JPH0967407A - Catalyst for polymerization of vinyl compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for polymerization of a vinyl compound, excellent in durability of activity, polymer properties and stability by carrying a transition metal compound through an unsaturated bond in a non-crosslinked copolymer of α-olefin and diene. SOLUTION: This catalyst for polymerization of a vinyl compound is composed of a carrier carrying a transition metal compound such as titanium trichloride. The carrier is a substantially non-crosslinked copolymer of an α-monoolefin such as ethylene and a diene such as butadiene and carries the transition metal compound by bonding the transition metal compound through an unsaturated bond in the copolymer. Preferably, the catalyst for polymerization of the vinyl compound is combined with an organic metal compound component.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for vinyl compound polymerization. Specifically, the present invention relates to a catalyst obtained by supporting a transition metal compound on an olefin / diene copolymer.

The present invention also relates to a catalyst capable of highly sustainable polymerization, which comprises this catalyst component as a transition metal component, and to the production of vinyl compound polymers using this catalyst. Furthermore, the present invention relates to a composite material of the catalyst support polymer and the vinyl compound polymer obtained by the polymerization, which is obtained by this polymerization.

In the present invention, the term "catalyst" refers to a catalyst which substantially functions as a catalyst by combining promoters (in which case, the catalyst of the present invention may be particularly referred to as a catalyst component), Also, it means both of those having a function as a catalyst by themselves even if the promoters are not combined. This difference depends on the type of vinyl compound to be polymerized. That is, although a co-catalyst is unnecessary for monomers polymerized by cationic polymerization such as vinyl ether, a so-called Ziegler-type catalyst or Kaminski-type catalyst using an organoaluminum compound as a co-catalyst for α-monoolefins such as ethylene The catalytic ability is substantially expressed by forming. Therefore,
The term "catalyst" as used hereinafter includes the case where it is used as a "catalyst component".

Further, in the present invention, the term "vinyl compound" as a polymerization target in the broadest sense is used as having the same meaning as "ethylenically unsaturated compound", and ethylene, propylene and the like α- Monoolefins and vinyl ethers, styrene, (meth) acrylates and the like are included (details described later).

[0005]

PRIOR ART A combination of a transition metal compound component, for example, a component consisting of a halogen-containing compound of a periodic table group 4 metal, and an organometallic compound component, for example, a periodic table group 1 to 3 metallic organometallic compound. Both so-called Ziegler catalysts comprising the above and so-called Kaminski catalysts using metallocene compounds as the transition metal compound component are useful as catalysts for the polymerization of vinyl compounds, in particular α-olefins.

Since these catalysts are well known, and in particular the former Ziegler type catalysts were relatively early in their birth, various modifications have been proposed.

One of the modifications of such Ziegler type catalysts is that a transition metal component is supported on a carrier, and one using an inorganic compound such as magnesium halide as a carrier is a so-called high activity catalyst. It is also known to be advantageous from the viewpoint of labor saving, since it is known that there is no need to remove the polymerization catalyst residue from the resulting polymer after polymerization.

The transition metal compound catalyst component having magnesium halide as a carrier supports formation and support of carrier solid by precipitation of solubilized magnesium halide in situ
In addition to the method described in the above, methods of supporting a transition metal compound on a carrier that is already solid are also known. In addition, as other carriers, inorganic oxides such as alumina,
Silica, titania, magnesia and the like are known.

However, in the case of using these inorganic carriers, even if a high activity catalyst is used, a small amount of carrier used remains in the produced polymer. The problems become apparent. That is, for example, an inorganic salt used as a carrier or an inorganic salt generated from an inorganic oxide used as a carrier remains as a catalyst residue, and particularly when the inorganic oxide is used as a carrier, the polymerization activity decreases with time. Thus, it may be difficult to obtain a desired polymer, for example, a block copolymer by long-term polymerization.

As a solution to the problem based on such catalyst residue, techniques using a polymer carrier are also known. For example, JP-A-63-289004 and JP-A-1-115909 disclose a catalyst in which a catalyst component compound (magnesium, titanium and electron donor compounds) is supported on a styrene-divinylbenzene copolymer, Journal of Polymer Science, Polymer Chemistry
Ed., 31 1561 pp (1993) discloses a catalyst component carrying titanium tetrachloride in the same manner as polystyrene beads (styrene-divinylbenzene copolymer).

However, as far as disclosed, the loading of the catalyst component compound seems to be insufficient, and the dropping of the loading component occurs from the beginning or during the polymerization to generate a fine particle polymer due to the non-supported catalyst component. It seems that there is a disadvantage that the catalyst activity is lowered.

[0012]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems observed in conventional supported catalyst components, specifically, in particular, the activity persistence and polymerization when used for the polymerization of vinyl compounds. An object of the present invention is to improve polymer properties such as particle properties of a produced polymer.

[0013]

[Means for Solving the Problems]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention uses a specific unsaturated polymer as a carrier polymer and specifies a transition metal component utilizing the unsaturated bond of this specific unsaturated polymer. The purpose of the invention is to achieve this object by adopting a carrier mode of <Summary> That is, the catalyst for vinyl compound polymerization according to the present invention comprises one carrying a transition metal compound component that should constitute the catalyst for vinyl compound polymerization, and this support is substantially non-crosslinked with α-monoolefin and diene. And a transition metal compound supported by bonding the transition metal compound through the unsaturated bond.

The vinyl compound polymerization catalyst according to the present invention is characterized in that it comprises the combination of the vinyl compound polymerization catalyst and an organic metal compound.

Furthermore, the method for polymerizing a vinyl compound according to the present invention is characterized in that the above-mentioned catalyst for polymerizing a vinyl compound is brought into contact with a vinyl compound for polymerization.

The present invention also provides a chemical blend composition of the carrier polymer and the resulting vinyl compound polymer as a result of the use of a catalyst comprising the polymeric supported catalyst component.

That is, the chemical blend composition according to the present invention is a copolymer of an α-monoolefin and a diene, wherein the diene-derived unsaturated bond is at least partially saturated by the addition of a transition metal compound. It consists of a complex of a polymer (1) and a polymer (2) of a vinyl compound, It is characterized by the above-mentioned. <Advantage> According to the present invention, by using a polymer having a unsaturated bond as a carrier polymer and supporting the transition metal compound component using the unsaturated bond, it is recognized in the above-mentioned conventional supported catalyst component. Problems are solved. That is, since the support of the transition metal compound is strong, the problem of the formation of the particulate polymer by the non-supported substance is virtually absent, and the catalyst composed of this supported catalyst has a long duration of activity and is livingly Since it seems to behave, it is useful for the production of block copolymers and the like.

The polymer of the vinyl compound obtained as a result of using this polymer-supported catalyst component is a chemical blend composition with the polymer used as a carrier, which is different from a simple blend composition of both polymers. It is a useful novel polymer having mechanical properties. DETAILED DESCRIPTION OF THE INVENTION The present invention basically relates to a catalyst component for vinyl compound polymerization. <Supported Catalyst Component> (1) Carrier The carrier used in the present invention is a copolymer of an α-monoolefin and a diene. Here, “copolymer of α-monoolefin and diene” is not limited to the copolymer of only the two monomers listed, and a plurality of α-monoolefins and / or a plurality of It is intended to include terpolymers and multicomponent copolymers copolymerized with dienes. The copolymer may be crystalline or amorphous.

As this α-monoolefin, ethylene and its homologues, such as α-monoolefins (for example, those having up to about 10 carbon atoms) are typical. Specifically, ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, and the like can be exemplified.

As a diene which is a comonomer constituting the copolymer, butadiene and a homologue thereof, a conjugated or non-conjugated diene is one of the typical examples.

Other typical examples of dienes are non-conjugated dienes other than those mentioned above, in particular those having a cyclic structure, such as ethylidene norbornene.

Suitable non-conjugated dienes are so-called EPDs.
An example can be found in non-conjugated dienes for ethylene-propylene based elastomers known as M.

That is, as the diene which can be used in the present invention, butadiene, isoprene, 1,3-pentadiene, 1,4-hexadiene, methyl-1,4-
Hexadiene, 1,5-hexadiene, 1,7-octadiene, methyl-1,6-octadiene, 1,9-decadiene, ethylidene norbornene, vinylcyclohexene, vinyl norbornene, etc. are exemplified. Among these, 1,4-hexadiene, methyl-1,4-hexadiene, methyl-1,6-octadiene, and ethylidene norbornene are preferable.

Specific examples of comonomers which can be further copolymerized as required can be found in the examples of vinyl compounds described later.

This α-monoolefin / diene copolymer is easy to synthesize even if a suitable one is not available, and can be obtained by copolymerization of certain monomers.

A process for producing such an α-monoolefin / diene copolymer is described, for example, in JP-B-64-2128,
No. 64-9327, Japanese Examined Patent No. 6-9327, Japanese Patent Laid-Open No. 2
-311507 etc. are disclosed by each gazette. A crystalline or non-crystalline polymer can be obtained by homopolymerization or copolymerization of ethylene, propylene and the like. Although the method of introducing a diene is not particularly specified, a method of randomly copolymerizing in coexistence with an olefin and a method of copolymerizing a diene and an olefin after polymerization of an olefin are exemplified.

The diene content of the α-monoolefin / diene copolymer as a carrier is determined by the transition metal content when the transition metal compound is supported and the carrier-derived polymer in the chemical blend to be formed after vinyl compound polymerization. The content can be determined to be a predetermined value. In general, the molar content of the diene in total is 0.1 to 30 mol%, preferably 0.3 to 15 mol%.

Whether the copolymer is amorphous or crystalline depends on the type and composition of the olefin and the stereoregularity. Which one is preferable depends on the target catalytic property and / or chemical blend / composite material and the like.

The carrier polymer is preferably a non-crosslinkable meltable, considering its use as a component of a chemical blend. <Transition Metal Compound> As the transition metal compound to be supported on the above-mentioned carrier polymer, any compound which can be used as a transition metal compound of a Ziegler type catalyst and a Kaminski type catalyst can be targeted in the present invention.

First, as the metal, those of Group 4 of the periodic table, in particular, Ti, Zr and Hf can be mentioned. And, as the compound, a halogen compound and / or an alkoxy compound are typically used. Although compounds in which all of the valences of these transition metals are satisfied with halogen atoms and / or alkoxy groups are typical, some or all of the valences are other groups and / or ligands. It may be satisfied. As such groups or ligands, generally, five-membered conjugated members such as hydride groups, allyl groups such as phenyl groups and benzyl groups, cyclopentadienyl groups, substituted cyclopentadienyl groups, indenyl groups and fluorenyl groups A ring ligand, an amido group, etc. are illustrated.

Preferred Group 4 transition metal compounds are halogen compounds such as titanium trichloride, titanium tetrachloride, zirconium tetrachloride, titanocene dichloride, zirconocene dichloride and the like. Particularly preferred are halogen compounds such as titanium trichloride, titanium tetrachloride, and zirconium tetrachloride. <Support of Transition Metal Compound> The supported catalyst component according to the present invention is obtained by supporting a transition metal compound on the above-mentioned carrier unsaturated polymer using its unsaturated bond.

The formation of covalent bonds can be carried out by any suitable method depending on the unsaturated bond of the carrier polymer as one reactive group and the type of given transition metal compound giving the other reactive group. It can be implemented.

Since direct reaction of both reactive groups is usually not easy, it is often convenient to convert one or both into reactive derivatives prior to reaction.

One example of such an indirect reaction method is the unsaturated bond of the carrier polymer is brominated by halogenation, eg addition of bromine or addition of hydrogen bromide, and reacted with an alkali metal such as lithium or sodium ( Lithium halides, etc.), such that alkali metalated polymers are reacted with transition metal halides (such as dehalogenated lithium) to form carbon-metal bonds. These reactions are usually carried out in solution or in suspension in a solvent for at least one of the participating reactants. The weight ratio of carrier polymer / transition metal compound is usually about 100/1 to 1/100. The resulting supported catalyst can also be washed with a solvent for the unsupported transition metal compound.

For uniform loading, fine particles (for example, an average particle size of 7) may be used if the carrier polymer is not solubilized.
It is preferable that it is 00 micrometer or less.

Generally, the amount of transition metal compound in the catalyst component is 0.01 to 15% by weight in terms of weight of transition metal atom,
Preferably, it is 0.1 to 5% by weight. <Formation of Catalyst> The catalyst component of the present invention not only functions as a catalyst itself but also according to a place commonly used for Ziegler type catalysts or Kaminski type catalysts, depending on the kind of vinyl compound to be polymerized. It has been mentioned above that the catalyst may be formed in combination with the organoaluminum compound to be a co-catalyst.

As the organoaluminum compound in that case, those which can be used for Ziegler type and Kaminsky type catalysts can generally be used also in the present invention.

Examples of such organoaluminum compounds include (i) trialkylaluminums such as trimethylaluminum, triethylaluminum and tri-aluminum.
n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum etc., (ii) halogen-containing organoaluminums such as dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, Diethylaluminum fluoride, diethylaluminum iodide, etc., (iii) organic alkoxyaluminum compounds, such as diethylaluminum ethoxide, diethylaluminum phenoxide, ethylaluminum diethoxide, etc., (ii) organic aluminum hydride compounds, such as diethylaluminum hydride , Diisobutylaluminum hydride, etc. (E)
Organoaluminum oxy compounds such as methylalumoxane, ethylalumoxane, isobutylalumoxane, methyl isobutylalumoxane, diisobutylaluminoxybutylboronic acid and the like are exemplified. Among these, trialkylaluminums, halogen-containing organoaluminums, organoaluminum oxy compounds and the like are preferably used.

Although organoaluminum compounds are highly necessary for the polymerization of α-monoolefins and aromatic unsaturated compounds, etc., they need not be used for the polymerization of cationically polymerizable monomers such as vinyl ethers, or they may be poisoned. It can not be used because it causes.

The amount of the supported catalyst used in the present invention and, if necessary, the organoaluminum compound used is optional. For example, in the case of solvent polymerization, the amount of the former used is 10 ⁻⁷ to 10 ³ millimoles / liter as a transition metal atom, preferably 10 ⁻⁴ to 10 millimoles / liter. When the latter is used, the molar ratio of Al / transition metal is usually 1 to 10
It is in the range of 0000, preferably 5 to 10,000.

For polymerization of the vinyl compound, the supported catalyst of the present invention and, if necessary, the organoaluminum compound used may be introduced separately into the reaction vessel, or those prepared by bringing the two into contact in advance are introduced into the reaction vessel. May be When the two are brought into contact in advance, it is also possible to carry out this in the presence of the monomer to be polymerized to partially polymerize the monomer (so-called prepolymerization). The catalyst of the present invention may contain other components in addition to the above components. As the third component (optional component) that can be added, for example, active hydrogen-containing compounds such as H ₂ O, methanol, ethanol, butanol, etc., electron donating compounds such as ethers, esters, amines, phenyl borate, phosphorous Alkoxy-containing compounds such as phenyl acid, tetraethoxysilane, diphenyldimethoxysilane, etc.
Lewis acids such as triphenylboron, tris (pentafluorophenyl) boron, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbinium tetrakis (pentafluorophenyl)
It is possible to illustrate ionic compounds such as borate and the like. <Polymerization of Vinyl Compound><VinylCompound> In the present invention, the “vinyl compound” to be polymerized is as described above in the broadest sense of the term. . Accordingly, this should be synonymous with "ethylenically unsaturated compound", and ethylene and its homologue α-monoolefin (for example, one having about 12 carbon atoms) and its unsaturated derivative conjugated and Besides non-conjugated diolefins,
Styrene and vinyl naphthalene and their side chain and / or nuclear substitution (substituents are lower alkyl (C _1-
C ₄ about), halomethyl, halogen, etc.), vinyl halides, until (meth) acrylic acid and its derivatives (such as esters (about 10 carbon atoms, alkyl esters), amides, etc.), the different non-conjugated diene Compounds (for example ethylidene norbornene), vinyl ethers (for example C ₁ -C ₈ alkyl vinyl ethers), vinyl or allylsilanes (for example tri C _1-
C ₈ alkyl vinyl silane and tri _C 1 -C ₈ alkyl aryl silanes), is intended to cover, (meth) acrylonitrile.

Specifically, for example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 3-
Α-olefins such as methylbutene-1, 4-methylpentene-1, butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, methylhexadiene,
Diene compounds such as 1,7-octadiene, methyl-1,6-octadiene, etc., aromatic unsaturated compounds such as styrene, divinylbenzene, vinylnaphthalene, trimethylvinylsilane, trimethylallylsilane, isobutyl vinyl ether, acrylic acid, ethyl acrylate, methacrylic Examples thereof include polar vinyl compounds such as methyl acid, acrylonitrile and vinyl chloride.

Among these, typical are α-monoolefins, particularly those having about 2 to 12 carbon atoms, alone or in combination. Thus, vinyl compounds representative of the present invention are ethylene, propylene, butene-1, hexene-
1, octene-1, and a combination of two or more thereof and a combination of ethylene and propylene with a conjugated or non-conjugated diene (eg, ethylidene norbornene).

The supported catalyst according to the present invention is of course applied to solvent polymerization using a solvent, but is also applied to liquid phase non-solvent polymerization, gas phase polymerization and melt polymerization substantially using no solvent. . Moreover, it applies also to continuous polymerization and batch polymerization.

As the solvent in the case of solvent polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene and toluene is used.

The polymerization temperature is about -100 to 230.degree. C., preferably -20 to 100.degree. The pressure of the reaction system is not particularly limited, but in the case of gaseous monomers, generally,
The pressure is in the range of normal pressure to 2000 atm, preferably normal pressure to 100 atm.

In polymerization, molecular weight control can be carried out by known means such as selection of temperature and pressure or introduction of hydrogen. <Generated Polymer> One of the features of the present invention is that the polymer obtained by polymerizing a vinyl compound using the catalyst of the present invention together with a co-catalyst as required is not a simple polymer of the vinyl compound. And an α-monoolefin / diene copolymer used as a catalyst carrier (wherein at least a portion of the diene-derived unsaturated bond is lost by being covalently bonded to the transition metal compound) Is a chemical blend of

The composition of such a chemical blend or complex corresponds to the ratio of the amount of α-monoolefin / diene copolymer used as a carrier to the amount of polymerization of the resulting vinyl polymer.

An alpha-monoolefin / diene copolymer,
Although the quantitative ratio to the vinyl compound polymer obtained by using the present catalyst is arbitrary, in general, the weight ratio of the former to the latter is 1/9.
9 to 99/1, preferably 10/90 to 90/1
The range is 0.

If no diene or polyene compound is used as the vinyl compound to be polymerized, or if a crosslinking reaction does not occur during the polymerization, the resulting polymer, ie the chemical blend / complex is essentially within the category of thermoplastic polymers. Belongs to Thus, the product polymers according to the invention are also, according to the customary use of such polymers,
Various auxiliary materials such as resinous or rubbery polymers, inorganic or organic fillers, stabilizers, lubricants, crystal nucleating agents, dyes and pigments, etc. can be blended.

[0051]

【Example】

Example 1 <Production of carrier polymer> Propylene / methyl- was prepared according to the method described in Example 2 of JP-A-2-311507.
A 1,6-octadiene copolymer was prepared. The copolymer contained 2.7 mol% of 1,6-octadiene and 97.3 mol% of propylene. As a result of the measurement of ¹³ C-NMR, the [mm mm] pentad fraction was 0.91. As a result of GPC measurement, the number average molecular weight is 2.9 × 10
^4, and the ratio of the weight average molecular weight to number average molecular weight (Q value)
Was 5.1.

Ten grams of this copolymer is added to 200 ml of o-dichlorobenzene and dissolved at 130 ° C. Then, the insoluble portion is removed by filtration under a nitrogen stream, and then precipitated with ethanol, and the precipitate is dried. It was used for the subsequent study. <Preparation of Supported Catalyst> Three grams of this dried polymer is suspended in 100 ml of carbon tetrachloride, and then 50 ml of a solution of bromine in carbon tetrachloride (0.03 mol / l) is added dropwise to react at room temperature for 8 hours. The solid component was separated by filtration, washed with 500 ml of carbon tetrachloride, and then dried at 45 ° C. under reduced pressure. The bromide was then suspended in 100 ml of toluene solvent, 0.3 gram of lithium metal was added and allowed to react at room temperature for 8 hours. After completion of the reaction, unreacted metal lithium is removed, 50 ml of a toluene solution of titanium tetrachloride (0.06 mol / l) is added dropwise, and the reaction is carried out for a further 8 hours, then washed with toluene and dried. A supported catalyst was obtained. In this catalyst, 0.18% by weight of titanium was supported. <Polymerization of ethylene> A 300 ml three-necked flask was sufficiently dried and purged with nitrogen, and then 100 ml of dehydrated and degassed toluene and 0.40 g of the supported catalyst synthesized above were obtained (15 as titanium atoms). Micromoles), then 3 millimoles of triethylaluminum was introduced as a cocatalyst, and ethylene was introduced at normal pressure.
The polymerization was carried out for 1 hour at ° C. After completion of the polymerization, add about 20 ml of hydrochloric acid / ethanol to the obtained slurry
After stirring for a minute, the whole was added to 700 ml of ethanol, and after stirring for an additional hour, it was separated by filtration and dried. This resulted in 0.59 grams of a chemical blend / composite material containing 0.19 grams of polyethylene. [Examples 2 to 5] Polymerization time is 3 hours, 25 hours, 50
The reaction was carried out under the same conditions as in Example 1 except that the time was changed to 100 hours. The results are as shown in Table 1 (the results of Example 1 are also described).

Table 1 Polymerization time (h) Chemical blend (g) ^{(Polyethylene content (g))} Example 1 1.0 0.59 (0.19) -2 3.0 0.92 (0.52) -3 25.0 3.20 (2.80) -4 50.0 4.55 ( 4.15) -5 100.0 8.26 (7.86) Example 6 <Polymerization of Styrene> Using the same flask as in Example 1, 100 ml of toluene, 1 mmol of toluethylaluminum and 1 ml of styrene were charged, and then the mixture was manufactured in Example 1. After charging 0.45 grams of the catalyst, polymerization was carried out at 50 ° C. for 13.5 hours. After completion of the polymerization, the same post-treatment as in Example 1 was carried out,
0.56 grams of a chemical blend / composite material containing 0.11 grams of polystyrene was obtained. EXAMPLE 7 <Polymerization of isobutyl vinyl ether> Using the same flask as in Example 1, 10 ml of isobutyl vinyl ether and 0.50 of the catalyst component prepared in Example 1 were used.
The polymerization was carried out at 0 ° C. for 1 hour by charging a gram. After completion of the polymerization, as a result of performing the same post-treatment as in Example 1, 0.2
0.71 grams of a chemical blend / composite material containing 1 gram of polyisobutyl vinyl ether was obtained. Example 8 Preparation of Carrier Polymer Ethylene / Propylene / 1,4
As the hexadiene copolymer, DuPont "Nodel 1145" was used. This copolymer contains 1.2 mol% of 1,4-hexadiene, 80.0 mol% of ethylene,
It contained 18.8 mol% of propylene. As a result of GPC measurement, the number average molecular weight is 1.4 × 10 ⁵ (polystyrene standard), and the ratio of weight average molecular weight to number average molecular weight (Q
Value) was 3.3.

Ten grams of the above carrier polymer is toluene 2
It was dissolved in 00 ml, the polymer was precipitated with ethanol, this operation was performed three times, and then it was dried and used for the subsequent examination. <Preparation of catalyst> 3 grams of dried polymer is dissolved in 100 ml of chloroform, and then hydrogen bromide (9 m
1 ml of mol / l) was introduced and allowed to react at room temperature for 8 hours. Then, the bromide was dissolved in 100 ml of toluene, 0.3 g of lithium metal was added, and the mixture was allowed to react at room temperature for 8 hours. After completion of the reaction, unreacted metal lithium is removed, and then a solution of titanium tetrachloride in toluene (0.
50 ml of 06 mol / l) was added dropwise, reacted for further 8 hours, concentrated, and the concentrate was washed with ethyl ether to obtain a catalyst. The catalyst was loaded with 0.23% by weight of titanium. <Polymerization of Ethylene> Polymerization was carried out under the same conditions as in Example 1 except that 0.4 g of the catalyst obtained above was used. As a result, 0.53 grams of a chemical blend / composite material containing 0.13 grams of polyethylene was obtained. Example 9 Polymerization of Styrene Polymerization was carried out under the same conditions as in Example 6 except that 0.34 grams of the catalyst obtained in Example 8 was used. As a result, 0.47 grams of a chemical blend / composite material containing 0.23 grams of polystyrene was obtained. Example 10 <Polymerization of isobutyl vinyl ether> Polymerization was carried out under the same conditions as in Example 7 except that 1.0 gram of the catalyst obtained in Example 8 was used. As a result, 1.56 grams of a chemical blend / composite material containing 0.56 grams of polyisobutyl vinyl ether was obtained.

[0055]

When a transition metal compound is used as a catalyst and this is supported on a carrier, the transition metal compound is utilized by utilizing its unsaturated bond using an α-monoolefin / diene copolymer as the carrier. The covalent bonding to the support solves the problems encountered when the transition metal compound is not strongly supported, and the resulting polymer is obtained as a chemical blend with the support polymer to give a novel composite material. Further, the catalyst of the present invention is excellent in stability because the catalyst activity is maintained for a long time, as described above in the “General Description of the Invention”.

 ── ── ── ── ──続 き 続 き Continuation of the front page (72) Inventor Shin Taira Shinichi Ishikawa Prefecture Nomi-gun Oguchi No. 1-1 University lodging C-34 (72) Inventor Mori Hideharu Ishikawa Prefecture Nomi-gun Oguchi No 1 -1 University lodgings D-54 (72) Inventors Hiroshi Nishi Nishiki Ishikawa Prefecture Nomi-gun Higuchi-cho Miyatakeka 59-1 ABILOL 205

Claims (4)

[Claim of claim] 1. A support for a transition metal compound component to constitute a catalyst for vinyl compound polymerization, comprising:
A substantially non-crosslinked copolymer of a monoolefin and a diene, characterized in that the transition metal compound is supported by bonding the transition metal compound via its unsaturated bond , Catalysts for vinyl compound polymerization. 2. A catalyst for vinyl compound polymerization comprising a combination of the catalyst for vinyl compound polymerization according to claim 1 and an organic metal compound component. 3. A process for polymerizing a vinyl compound, which comprises contacting the vinyl compound according to claim 1 or 2 with a vinyl compound for polymerization. 4. A substantially non-crosslinked copolymer of an α-monoolefin and a diene, wherein the diene-derived unsaturated bond is saturated at least partially by the transition metal compound bonding. Chemical blend composition which consists of a composite of a polymer (1) and a polymer (2) of a vinyl compound.