JPH0517539A - Production of graft copolymer - Google Patents

Abstract

PURPOSE:To produce the subject copolymer having a high graft degree and a graft efficiency and not producing gels by reacting (A) a swelling state copolymer comprising ethylene, etc., and a dialkenyl benzene with (B) a polymer containing a metal bonded to the end thereof. CONSTITUTION:(A) A swelling state copolymer comprising (i) ethylene or one kind or more of 1-12C alpha-olefins and (ii) 0.01-50mol.% (preferably 0.05-30mol.%) of a dialkenyl benzene of the formula (R<1> is H, methyl; R<2> is 1-6C hydrocarbon; (n) is 0, 1) is reacted with (B) one kind or more of anionic polymerizable monomers containing a metal bonded to the end thereof in the presence of a metal-containing anionic polymerization catalyst, in a solvent such as toluene to provide the objective graft copolymer.

Description

Detailed Description of the Invention

[0001]

The present invention relates to ethylene or α-
The present invention relates to a method for producing a graft copolymer comprising a copolymer composed of an olefin and a specific dialkenylbenzene and a polymer derived from a specific living anion polymerizable monomer. The graft copolymer itself is a thermoplastic resin having excellent physical properties, and at the same time is an excellent resin modifier and resin compatibilizer.

[0002]

2. Description of the Related Art Many techniques for graft-polymerizing a radical-polymerizable monomer such as maleic anhydride or acrylic acid onto a polyolefin have been tried for a long time. For example, JP-A-49-55790 and JP-A-50-32287 are disclosed. It has been known. However, in general, the radical graft polymerization method does not have a sufficiently high degree of grafting or grafting efficiency, and in many cases radical polymerization initiators such as organic peroxides are used. Is likely to occur, and the desired graft copolymer cannot be obtained efficiently.

On the other hand, a specific vanadium-based Ziegler-Natta type catalyst having a living polymerization ability of α-olefin is used to form a radical group at the active end of the living polyolefin to polymerize methyl methacrylate to obtain an α-olefin. Method for producing block copolymer of methyl methacrylate (Makromol. Chem. 186 ,
11, 1985), and similarly, a halogen is added to the active end of the living polyolefin, and α is formed by a coupling reaction between this and the living polystyryllithium.
-Method to obtain block copolymer of olefin and styrene (CC Price edition, "Coordination Polymerization", Pl
enum Pub. New York, 1983, p. 246). Furthermore, as a method similar to the above, a halogen is added to the terminal double bond of the polyolefin obtained by a so-called Kaminsky type Ziegler-Natta type catalyst, and α-olefin and styrene of the α-olefin and styrene are coupled by a coupling reaction with the halogen. There is a method of obtaining a block copolymer (JP-A-62-158709).

However, since these methods use a specific special Ziegler-Natta type catalyst to polymerize α-olefins, the polymer structure of the chain block portion of the produced polyolefin is specialized. ..
Therefore, it is inevitable that the use of the block copolymer obtained by these methods will be limited. Further, a method of obtaining a block copolymer of polyolefin, polystyrene and polybutadiene by a so-called active point conversion method of anionic polymerization active points and Ziegler-Natta type polymerization active points (JP-A-60-20918, Eur. Polym). . J. 1
7 , 1175, 1981. , Makromol. Chem. 181 ,
1815, 1980). However, these methods have various problems such as a decrease in catalytic activity and a decrease in block efficiency due to a low active site conversion efficiency, and it is difficult to obtain a target copolymer having a controlled molecular weight. have.

Also, is a radical polymerizable monomer grafted onto a copolymer of ethylene or α-olefin and a specific dialkenylbenzene?
Or a method of grafting an anionic polymerizable monomer using an anionic polymerization initiator (JP-A-1-1)
18510), both of which do not produce a solvent-free gel together with the graft copolymer during the synthesis of the graft copolymer, and the graft copolymer cannot be efficiently produced, and the physical properties of the graft copolymer (gloss, impact resistance) are also present. ) Is adversely affected. In addition, since the monomer is polymerized in the presence of a copolymer of ethylene or α-olefin and a specific dialkenylbenzene, the molecular weight distribution of the branched polymer to be grafted becomes wide even using an anionic polymerization initiator,
A graft copolymer having a sufficiently controlled structure of the branch component of the graft copolymer cannot be obtained.

[0006]

SUMMARY OF THE INVENTION The present invention is intended to provide a solution to these problems, in which a copolymer of ethylene or α-olefin and a specific dialkenylbenzene is prepared in advance with a metal. A terminal metal-bonded polymer having a regulated molecular weight and molecular weight distribution obtained by polymerizing at least one anionic polymerizable monomer in the presence of an anionic polymerization catalyst containing ethylene or α-olefin and a specific dialkenylbenzene copolymer It is intended to achieve this object by reacting in a swollen state.

[0007]

That is, the present invention comprises (a) at least one kind of ethylene or an α-olefin having 3 to 12 carbon atoms and at least one kind of dialkenylbenzene represented by the following formula (1). And a terminal metal bond obtained by polymerizing at least one anionic polymerizable monomer in the presence of a copolymer having a dialkenylbenzene content of 0.01 to 50 mol% and (b) a metal-containing anionic polymerization catalyst. A method for producing a graft copolymer, which comprises reacting a polymer in a solvent in a swollen state of the copolymer (a).

[Chemical 1] (R ¹ = hydrogen or methyl group, R ² = hydrocarbon residue having 1 to 6 carbon atoms, n = 0 or 1)

The method for producing a graft copolymer according to the present invention uses an unreacted unsaturated group of a specific dialkenylbenzene as a side chain formation starting point, and is polymerized by an anionic polymerization catalyst as a branch of the graft copolymer. Molecular weight distribution and molecular weight distribution without the need for post-treatment including complicated operations and reactions by using a terminal metal-bonded polymer and carrying out the grafting reaction in the swollen state of the copolymer containing dialkenylbenzene. It is possible to form a graft-modified poly α-olefin having a high degree of grafting and a high grafting efficiency, and without losing the properties of the poly α-olefin without forming a gel or the like. ..

The manufacturing method of the present invention will be described in detail below. <“Stem” Copolymer> The “stem” copolymer used in the present invention is a copolymer of ethylene or an α-olefin having 3 to 12 carbon atoms and a dialkenylbenzene represented by the above formula (1). The combined content of the dialkenylbenzene (1) is 0.01 to 50 mol%, preferably 0.05 to 3
It is 0 mol%. This "trunk" copolymer is crystalline. Crystallinity is 10 by X-ray analysis.
It is indicated by the above, preferably 20 or more. The "stem" copolymer may further contain a small amount of monomer up to about 15 mol% based on the total amount of both monomers. The "trunk" copolymer should have a molecular weight and / or melting point sufficient to call it a resin. The molecular weight is typically 3,000 or more in terms of number average molecular weight, or the melting point is typically 40 ° C. or more.

<Α-Olefin> Examples of the above ethylene or α-olefin which is one of the constituents of the "stem" copolymer resin include ethylene, propylene, 1-butene, 1-hexene and 3-methyl-olefin. 1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3
-Dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene , Allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-
Butene, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2,2,1] -heptane and the like can be mentioned.

Of these, preferred examples are ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 3. -Methyl-1-hexene and the like, especially ethylene, propylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1
-Pentene is preferred. These ethylene or α-
One olefin may be used, or two or more olefins may be used. In particular, when 1-hexene is used as the α-olefin, it is preferably used in combination with at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 3-methyl-1-butene. When two or more kinds of α-olefins are used, the α-olefins may be randomly distributed in the unsaturated copolymer resin or may be distributed in blocks.

<Dialkenylbenzene> These dialkenylbenzenes used in the present invention are represented by the following structural formulas, and may be isomers such as o-form, m-form and p-form. It may be a mixture of these isomers.
Also, various derivatives in which the benzene ring is substituted may be used.

[Chemical 1] R ¹ = hydrogen or methyl group, R ² = hydrocarbon residue having 1 to 6 carbon atoms, n = 0 or 1) Specific examples include divinylbenzene, isopropenylstyrene, divinyltoluene, divinylnaphthalene (ie, , R ² includes a bonded benzene ring) and the like. The commercially available crude divinylbenzene also contains ethylvinylbenzene, diethylhenzene and the like, but these can be used without separate separation.

This copolymerization can be carried out under the same conditions as in ordinary Ziegler-Natta type polymerization. For example, in so-called solvent polymerization using an inert diluent, a hydrocarbon solvent such as hexane, heptane, cyclohexane, benzene, toluene and xylene can be used, and the polymerization temperature is 0 ° C to 120 ° C, preferably 20 ° C to 90 ° C,
It is usual to carry out at the temperature of. The polymerization pressure can also be widely changed. Further, hydrogen can be used as a molecular weight regulator of the copolymer. What is important in the present invention is that ethylene or α-olefin is copolymerized with dialkenylbenzene, and more interestingly, in that case, one of the two alkenyl groups is α-olefin. That is, it seems that they remain as monoalkenylbenzene in the copolymer without being involved in the copolymerization.
Therefore, the copolymer formed in this step is preferably solvent-soluble (previously added with Br ₂ in order to prevent thermal polymerization of unreacted alkenyl groups which may occur) (solvent: xylene , Soxhlet extraction, 8 hours, 8
It can be said that 0 mesh gold net is used).

These dialkenylbenzenes may be randomly distributed in the copolymer resin or may be distributed in blocks. The preferred content of monoalkenylbenzene in the unsaturated copolymer resin is 0.05 to
It is 30 mol%, particularly preferably 0.1 to 15 mol%. If it is less than 0.01 mol%, there is a drawback that it is difficult to improve the grafting efficiency because the unsaturated copolymer resin contains few unsaturated groups. On the other hand, if it exceeds 50 mol%, the copolymerization rate will be slow during the production of the copolymer resin, and in the case of slurry polymerization, the solvent-soluble by-product polymer will increase and the viscosity of the polymerization system will increase, resulting in poor productivity. At the same time, there are drawbacks such that the resulting unsaturated copolymer becomes sticky and the resinous state is not maintained.

When the α-olefin is mainly composed of propylene, the melt flow rate of the copolymer resin is usually 0.001 to 1000 g when the melt flow rate (MFR) measured according to JIS-K-6758. /
The molecular weight corresponds to 10 minutes, preferably 0.01 to 500 g / 10 minutes, particularly preferably 0.05 to 100 g / 10 minutes. In addition, this copolymer resin is JIS-K-
Elastic modulus according to 7203 is 500-80,000 kg / c
It is preferably m ² .

The preferred type from the viewpoint of the molecular structure of the "stem" copolymer resin is as follows. (1) A random copolymer of one or more ethylene or α-olefins and one or more dialkenylbenzenes. (2) A block copolymer composed of one or more ethylene or α-olefin polymerized blocks and a random copolymerized block of one or more α-olefins and one or more dialkenylbenzenes. (The type and amount ratio of ethylene or α-olefin in the ethylene or α-olefin polymer block may be the same as or different from those of ethylene or α-olefin in the random copolymer block). (3) Random copolymerization block of one or two or more kinds of ethylene or α-olefin with one or more kinds of dialkenylbenzene (block a) and random copolymerization of ethylene or α-olefin and dialkenylbenzene. A block (block b), wherein at least one of the type, number, and amount ratio of ethylene or α-olefin contained in this block b, and the type, number, and amount ratio of dialkenylbenzene is block a. A block copolymer composed of different blocks.

Here, the term "block copolymer" means the following copolymers. For example, "a block copolymer composed of a homopolymerized block of monomer A and a random copolymerized block of monomer A and monomer B" means a homopolymerized block of monomer A and a random copolymer of monomer A and monomer B. In addition to those in which the combined block is chemically bonded to form a structure such as A ... A-AABABAAAAB .. It also includes a copolymer in which a polymer block and a random copolymer block of a monomer A and a monomer B are chemically bonded, and also includes a homopolymer of the monomer A, a random copolymer of the monomer A and a monomer B, and the like. Also included as a mixture.

Similarly, "a block copolymer comprising a polymerized block a and a polymerized block b" means that a composition in which the polymerized block a and the polymerized block b are chemically bonded constitutes the entire composition. In addition to the above, a mixture containing a copolymer in which the polymerized block a and the polymerized block b are chemically bonded, and a polymer composed only of the polymerized block a, a polymer composed only of the polymerized block b, and the like are also contained. But
Is also meant and has the same meaning as a so-called "block copolymer" synthesized using a Ziegler-Natta catalyst.

<“Branch” Polymer> The “branch” polymer to be grafted to the above “trunk” copolymer is a metal-containing anionic polymerization catalyst which is used to polymerize an anion-polymerizable monomer to remove a metal derived from the catalyst. It is a terminal metal-bonded polymer having a terminal. This polymerization is called living anionic polymerization. First, as the metal-containing initiator for living anionic polymerization, known ones can be used. For example, (a) organic alkali metal such as n-butyllithium, sec-butyllithium, t
ert-Butyllithium, ethyllithium, benzyllithium, allyllithium, phenyllithium, phenylsodium, α-methylstyrene tetramer dianion-N
a, Na-naphthalene, Na-biphenyl, Na-anthracene, and α-methylstyrene dimer dianion-K, (b) alkali metal alkoxide (including phenoxide), for example, tert-butoxy potassium, t
ert-butoxysodium, and tert-butoxylithium, (c) alkali metals such as lithium, sodium and potassium, (d) organic alkaline earth and alkaline earth alkoxides, (v) alkaline earth metals, and (f). Such compounds include compounds having a metal-nitrogen bond of these metals. Particularly preferred are organic alkali metals and alkali metals.

Well-known anion-polymerizable monomers are used, but specific examples include the following. (I) General formula

[Chemical 2] (R is hydrogen, alkyl having 1 to 8 carbons or chlorine, X is chlorine, phenyl group, substituted phenyl group, -CH =
CHR ^I, -CN,

[Chemical 3] A vinylic compound represented by (R ^I is hydrogen, an alkyl or phenyl group having 1 to 8 carbon atoms), (ii) the general formula

[Chemical 4] (R ^II and R ^III are alkyl having 1 to 8 carbons, phenyl group, n = 3 or 4), cyclic organosiloxanes, (iii) alkyl or phenyl isocyanates, (iv) 1,2-epoxy Alkanes, (v)
Cyclic lactones.

Specific examples of the anion-polymerizable monomer are as follows. (A) Styrene, α-methylstyrene, (o, m, p) -methylstyrene, (o,
m, p) -chlorostyrene, (m, p) -divinylbenzene, (m, p) -diisopropenylbenzene, (m, p)
p) -vinylisopropenylbenzene, vinylnaphthalene, acenaphthalene, (b) butadiene, isoprene,
2,3-dimethylbutadiene, 1,3-pentadiene,
2-cyanobutadiene, 2-chlorobutadiene, 2-phenylbutadiene, (c) vinyl chloride, vinylidene chloride, acrylonitrile, α-methacrylonitrile, α-ethacrylonitrile, α-octylacrylonitrile, (e) N, N- Dimethyl acrylamide,
N, N-dioctylacrylamide, N-methyl-N-
Ethyl acrylamide, (f) methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-methylhexyl acrylate, octyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl methacrylate, phenyl methacrylate, (to) 2-vinyl pyridine, 4 -Vinyl pyridine, (thi) ethyl vinyl ketone, t-butyl vinyl ketone, (ri) N-vinyl carbazole,

(N) Trimethoxyvinylsilane, triethoxyvinylsilane, tri-2-methoxyethoxysilane, triacetoxyvinylsilane, trimethylvinylsilane, tributylvinylsilane, dimethyldivinylsilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclo Trisiloxane, octaphenylcyclotetrasiloxane,
2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane, trimethyltriethylcyclotrisiloxane, tetramethyltetraethylcyclotrisiloxane, trimethyltrivinylcyclotrisiloxane,
(L) Ethyl isocyanate, propyl isocyanate, n-butyl isocyanate, isobutyl isocyanate, amyl isocyanate, hexyl isocyanate, octadecyl isocyanate, phenyl isocyanate, benzyl isocyanate, allyl isocyanate, tolyl isocyanate, p-methoxyphenyl isocyanate, (wo) ethylene oxide, propylene Oxide, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 2-phenyl-1,
2-epoxyethane, 4-phenyl-1,2-epoxybutane, and (wa) ε-caprolactone, δ-valerolactone. These anion-polymerizable monomers may be used alone or in admixture of two or more, or they may be used sequentially. That is, the living polymer obtained may be a single, random or block polymer chain.

The polymerization of the anionically polymerizable monomer is -100.
℃ or more and 200 ℃ or less, preferably -90 ℃ or more 180 ℃
Hereafter, it can be carried out at a temperature of −80 ° C. or higher and 150 ° C. or lower under normal pressure, reduced pressure or increased pressure.
As the solvent that can be used in the above polymerization,
For example, n-hexane, n-heptane as an aliphatic hydrocarbon, cyclohexane, decahydronaphthalene as an alicyclic hydrocarbon, benzene, toluene, xylene (o-, m-, p-) as an aromatic hydrocarbon, aproton Tetrahydrofuran, dioxane, ethyl ether, pyridine, diglyme and the like can be used as the polar solvent. These solvents may be used alone or as a mixture.

<Graft Copolymerization> In the production of the graft copolymer of the present invention, a copolymer of ethylene or α-olefin and a specific dialkenylbenzene is reacted with an anionically polymerizable living polymer in a swollen state. It depends. Here, the swelled state means 1 to 300% by weight, preferably 1 to 200% by weight, particularly preferably 5 to 100% by weight, based on the dry weight of the copolymer of ethylene or α-olefin and a specific dialkenylbenzene. It means a granular or powdery material in a wet state containing the solvent. The graft reaction is carried out by immersing a solution of ethylene or α-olefin swollen in a solution, a specific dialkenylbenzene copolymer, and a living polymer solution of an anionically polymerizable monomer in an inert gas atmosphere such as a nitrogen gas atmosphere at −100 ° C. or higher. 200 ° C or lower, preferably -90 ° C or higher and 180 ° C or lower,
Particularly preferably, the reaction is carried out at -80 ° C or higher and 150 ° C or lower. Purification of the graft copolymer can be performed according to a known method.

The graft copolymer of the present invention is itself
Used as an adhesive film for lamination. or,
It may be used as a modifier for polyolefins and polyphenylene ethers, or as a compatibilizer for polymer blends of both. When used as a modifier, it is used in a proportion of 0.05 to 50 parts by weight with respect to 100 parts by weight of the resin to be modified. When used as a compatibilizer, the mixture is composed of 100 to 100 parts by weight of a mixture of 90 to 10% by weight of polyolefin and 10 to 90% by weight of polyphenylene ether.
It is used in a proportion of 0.05 to 50 parts by weight.

[0026]

【Example】

<Production Example of Solid Catalyst -1> (1) component (A ₁₎ n of dehydrated and deoxygenated synthetic thoroughly purged with nitrogen flask
Introducing 100 ml of heptane, then MgC
l ₂ of 0.1 mol and Ti (O-nBu) ₄ of 0.2
0 mol was introduced and the reaction was carried out at 100 ° C. for 2 hours. After the reaction was completed, the temperature was lowered to 40 ° C., 15 ml of methylhydrogen polysiloxane was introduced, and the reaction was carried out for 3 hours. After completion of the reaction, the produced solid component was washed with n-heptane, and a part thereof was taken out for composition analysis. Ti = 15.2 weight percent, Mg = 4.
It was 2 weight percent. (2) Manufacture of catalyst component n was dewatered and deoxygenated in a flask that had been sufficiently replaced with nitrogen.
100 ml of heptane was introduced, and 0.03 mol of the component (A ₁ ) synthesized above was converted in terms of Mg atom. 0.05 mol of SiCl ₄ was introduced at 30 ° C. for 15 minutes and reacted at 90 ° C. for 2 hours. After completion of the reaction, it was washed with purified n-heptane. Then n-heptane 2
Ortho-C ₆ H ₄ (COCl) _{2 in} 5 ml
0.004 moles are mixed and introduced at 50 ° C., then S
0.05 mol of iCl ₄ was introduced and reacted at 90 ° C. for 2 hours. After completion of the reaction, it was washed with n-heptane to obtain a catalyst component. The Ti content was 2.05 wt% (solid catalyst A).

Production Example of "Stem" Copolymer-1 A stainless steel autoclave having an internal volume of 1 liter equipped with a stirrer and a temperature controller was subjected to repeated vacuum / propylene substitution several times, and then sufficiently dehydrated and deoxygenated. -500 ml of heptane, 50 ml of divinylbenzene (Tokyo Kasei Co., Ltd., mixture of m-form and p-form, divinylbenzene content 53%) 50 ml, triethylaluminum 500 m.
g, and 100 mg of the solid catalyst A were introduced in this order, and 2000 ml of hydrogen was added to start the copolymerization of propylene and divinylbenzene. Copolymerization is propylene pressure 7kg /
cm 2 hours was carried out at ² G, 70 ℃. After the completion of the copolymerization, residual monomers were purged, and the polymer slurry was filtered to obtain 20.52 g of a copolymer powder polymer. The catalytic activity of the copolymer is 205 g copolymer / g Ti component solid catalyst, GP
The number average molecular weight in terms of polystyrene in C is 6540.
0, the weight average molecular weight was 329000, and when the remaining double bonds of the copolymer were brominated and subjected to Soxhlet extraction with xylene, no gel (insoluble matter) was found. The divinylbenzene content measured by UV was 1.4 mol%. This copolymer is referred to as resin I.

Example 1 60 ml of sufficiently dehydrated and purified xylene and 1.8 g of styrene were placed in a flask at room temperature using a break seal method under high vacuum, and styrene was polymerized with 12.8 mg of n-butyllithium to start living. A polystyrene polymer was obtained. A portion of this polymer was collected and precipitated in methanol
When the molecular weight was examined with C, the number average molecular weight was 9300,
The weight average molecular weight was 10,000. After 1.0 g of Resin I was placed in a flask and deaerated in a high vacuum, a xylene solution of synthetic living living polystyrene polymer was added thereto, and the reaction was carried out at 80 ° C. for 144 hours while stirring. During the reaction, Resin I retained its original powder form (contains 28 wt% solvent, based on Resin I dry weight). After the reaction, the solution was added to a large amount of methanol to precipitate the polymer dissolved in the solvent, and then the polymer was recovered and dried. Then, this polymer was subjected to Soxhlet extraction with methyl ethyl ketone for 8 hours, and as a result, 1.15 g of a polymer was obtained. As a result of IR analysis of this polymer, absorption of propylene and styrene was recognized, and as a result of this analysis, the styrene content was 13.3% by weight. Furthermore, when this polymer was subjected to Soxhlet extraction with xylene for 8 hours using a wire mesh of 80 mesh, there was no gel (insoluble matter).

Example 2 50 ml of sufficiently dehydrated and purified decahydronaphthalene, styrene 3 was substituted with nitrogen in a sufficiently dried flask.
g and 4.2 mg of tetramethylethylenediamine were added and sec-butyllithium 11.7 mg was added with stirring at room temperature to obtain a living polystyrene polymer. A part of this polymer was collected and precipitated in methanol, and the molecular weight was examined by GPC. The number average molecular weight was 18200 and the weight average molecular weight was 22000. The fully dried flask was replaced with nitrogen, and 50 ml of sufficiently dehydrated and purified decahydronaphthalene and 1 g of Resin I were added and stirred at 80 ° C. (Resin I contains 21% by weight of solvent on a dry basis). Living polystyrene polymer was added thereto under nitrogen and reacted at 80 ° C. for 20 hours. After the reaction, the solution was added to a large amount of methanol to precipitate a polymer, which was then collected and dried. Then, the polymer was subjected to Soxhlet extraction for 8 hours with methyl ethyl ketone. As a result, 1.24
g of polymer was obtained. As a result of IR analysis of this polymer, absorption of propylene and styrene was recognized, and from this analysis, the styrene content was 20.2% by weight. Furthermore, when this polymer was subjected to Soxhlet extraction with xylene for 8 hours using a wire mesh of 80 mesh, there was no gel (insoluble matter).

Comparative Example-1 100 ml of fully dehydrated and purified decahydronaphthalene and resin I 1 were substituted with nitrogen in a sufficiently dried flask.
g was added, and Resin I was completely dissolved under stirring at 110 ° C.
Then, 3 g of styrene was added at 110 ° C. with stirring, and then 50 mg of sec-butyllithium was added. After reacting for 20 hours, the solution was added to a large amount of methanol to precipitate a polymer, which was then collected and dried. Then, this polymer was subjected to Soxhlet extraction for 8 hours with methyl ethyl ketone, and as a result, 1.22 g of polymer was obtained. As a result of IR analysis of this polymer, absorption of propylene and styrene was recognized, and from this analysis, the styrene content was 18.0% by weight.
Met. Further, when the methylethyl-soluble component was recovered and IR analysis was carried out, absorption of styrene was observed, and as a result of GPC analysis, the number average molecular weight was 16100 and the weight average molecular weight was 29.
It was 500. Methyl ethyl ketone insoluble matter 8 more
Soxhlet extraction was performed for 8 hours with xylene using a 0 mesh wire net, and the gel (insoluble content) was 22.3% by weight.

Application Example-1 The graft copolymer obtained in Example-1 was press-molded at 230 ° C. to prepare a sheet having a thickness of 2 mm. Various test pieces were cut out from this sheet and evaluated for physical properties. <Measurement and Evaluation Method> (1) Bending Elastic Modulus A test piece having a width of 25 mm and a length of 80 mm was cut and subjected to JI.
It measured using the Instron tester based on SK7203. (2) Izod impact strength Impact resistance strength is 2 mm thick according to JIS K7110.
The Izod impact strength with a notch at 23 ° C. was measured by stacking three test pieces. The results are shown in Table 1.

Application Example-2 Polypropylene resin (trade name MA manufactured by Mitsubishi Petrochemical Co., Ltd.)
8) 50 parts by weight and poly (2,6-dimethyl-1,4-
Phenine ether) (manufactured by Nippon Polyether Co., intrinsic viscosity 0.4 dl / measured in chloroform at 30 ° C.)
g) 50 parts by weight and 15 parts by weight of the graft copolymer obtained in Example-1 were melt-kneaded in a plastomill manufactured by Toyo Seiki Co., Ltd. having an internal volume of 60 ml at 250 ° C. for 6 minutes at a rotation speed of 60 rpm. The obtained resin mixture was press-molded at 280 ° C. to prepare a sheet having a thickness of 2 mm, and then evaluated under the same conditions as in Application Example-1. The results are shown in Table 1.

Comparative Application Example Polypropylene resin “MA8” 65 parts by weight and poly (2,2)
A sheet having the physical properties shown in Table 1 was prepared in the same manner as in Application Example 2 except that a mixture with 50 parts by weight of 6-dimethyl-1,4-phenine ether) was used.

[0034]

[Table 1]

Claims (1)

Claims: (a) Ethylene or C3-12
And at least one of the following formula (1)
And at least one dialkenylbenzene represented by
0 mol% of the copolymer and (R ¹ = hydrogen or methyl group, R ² = hydrocarbon residue having 1 to 6 carbon atoms, n = 0 or 1) (b) Polymerizing at least one anionic polymerizable monomer in the presence of a metal-containing anionic polymerization catalyst A method for producing a graft copolymer, which comprises reacting the resulting terminal metal-bonded polymer in a solvent in a swollen state of the copolymer (a).