content of silane-treated layered compound in the polymer is 3.7 wt%
Met. Viscoelasticity measurement of polymers Obtained by using a mold (disk with a diameter of 30 mm and a thickness of 1 mm)
The prepared polymer (silane-containing layered compound-containing polymer)
It pressed (molding temperature 210 degreeC). And the following Ares viscosity
Melting characteristics of polymer using elasticity measuring device [steady rotation angular velocity
[Degree (horizontal axis) -complex viscosity η * (vertical axis)]. This conclusion
The results are shown in FIG. As a result, complex viscosity η * (Pa · s)
Increases as the steady rotational angular velocity (rad / s) decreases.
Increased in width. The melting characteristics of this polymer are non-Newtonian.
Was found to be high. For this reason,
It is thought that the form is improved. For example. By extrusion
Can increase the amount of resin discharged under constant torque.
Therefore, productivity can be improved. By injection molding
Can shorten the molding cycle and improve productivity
You can In addition, it becomes easy to mold a large molded product. (A) Measuring device Rheometric Scientific ARES
 Viscoelasticity measurement system (extended type) Transducer: 2
k, FRT, NI Frequency (rad / sec): 10^-Five~ 100 Normal stress range (g): 2.0 to 2000 Environmental system: FCO (A) Measurement conditions Measurement temperature: 175 ° C, strain (displacement angle): 20%, steady time
Rolling angular velocity: 10^-2-10 ²rad / s]

Comparative Example 1 Preparation of Layered Compound Treated with Ethylsilane The same as Example 2 except that allylmethyldichlorosilane [(CH ₂ ═CHCH ₂ ) CH ₃ SiCl ₂ ] was not added. The silane treatment (diethyldichlorosilane [(C ₂ H ₅ ) ₂ SiCl ₂ ] 5
ml alone) to obtain a hydrophobic slurry. Next, 25 g of the powder obtained by filtration and drying was treated with organoaluminum in the same manner as in Example 2 to obtain a silane-treated compound slurry C. Polymerization of Propylene Using Dimethylsilylene Bis (4-phenyl-2-methylindenyl) Zirconyl Dichloride Complex Propylene as in Example 2 except that 100 ml of the silanized compound slurry B of Example 2 was replaced with 100 ml of the above slurry C. Polymerization was carried out. The polymerization was stopped 16 minutes after the initiation of the polymerization. The dry weight of the obtained polymer was 153 g. The silane-treated clay content of the polymer was 3.3 wt%. The polymer (polymer containing a silane-treated layered compound) obtained in (1) was hot-pressed (molding temperature: 210 ° C.) using a die for measuring viscoelasticity of the polymer (disk having a diameter of 30 mm and a thickness of 1 mm). Then, the melting characteristics of the polymer were determined using an Ares viscoelasticity measuring device (also shown in FIG. 2). As a result, the complex viscosity η * (Pa · s) hardly changed even when the steady rotation angular velocity changed. It has been found that the melting properties of this polymer show low non-Newtonian properties.

Example 3 Preparation of Layered Compound Treated with Vinylsilane (Silane Content 2/5) Vinyltrichlorosilane of Example 1 [(CH ₂ = C
H) SiCl ₃ ] 2.5 ml was changed to 1.0 ml, and silane treatment was carried out in the same manner as in Example 1 to obtain a hydrophobic slurry. Next, 25 g of the powder obtained by filtration and drying was treated with organoaluminum in the same manner as in Example 1 to obtain a vinylsilane-treated compound slurry D. Polymerization of ethylene using dimethylsilylene bis (2-methylindenyl) zirconyl dichloride complex 2.0 L of dry toluene in an autoclave having an internal volume of 5 L.
100 ml of the silane-treated compound slurry D prepared with 3.0 mmol of triisobutylaluminum (5.0 g of the silane-treated layered compound) was sequentially added and the temperature was raised to 55 ° C. Next, the pressure was raised while continuously supplying ethylene gas, and the internal pressure was maintained at 1 kg / cm ² · G. Next, 30 ml of a toluene solution containing 3 ml of a solution of dimethylsilylenebis (2-methylindenyl) zirconium dichloride (1 μmol / ml) suspended in heptane was added to the polymerization system. Further, while keeping the temperature in the range of 55 to 60 ° C., ethylene was continuously fed so that the polymerization pressure was maintained at 1 kg / cm ² · G, and the polymerization was carried out. When 1 hour had passed from the start of the polymerization, the polymerization was stopped by adding methanol. Next, the polymer was separated by filtration and dried under reduced pressure at 90 ° C. for 12 hours. As a result, 254 g of an addition polymer was obtained. Silane-treated layered compound content of polymer is 2.0
It was wt%. Immediately after taking out the polymer from the autoclave (wet state of the toluene-methanol mixed solution), no spots of the silane-treated layered compound (yellow) were visually detected in the white polymer powder. 8 g of a polymer (a polymer containing a silane-treated layered compound) obtained by the preparation of a composite resin (a pellet containing a kneaded mixture of a polymer and polyethylene) and 32 g of HDPE (640 IUF, manufactured by Idemitsu Petrochemical Co., Ltd.) produced with a Ziegler catalyst, Inner volume 60 ml
The kneading was carried out at 50 rpm for 5 minutes using the Plastomill mixer (No. 230 ° C.). Next, the kneaded mixture was hot-pressed using a mold having a length of 20 cm × 20 cm and a thickness of 1 mm. Press conditions are 230 ℃, 50kg / c
m ² , 4 minutes. The obtained sheet was cut to prepare composite resin (kneading compound) pellets. Preparation of test sample, bending test and Izod impact test composite resin (kneading compound) pellets were applied to Niigata Iron Works injection molding machine (MIN-7), bending test sample (length x width = 10 mm x 114 mm, thickness) 4 mm) and impact test sample (length x width = 12 mm x 60 mm,
A thickness of 4 mm) was created. The bending test method is JIS
-K-7116, the measurement method of Izod impact test is JI
It was based on SK-7110. The flexural strength and flexural modulus at the test temperature of 23 ° C. were 24.3 MPa and 857 MPa, respectively. Also, the Izod impact test is
Tested at 23 ° C with notched conditions and impact value was 6
It was 9.3 KJ / m ² .

Comparative Example 2 Preparation of Kneaded Pellets of Polyethylene 40 g of HDPE (640UF, manufactured by Idemitsu Petrochemical Co., Ltd.) produced with a Ziegler catalyst was mixed with a plastomill mixer (set temperature: 230 ° C.) having an internal volume of 60 ml at 50 rp.
kneaded for 5 minutes. Next, the kneaded mixture is length × width = 20.
It was hot pressed using a metal mold of cm × 20 cm and thickness of 1 mm. The press conditions are 230 ° C., 50 kg / cm ² , and 4 minutes. The obtained sheet was cut to prepare kneaded pellets. Preparation of Test Sample, Kneading Blend Pellets Prepared by Bending Test and Izod Impact Test were applied to an injection molding machine (MIN-7) manufactured by Niigata Iron Works, and a bending test sample and an impact test sample were prepared in the same manner as in Example 3. . As a result of the bending test, the bending strength and elastic modulus at the test temperature of 23 ° C. were 21.3 MPa and 776 MPa, respectively. The Izod impact test was conducted at a test temperature of 23 ° C. with a notch, and the impact value was 58.0 KJ / m ²
Met.

Examples 4 and 5 [(t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane] titanium dichloride complex and dimethylsilylenebis (2-methylindenyl) zirconyl dichloride complex polymerization content of ethylene 2.0 L of dry toluene in a 5 L autoclave,
Triisobutylaluminum 3.0 mmol, Example 1
100 ml of the silane-treated compound slurry A prepared in
(Silane-treated layered compound 5.0 g) was sequentially added, and 55
The temperature was raised to ° C. Next, the internal pressure was maintained at 7 kg / cm 2 (gauge pressure) while continuously supplying ethylene gas. Further, [(t-butylamido) dimethyl (tetramethyldiclopentadienyl) silane] titanium dichloride complex (Example 4) dissolved in toluene or dimethylsilylenebis (4-phenyl-2-methyl) suspended in heptane. 3 ml of solution of indenyl) zirconyl dichloride complex (Example 5) (1 micromol / ml each)
30 ml of a toluene solution containing the above was added to each of the polymerization systems. After that, the temperature is gradually raised from 55 ° C (about 0.
Polymerization was stopped when the temperature reached 70 ° C. Next, the polymer was separated by filtration and dried under reduced pressure at 90 ° C. for 12 hours. As a result, 104 g (Example 4) and 190 g (Example 5) of the addition polymer were obtained, respectively. Heat resistance test A plastomill mixer with an internal volume of 30 cc was kept at 230 ° C., 20 g of each of the polymer powders obtained in this was charged, and heating and melting were attempted for 5 minutes at 50 rpm. Both powders were not melted at all. It was recovered in the state of. Next, when the temperature of the mixer was set to 250 ° C. and the polymerized powder was heated and melted again, the polymerized powder obtained by using the dimethylsilylenebis (4-phenyl-2-methylindenyl) zirconyl dichloride complex was melted. . However, the powder polymerized with the [(t-butylamido) dimethyl (tetramethyldiclopentadienyl) silane] titanium dichloride complex did not melt. As shown in this example, the polymer created using the alkenylsilane-treated layered compound exhibited extremely high heat resistance.

[Example 6] Polymerization of ethylene using dimethylsilylenebis (4-phenyl-2-methylindenyl) zirconyl dichloride complex 2.0 L of dry toluene was added to an autoclave having an internal volume of 5 L.
Triisobutylaluminum 2.0 mmol, Example 1
Silane-treated layered compound slurry A100 prepared in
ml (silane-treated layered compound 5.0 g) was sequentially added,
The temperature was raised to 55 ° C. Next, the pressure was increased while continuously supplying ethylene gas, and the internal pressure was maintained at 4 kg / cm ² · G. Further, while maintaining the temperature at 55 ° C., a heptane solution 30 m containing 3 ml of a solution of dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride (1 μmol / ml heptane) suspended in heptane was added.
1 was added to the polymerization system. Polymerization pressure is 4 kg / cm ² · G,
While maintaining the polymerization temperature at 55 ° C., ethylene was continuously supplied to carry out polymerization. After 20 minutes from the start of the polymerization, ethylene was continuously supplied while gradually increasing the polymerization temperature (10 ° C./15 minutes) while maintaining the polymerization pressure at 4 kg / cm ² · G. Keep the same temperature after reaching 75 ℃, 4k
Polymerization was continued at g / cm ² · G. After 3 hours from the start of the polymerization, the polymerization was stopped by adding methanol. Next, the polymer was separated by filtration and dried under reduced pressure at 90 ° C. for 12 hours. As a result, 207 g of an addition polymer was obtained. Silane-treated layered compound content of polymer is 2.4 wt%
Met. Immediately after taking out the polymer from the autoclave (wet state of the toluene-methanol mixed solution), no spots of the silane-treated layered compound (yellow) were visually detected in the white polymer powder. 8 g of a polymer (a polymer containing a silane-treated layered compound) obtained by the preparation of a composite resin (a pellet containing a kneaded mixture of a polymer and polyethylene) and 32 g of HDPE (640 IUF, manufactured by Idemitsu Petrochemical Co., Ltd.) produced with a Ziegler catalyst, Inner volume 60 ml
The kneading was carried out at 50 rpm for 5 minutes using a Plastomill mixer (No. 210 ° C.). Next, the kneaded mixture was hot-pressed using a mold having a length of 15 cm × 15 cm and a thickness of 1 mm. Press conditions are 200 ℃, 50kg / c
m ² , 2 minutes. The obtained sheet was cut to prepare composite resin (kneading compound) pellets. Preparation of test samples and composite resin (kneading and compounding) pellets prepared by various mechanical property tests were applied to an injection molding machine (MIN-7) manufactured by Niigata Iron Works, and a bending test sample (length x width = 10 mm x 114 mm, thickness 4 mm). ,
Impact test sample (length x width = 12 mm x 60 mm, thickness 4 mm), tensile test sample (width 6 mm) and load deflection temperature test sample (length x width = 10 mm x 11)
4 mm, thickness 4 mm) was created. The bending test method and the Izod impact test method are the same as in Example 3. Further, the measuring method of the tensile test is JIS-K-716.
1, the measurement condition is a test speed of 50 mm / min,
It was performed at a chuck distance of 80 mm and a temperature of 23 ° C. The measurement method of the deflection temperature under load test is based on JIS-K-7191, the measurement is without annealing, the load is 0.45 MPa,
The heating rate was 120 ° C./hr. As a result, temperature 2
Flexural strength and flexural modulus at 3 ℃ are 2
It was 2.5 MPa and 804 MPa. The Izod impact test is conducted at a test temperature of 23 ° C. with a notch,
The impact value was 60.0 KJ / m ² . The result of the tensile test shows that the yield strength is 21.1 MPa and the breaking strength is 40.1 MP.
a, elongation at break 490%, and elastic modulus 1150 MPa. The deflection temperature under load was 63.3 ° C. The results are shown in a radar chart and shown in FIG.

Comparative Example 3 Preparation of Kneaded Pellets of Polyethylene 40 g of HDPE (640UF, manufactured by Idemitsu Petrochemical Co., Ltd.) produced with a Ziegler catalyst was mixed with a plastomill mixer (set temperature 210 ° C.) having an internal volume of 60 ml at 50 rp.
kneaded for 5 minutes. Next, the kneaded mixture is length × width = 20.
It was hot pressed using a metal mold of cm × 20 cm and thickness of 1 mm. The press conditions are 200 ° C., 50 kg / cm ² , and 2 minutes. The obtained sheet was cut to prepare kneaded pellets. Preparation of test sample, kneading blended pellets prepared by bending test and Izod impact test were applied to an injection molding machine (MIN-7) manufactured by Niigata Iron Works, and a test sample was prepared in the same manner as in Example 6. As a result, the flexural strength and flexural modulus at a temperature of 23 ° C. were 21.9 MPa and 784 MPa, respectively. The Izod impact test is performed at a test temperature of 23 ° C. with a notch, and the impact value is 52.0.
It was KJ / m ² . The result of the tensile test shows that the yield strength is 2
0.3 MPa, breaking strength 33.0 MPa, breaking elongation 42
It was 0% and the elastic modulus was 1070 MPa. The deflection temperature under load was 64.3 ° C. These results are displayed on a radar chart and also shown in FIG.

Example 7 Block Copolymerization of Propylene and Ethylene Using Dimethylsilylene Bis (4-phenyl-2-methylindenyl) Zirconyl Dichloride Complex 2.0 L of dry toluene in an autoclave having an internal volume of 5 L,
Triisobutylaluminum 2.0 mmol, Example 1
Silane-treated layered compound slurry A100 prepared in
ml (silane-treated layered compound 5.0 g) was sequentially added,
The temperature was raised to 70 ° C. Next, the pressure was increased while continuously supplying propylene gas, and the internal pressure was maintained at 7 kg / cm ² · G.
Next, dimethylsilylene bis (4
-Phenyl-2-methylindenyl) zirconium dichloride solution (1 micromol / ml heptane) 4 m
30 ml of a heptane solution containing 1 was added to the polymerization system. While maintaining the polymerization pressure at 7 kg / cm ² · G and the polymerization temperature at 70 ° C., ethylene was continuously supplied to perform polymerization. When 25 minutes have passed from the start of the polymerization, the polymerization temperature was lowered to 50 ° C,
At the same time, depressurize propylene (gauge pressure 0 kg / cm ² ).
Removed. The temperature of the polymerization was again raised to 60 ° C., ethylene was supplied, and the polymerization was continued at ² kg / cm ² · G while maintaining the temperature at 60 to 70 ° C. After 10 minutes from the ethylene supply, the polymerization was stopped by adding methanol. Next, the polymer was separated by filtration and dried under reduced pressure at 90 ° C. for 12 hours. As a result, 214 g of an addition polymer was obtained. The silane-treated layered compound content of the polymer was 2.3 wt%. Immediately after taking out the polymer from the autoclave (wet state of the toluene-methanol mixed solution), no spots of the silane-treated layered compound (yellow) were visually detected in the white polymer powder. A solution of 22 mg of the polymer obtained by measuring the amount and distribution of ethylene in the polymer (silane-treated layered compound-containing polymer) and 10 ml of trichlorobenzene was heated to a temperature of 150 ° C, and the insoluble layered compound was filtered (mesh). 5 μm). The filtrate is GPC-F
Subjected to TIR apparatus. GPC-FTIR uses the transfer tube and flow cell from the GPC main unit to
It was used in combination with the TIR body. The ethylene composition distribution in the polymer was measured according to the same method as in Example 1. As a result, it was found that the ethylene units contained in the polymer were uniformly distributed over each molecular weight, and the copolymerization of propylene and ethylene proceeded. The concentration of ethylene in the copolymer was 40 wt%. 50 parts by weight of the copolymer powder obtained in the production of the composite resin and isotactic polypropylene (H100M manufactured by Idemitsu Petrochemical Co., Ltd.) produced by homopolymerizing propylene with a Ziegler catalyst.
40 g of the compound consisting of 0 parts by weight was mixed with 50 g of a plastomill mixer (set temperature: 230 ° C.) having an internal volume of 50 ml.
The mixture was kneaded at rpm for 5 minutes. Next, add the kneaded mixture 1 length and 1 width.
Hot pressing was performed using a mold having a size of 5 cm × 15 cm and a thickness of 1 mm. Press conditions are 200 ° C., 50 kg / cm ² , 4
Minutes. The obtained sheet is cut and a composite resin (kneading compound)
Pellets were prepared. In this composite resin, the blending ratio of both was adjusted so that the ethylene content was 20% by weight. Preparation of test sample and bending test and the composite resin (kneading compound) pellets prepared at the deflection temperature under load were applied to an injection molding machine (MIN-7) manufactured by Niigata Iron Works, and the bending test sample and the deflection temperature under load test sample (respectively, (Length x width = 10 mm x 114 mm, thickness 4 mm) was created. The measuring method of the bending test is the same as that of the third embodiment.
The measuring method of the deflection temperature under load test is the same as in Example 6. As a result, the bending strength and the bending elastic modulus at a temperature of 23 ° C. are 43.1 MPa and 1628 M, respectively.
It was Pa. The deflection temperature under load was 115.5 ° C.

Comparative Example 4 Preparation of Kneaded Pellets of Propylene / Ethylene Block Copolymer Polypropylene prepared by block copolymerizing propylene and ethylene with a Ziegler catalyst (Idemitsu Petrochemical Co., Ltd., J
763HP, ethylene content 20wt% 40g, 60ml internal volume plastomill mixer (set temperature 210
K)) and kneaded at 50 rpm for 5 minutes. Next, the kneaded mixture was hot pressed using a metal mold having a length × width = 20 cm × 20 cm and a thickness of 1 mm. Press conditions are 200 ℃, 5
0 kg / cm ² , for 2 minutes. The obtained sheet was cut to prepare kneaded pellets. Preparation of test sample and kneading compounded pellets prepared by various mechanical property tests were applied to an injection molding machine (MIN-7) manufactured by Niigata Iron Works, and a test sample was prepared in the same manner as in Example 6. As a result, the flexural strength and flexural modulus at a temperature of 23 ° C. were 35.2 MPa and 1346 MPa, respectively. The deflection temperature under load is 10
It was 7 ° C.

[0034]

According to the present invention, the alkenylsilane-treated product obtained by treating the layered compound with alkenylsilane
By using a polymerization catalyst comprising a (A component) and a transition metal complex of Group 4 to 6 or 8 to 10 (B component) in the polymerization of a vinyl compound, the melt viscoelasticity of the vinyl compound polymer or Mechanical properties are significantly improved, and a composite resin made of a vinyl polymer is also excellent in various mechanical properties.

[Brief description of drawings]

FIG. 1 is a diagram showing a vinylsilane composition curve of Example 1.

FIG. 2 is a diagram showing melting characteristics of the polymers of Example 2 and Comparative Example 1.

FIG. 3 is a radar chart showing various mechanical properties of the composite resin of Example 6 and the polymer of Comparative Example 3.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Satoshi Yasuhiko             1 Iezaki coast, Ichihara city, Chiba prefecture F-term (reference) 4J002 AC02W AC02X BB03W BB03X                       BB05W BB05X BB06W BB06X                       BB07W BB07X BB08W BB08X                       BB10W BB10X BB12W BB12X                       BB141 BB15W BB15X BB16W                       BB16X BB17W BB17X BB19W                       BB19X BC03W BC03X BC04W                       BC04X BC05W BC05X BC08W                       BC08X BC09W BC09X BC10W                       BC10X BC11W BC11X BC12W                       BC12X BD12W BD12X BD13W                       BD13X BE03W BE03X BF02W                       BF02X BF03W BF03X BL00W                       BL00X BQ001 DJ036 FD016                 4J028 AA01A AB00A AB01A AC01A                       AC10A AC28A AC31A AC39A                       AC41A AC42A AC44A AC45A                       AC46A AC47A AC48A BA00A                       BA01B BA02B BA03A BA03B                       BB00A BB00B BB01B BC15B                       BC16B BC17B BC19B BC25B                       BC27B BC33B BC34B BC35B                       BC39B CA30B EA01 EB02                       EB03 EB04 EB05 EB07 EB08                       EB09 EB10 EB13 EB15 EB17                       EB18 EB21 EB26 GA06 GA26

Claims (13)

[Claims] 1. A vinyl compound comprising an alkenylsilane-treated product (component A) obtained by treating a layered compound with alkenylsilane and a transition metal complex of group 4 to 6 or 8 to 10 of the periodic table (component B). Polymerization catalyst. 2. The catalyst for vinyl compound polymerization according to claim 1, wherein the layered compound is a 2: 1 type layered compound having a layer charge of 0.1 to 0.7. 3. The alkenylsilane is represented by the general formula R ⁹ _4-n SiX _n (wherein R ⁹ is a hydrocarbon-containing group and at least one is a group having a carbon-carbon double bond, and X is silicon. The element directly bonded to is a functional group of halogen, nitrogen or oxygen, and n is an integer of 1 to 3. However, when R ⁹ is plural, each R ⁹ may be the same or different.) The catalyst for vinyl compound polymerization according to claim 1 or 2, which is a silane compound represented by: 4. The alkenylsilane has the general formula H ₂ C═CH— (CH ₂ ) _k —SiH _m R _3-m (wherein R is an alkyl group having 1 to 5 carbon atoms, and k is 1
The above integer, m is an integer of 1 to 3. ). The vinyl compound polymerization catalyst according to claim 1 or 2, which is a silane compound containing a hydride represented by: 5. The vinyl compound polymerization according to claim 1, wherein the component (B) is a metal complex having a ligand having a carbon 5-membered ring or a chelate ligand of a hetero atom. catalyst. 6. A method for producing a vinyl compound polymerization catalyst, which comprises contacting a layered compound with an alkenylsilane, and then contacting the resulting component (A) with component (B). 7. When the layered compound and the alkenylsilane are contacted with each other, the layered compound is contacted with a treatment of an organosilane compound excluding the alkenylsilane compound in advance, or with the organosilane compound excluding the alkenylsilane compound simultaneously with the alkenylsilane or in a subsequent step. The method for producing a vinyl compound polymerization catalyst according to claim 6, wherein the component (A) is prepared by bringing them into contact with each other. 8. (B) per unit weight g of component (A)
7. The components are brought into contact with each other in an amount of 0.01 to 100 μmol.
8. The method for producing the vinyl compound polymerization catalyst according to any one of 7). 9. A method for polymerizing a vinyl compound (component C), which uses the polymerization catalyst according to any one of claims 1 to 5 or the polymerization catalyst produced by the method according to any one of claims 6 to 8. . 10. The method for polymerizing a vinyl compound according to claim 9, wherein the component (C) is one or more olefins selected from ethylene, propylene, butene, butadiene, cyclic olefins having 5 to 20 carbon atoms, and styrene. 11. A vinyl compound (C component) obtained by using the polymerization catalyst according to any one of claims 1 to 5 or the polymerization catalyst produced by the method according to any one of claims 6 to 8. ) Polymer. 12. The vinyl compound according to claim 11 (C
A composite resin composed of a polymer of component) and a thermoplastic resin. 13. A composite resin composition comprising a layered compound and a copolymer of alkenylsilane and propylene,
A composite resin composition in which a layered compound is dispersed in a copolymer as particles of 1 μm or less.