JPH11166025A - Alkenyl group-containing block copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the introduction ratio of an alkenyl group and to obtain the subject copolymer by a ready method, by reacting a specific two kinds of monomers with a prescribed monomer at an arbitrary stage for polymerizing the specific monomers in the presence of a specified compound. SOLUTION: (A) A monomer comprising isobutylene as a main component and (B) a monomer not comprising isobutylene as a main component are polymerized in the presence of (C) a compound of formula 1 (R<1> is H, a 1-6C monofunctional hydrocarbon; R<2> is a polyaromatic hydrocarbon or a polyfunctional aliphatic hydrocarbon; X is a halogen or a substituent group such as a 1-6C alkoxy or the like; (n) is 1-6) [e.g. 1,4-bis(1-chloro-1-methylethyl) benzene] and is reacted, at an arbitrary stage of the polymerization, with (D) a cationic polymerizable monomer containing plural alkenyl groups to give the objective copolymer. Preferably a compound of formula II or formula III [R<3> and R<4> are each H or a (non)substituted organic group; X is a single bond, a disubstituted Si or a (non)substituted bifunctional organic group] (e.g. 1,9- decadiene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a novel alkenyl group-containing isobutylene-based block copolymer. Further, the present invention relates to an alkenyl group-containing isobutylene-based block copolymer obtained by this production method.

[0002]

2. Description of the Related Art Isobutylene block copolymers have the same strength and elasticity as crosslinked rubbers while being non-crosslinked,
Since it has excellent impact resistance and flexibility, and exhibits the same moldability as a thermoplastic resin, use of an elastomer material or a thermoplastic resin as a material for improving impact resistance has been studied.

[0003] For example, Japanese Patent Publication No. 7-100763 discloses a composition of an isobutylene-based block copolymer and a thermoplastic resin. However, in such a composition, depending on the thermoplastic resin, the compatibility between the resin and the isobutylene-based block copolymer is not sufficient,
There were problems such as not exhibiting physical properties such as sufficient impact resistance and mechanical strength.

[0004] As a method of avoiding such a problem,
It is known to introduce a functional group into an isobutylene-based block copolymer. For example, JP-A-6-271751 discloses a composition of an isobutylene-based block copolymer having a hydroxyl group at a terminal and a polyester-based polymer. Further, in this publication, as an intermediate of an isobutylene-based block copolymer having a hydroxyl group at a terminal, 1,
Alkenyl-terminated isobutylene obtained by dehydrochlorination of a block copolymer having a chlorine atom at the terminal synthesized by a system using 4-di (2-methoxy-2-propyl) benzene and titanium tetrachloride as initiators A block copolymer is disclosed.

However, the above-mentioned method requires strict reaction conditions and it is difficult to improve the reaction rate.
There was a problem that the introduction ratio of the alkenyl group was not sufficient. Furthermore, this method has a problem that the introduction of the alkenyl group is limited to the terminal of the block copolymer. As described above, it has been desired to develop an isobutylene-based block copolymer that is easy to synthesize, has a high alkenyl group introduction rate, and has a high reactivity of the introduced alkenyl group.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an alkenyl group-containing isobutylene-based block copolymer obtained under specific polymerization conditions and a method for producing the same can solve the above problems. The present invention has been completed. This achieves the above object. The present invention provides an isobutylene-based block copolymer in which a monomer containing isobutylene as a main component and a monomer not containing isobutylene as a main component are polymerized in the presence of a compound represented by the following general formula (I). The present invention relates to a method for producing an alkenyl group-containing block copolymer, which comprises reacting a cationically polymerizable monomer having a plurality of alkenyl groups at any stage of polymerization.

[0007]

Embedded image

(Wherein R 1 is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms;
R2 is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group; X is a substituent selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group;
n represents a natural number of 1 to 6. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The method for producing an alkenyl group-containing isobutylene-based block copolymer of the present invention comprises a monomer having isobutylene as a main component and not having isobutylene as a main component in the presence of a compound represented by the following general formula (I). In a method for producing an isobutylene-based block copolymer in which a monomer is polymerized, a cationic polymerizable monomer having a plurality of alkenyl groups is reacted at an arbitrary stage of polymerization.

[0010]

Embedded image

(Wherein R 1 is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms;
R2 is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group; X is a substituent selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group;
n represents a natural number of 1 to 6. The cationic polymerizable monomer having a plurality of alkenyl groups used in the present invention reacts with the active site of cationic polymerization and is used to introduce an alkenyl group into the polymer. Further, the alkenyl groups in the cationically polymerizable monomer having a plurality of alkenyl groups of the present invention may or may not be conjugated. Cationic polymerizable monomer having a plurality of alkenyl groups used in the present invention,
A compound represented by the following general formula (II) or general formula (III) is preferable.

[0012]

Embedded image

(Where R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted organic group; X is a single bond, an oxygen atom, a disubstituted silicon atom, a substituted or unsubstituted It represents a divalent organic group.)

[0014]

Embedded image

(Wherein R 3 and R 4 have the same meanings as above; X has the same meaning as above.) In the compound represented by the formula (II) or (III), R 3 and R 4 are hydrogen. Atoms, hydrocarbon groups, alkoxy groups, phenoxy groups, carboxyl groups, ester groups, etc.
Specific examples of the hydrocarbon group include a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms, and preferably 6 to 20 carbon atoms. Examples include 6 to 14, more preferably 6 to 10 alkylaryl groups, and cycloalkyl groups. At least a portion of the hydrogen atoms of the hydrocarbon group may be replaced with any substituent, as long as the advantages of the present invention are not compromised.

R 3 and R 4 in the compound represented by the formula (II) or (III) represent a hydrogen atom,
A linear or branched alkyl group having 6 carbon atoms is preferable, and among them, a hydrogen atom and a methyl group are more preferable. Further, X of the formula (II) or (III)
Is preferably a single bond, an oxygen atom, a disubstituted silicon atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylaryl group having 6 to 10 carbon atoms. Among them, a single bond, an oxygen atom, a linear alkyl group having 1 to 6 carbon atoms, and an alkylaryl group having 6 to 10 carbon atoms are preferable.

The alkenyl group-containing cationic polymerizable monomer having such a substituent is easily available, and has excellent reactivity, so that an alkenyl group-containing isobutylene-based block copolymer can be easily produced. . Specific examples of the alkenyl group-containing cationic polymerizable monomer,
Butadiene, isoprene, 2,3-dimethyl-1,3-
Butadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene,
1,9-decadiene, 2-methyl-1,5-hexadiene, 2-methyl-1,7-octadiene, 2-methyl-
1,5-heptadiene, 2,5-dimethyl-1,5-hexadiene, 6-methyl-1,5-hexadiene, cyclopentadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1 , 3
-Cyclooctadiene, 1,5-cyclooctadiene,
Examples thereof include divinylbenzene, ethylidene norbornene, diallyl ether, divinyldimethylsilane, divinyldimethoxysilane, divinyldichlorosilane, and trivinylmethylsilane. These alkenyl group-containing cationically polymerizable monomers are used alone or in combination.

Of these, butadiene, isoprene, 1,5-hexadiene, 1,7-octadiene,
1,9-decadiene, divinylbenzene, diallyl ether and 2-methyl-1,5-hexadiene are preferred.
Since these compounds are easily available and excellent in reactivity, an alkenyl group-containing isobutylene-based block copolymer can be easily produced.

The amount of the cationically polymerizable monomer having a plurality of alkenyl groups is not particularly limited, but is usually 0.1 to 100 moles per mole of the compound represented by the formula (I). The amount used is preferably in the range of 2 to 30 moles. The cationically polymerizable monomer having a plurality of alkenyl groups can be reacted at any stage of the polymerization. When a cationic polymerizable monomer having a plurality of alkenyl groups is reacted during the polymerization of a monomer containing isobutylene as a main component and a monomer not containing isobutylene as a main component, the main component of the copolymer is When an alkenyl group is introduced into the chain and the reaction is carried out at the stage when the polymerization reaction is substantially completed, the alkenyl group is introduced at the terminal of the copolymer.

The compound represented by the general formula (I) used in the present invention is considered to be a starting point of cationic polymerization.
Specific examples of the compound represented by the general formula (I) used in the present invention include 1-chloro-1-methylethylbenzene [C6H5C (CH3) 2Cl], 1,4-bis (1-chloro-1-methyl) Ethyl) benzene [1,4-Cl (CH
3) 2CC6H4C (CH3) 2Cl], 1,3-bis (1-
Chloro-1-methylethyl) benzene [1,3-Cl
(CH3) 2CC6H4C (CH3) 2Cl], 1,3,5-
Tris (1-chloro-1-methylethyl) benzene [1,3,5-((ClC (CH3) 2) 3C6H3],
1,3-bis (1-chloro-1-methylethyl) -5
(Tert-butyl) benzene [1,3-((C (CH
3) 2Cl) 2-5- (C (CH3) 3) C6H3]. Bis (1-chloro-1-methylethyl)
Benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene, or dicumyl chloride.

Among them, in terms of reactivity and availability,
Bis (1-chloro-1-methylethyl) benzene is particularly preferred. The monomer component not containing isobutylene as the main component of the present invention means a monomer component having an isobutylene content of 30% by weight or less. The content of isobutylene in the monomer component containing no isobutylene as a main component is preferably 10% by weight or less, more preferably 3% by weight or less.

The monomer containing no isobutylene as the main component of the present invention is not particularly limited as long as it is a monomer which can be cationically polymerized. Examples of the monomer include aliphatic olefins, aromatic vinyls, dienes, vinyl ethers and silanes. And monomers such as vinyl carbazole, β-pinene and acenaphthylene. These are used alone or in combination of two or more.

Examples of the aliphatic olefin monomer include propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, vinyl Cyclohexene, octene, norbornene and the like can be mentioned. As the aromatic vinyl monomer, styrene, o-, m- or p-
Methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p -Methylstyrene, β-methyl-o-methylstyrene, β-methyl-m
-Methylstyrene, β-methyl-p-methylstyrene,
2,4,6-trimethylstyrene, α-methyl-2,6
-Dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-
Methyl-2,4-dimethylstyrene, o-, m- or p
-Chlorostyrene, 2,6-dichlorostyrene, 2,4
-Dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p
-Chlorostyrene, β-chloro-o-chlorostyrene,
β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-
Chloro-2,6-dichlorostyrene, α-chloro-2,
4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o
-, M- or pt-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-bromomethylstyrene, with a silyl group Substituted styrene derivatives, vinylnaphthalene derivatives, indene derivatives and the like are mentioned.

The vinyl ether monomers include methyl vinyl ether, ethyl vinyl ether, (n-, iso) propyl vinyl ether, (n-, sec-, te
rt-, iso) butyl vinyl ether, methylpropenyl ether, ethylpropenyl ether and the like. As the silane compound, vinyl trichlorosilane,
Examples include vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.

Of these, preferred are aromatic vinyl monomers, and particularly preferred are styrene and α-
One or more monomers selected from the group consisting of methylstyrene, p-methylstyrene, vinylnaphthalene derivatives, and indene derivatives. The monomer containing isobutylene as the main component of the present invention means a monomer component containing 60% by weight or more, preferably 80% by weight or more of isobutylene.

The monomer containing isobutylene as the main component of the present invention may or may not contain a monomer other than isobutylene. The monomer other than isobutylene is not particularly limited as long as it is a monomer capable of cationic polymerization, and examples thereof include the above-mentioned monomers. In the present invention, if necessary, a Lewis acid catalyst may be allowed to coexist. Such a Lewis acid may be any as long as it can be used for cationic polymerization, and TiCl4, TiBr4, BCl3, BF3,
BF3.OEt2, SnCl4, SbCl5, SbF5, WCl6,
TaCl5, VCl5, FeCl3, ZnBr2, AlCl3, A
metal halides such as lBr3; Et2AlCl, EtA
Organometallic halides such as 1Cl2 are preferred. Above all, TiC is preferred because of its ability as a catalyst and industrial availability.
I4, BCl3 and SnCl4 are preferred. In the present invention, the Lewis acid is usually used in a range of 0.1 to 100 times by mol with respect to the compound represented by the above general formula (I), but a preferable use amount is 0.3 to 50 times by mol. Range.

Further, in the present invention, an electron donor component can be used, if necessary. In the present invention, conventionally known electron donor components can be widely used as long as the number of donors is 15 to 60. Preferred electron donor components include, for example, pyridines, amines, amides, sulfoxides, and metal compounds having an oxygen atom bonded to a metal atom. In the present invention, as the electron donating system component in which the number of donors defined as a parameter indicating the strength of various compounds as an electron donor (electron donor) is 15 to 60, specifically, specifically, 2,6 -Di-t-butylpyridine, 2-t-butylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2-methylpyridine, pyridine, diethylamine, trimethylamine, triethylamine, tributylamine, N, N −
Dimethylaniline, N, N-dimethylformamide,
N, N-dimethylacetamide, N, N-diethylacetamide, dimethylsulfoxide, diethylether,
Titanium alkoxides such as methyl acetate, ethyl acetate, trimethyl phosphate, hexamethyl phosphate triamide, titanium (III) methoxide, titanium (IV) methoxide, titanium (IV) isopropoxide, and titanium (IV) butoxide;
Aluminum alkoxides such as aluminum triethoxide and aluminum tributoxide can be used,
Preferred are 2,6-di-t-butylpyridine, 2,6-dimethylpyridine, 2-methylpyridine,
Pyridine, diethylamine, trimethylamine, triethylamine, N, N-dimethylformamide, N, N-
Examples include dimethylacetamide, dimethylsulfoxide, titanium (IV) isopropoxide, and titanium (IV) butoxide. [For various numbers of donors, see Donors and Acceptors, by Goodman (Otaki, Okada translation) Gakkai Shuppan Center ( 1983))]. Among these, 2-methylpyridine, which has a remarkable effect of addition, and titanium (IV) isopropoxide, which makes the reaction system uniform, are particularly preferable. In the present invention, the electron donor component is usually added to the compound represented by the general formula (I) in an amount of 0.1 to 0.1.
It is used in an amount of from 01 to 10 moles, preferably from 0.2 to 4 moles.

The present invention can be carried out in a solvent, if necessary. In the present invention, any solvent which does not substantially inhibit cationic polymerization can be used. Specifically, methyl chloride, dichloromethane, n-propyl chloride, n-butyl chloride,
Halogenated hydrocarbons such as chlorobenzene; alkylbenzenes such as benzene, toluene, xylene, ethylbenzene, propylbenzene and butylbenzene; ethane;
Linear aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, nonane and decane;
2-methylpropane, 2-methylbutane, 2,3,3-
Branched aliphatic hydrocarbons such as trimethylpentane and 2,2,5-trimethylhexane; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; paraffin oil obtained by hydrogenating and purifying a petroleum fraction. Can be mentioned.

These solvents are used alone or in combination of two or more in consideration of the balance between the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer. The amount of the solvent to be used is generally from 1 to 1 in consideration of the viscosity of the obtained polymer solution and the ease of heat removal.
It is determined to be 50 wt%, preferably 5 to 35 wt%.

The amount of each component used in the present invention can be appropriately designed according to the properties required for the target polymer. The molecular weight of the resulting polymer can be determined by the molar equivalent relationship between the monomer having isobutylene as a main component, the monomer not having isobutylene as a main component, and the compound represented by the general formula (1). The number average molecular weight of the usually obtained block copolymer is set to be about 20,000 to 500,000.

In carrying out the polymerization according to the method of the present invention,
It is preferable to mix the components under cooling, for example, at a temperature of -100 ° C or more and less than 0 ° C. In order to balance the energy cost with the stability of the polymerization, a particularly preferred temperature range is -80C to -30C. The isobutylene-based block produced by the production method of the present invention may be any one having a polymer block containing isobutylene as a main component and a polymer block containing a monomer not containing isobutylene as a main component. The structure is not particularly limited, for example, any of a block copolymer having a linear, branched, or star-like structure, a diblock copolymer, a triblock copolymer, a multiblock copolymer, or the like. Can be selected. As the block copolymer, for example, when the monomer not containing isobutylene as a main component is mainly composed of an aromatic vinyl monomer, a polymer mainly composed of an aromatic vinyl monomer is used. Block-Polymer block mainly composed of isobutylene unit-Triblock copolymer composed of polymer block mainly composed of aromatic vinyl monomer, polymer block mainly composed of aromatic vinyl monomer-isobutylene A diblock copolymer composed of a polymer block mainly composed of units, or a mixture thereof is preferable.

When the block copolymer is produced, a Lewis acid, a compound represented by the general formula (I), an electron donor component,
The method and order of addition of the monomer components and the like are not particularly limited, but preferred methods include, for example,
(A) a step of polymerizing a monomer containing isobutylene as a main component in the presence of an initiator system comprising a compound represented by the general formula (I), a Lewis acid, and an electron donor component; A method comprising the step of adding a monomer not containing isobutylene as a main component to the system and polymerizing the same. In this method, after the polymerization of the monomer containing isobutylene as a main component is substantially completed in step (A), a monomer not containing isobutylene as a main component is generally added. When a monomer having a lower cationic polymerization activity than isobutylene is used as the cationically polymerizable monomer, the step (A) is carried out before the polymerization of the monomer containing isobutylene as a main component is substantially completed. Even if a monomer containing no isobutylene as a main component is added, a block copolymer can be synthesized. When a monomer not having isobutylene as a main component and having a cationic polymerization activity substantially equal to that of isobutylene and a copolymerizable monomer is used, in the step (A), an isobutylene unit is mainly used. If another kind of monomer is added before the polymerization of the monomer is substantially completed, a block copolymer having a random block in a part of the molecular chain can be produced.

The alkenyl group-containing cationic polymerizable monomer can be added at any stage of the above polymerization.
That is, in the above step (A), it may be added before the monomer containing isobutylene as a main component, or may be added simultaneously with the monomer containing isobutylene as a main component, It may be added after the addition or polymerization of the monomer containing isobutylene as a main component is completed. The above (B)
In the step (b), it may be added before adding a monomer not containing isobutylene as a main component, may be added simultaneously with a monomer containing no isobutylene as a main component, or may be added alone containing no isobutylene as a main component. It may be added after the addition of the monomer or the polymerization is completed.

The alkenyl group-containing isobutylene-based copolymer obtained by the production method of the present invention can be used for various applications similar to the conventional isobutylene-based block copolymer. For example, it can be used as a modifier of an elastomer material, a resin, asphalt or the like, or a component of a resin compound. The alkenyl group-containing isobutylene-based block copolymer of the present invention can arbitrarily control the melt viscosity by adding various crosslinking agents. By doing so, when the isobutylene-based block copolymer is blended with another resin or the like, the melt viscosities of both can be adjusted to improve the compatibility.

Further, the alkenyl group-containing isobutylene copolymer of the present invention can be converted into an arbitrary functional group by reacting with an appropriate reagent. Functional groups that can be converted include epoxy groups, carboxyl groups, hydroxyl groups,
Examples include an amino group and a cyano group. By appropriately selecting such a functional group, compatibility, reactivity, polarity, and the like with the other resin of the isobutylene-based block copolymer can be controlled.

[0036]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and can be appropriately modified and implemented within the scope of the invention. . Example 1 After replacing the inside of a polymerization vessel of a 500 mL separable flask with nitrogen, 120 mL of n-hexane (dried with molecular sieves) and 80 mL of methylene chloride (dried with molecular sieves) using a syringe,
0.0876 g (0.38 p-dikyl chloride)
mmol). After cooling the polymerization vessel in a dry ice / methanol bath at -70 ° C, 0.036 g (0.39 mmol) of 2-methylpyridine was added.
Next, 33.9 mL of isobutylene monomer (419.9 m
mol.) was connected to a pressure-resistant glass liquefaction sampling tube equipped with a three-way cock, and an isobutylene monomer was fed into the polymerization vessel under nitrogen pressure. Further, 1.50 mL (13.7 mmol) of titanium tetrachloride was added to initiate polymerization. After stirring at the same temperature for 1 hour from the start of the polymerization, about 1 mL of the polymerization solution was sampled from the polymerization solution for sampling. Then, in advance -70
12.15 g of styrene monomer (1
16.7 mmol), a mixed solution of 12 mL of n-hexane and 8 mL of methylene chloride was added into the polymerization vessel. Ten minutes after the addition of the mixed solution, 0.162 g (1.17 mmol) of 1,9-decadiene was added. After stirring at the same temperature for 60 minutes, about 10 mL of methanol was added to terminate the reaction.

After the solvent and the like were distilled off from the reaction solution, it was dissolved in toluene and washed twice with water. Further, a toluene solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain a target block copolymer. GPC analysis of the obtained polymer (measuring device: 510 type GPC system manufactured by Waters, mobile phase: chloroform, polymer concentration: 2 mg / m)
1, column temperature: 35 ° C., standard sample: polystyrene), the number average molecular weight Mn of the isobutylene polymer before the addition of styrene was 69000 and the molecular weight distribution Mw / Mn was 1.1.
The number average molecular weight Mn of the block copolymer after styrene polymerization was 100,000, and the molecular weight distribution Mw / Mn was 1.24.

1H-NMR spectrum of the obtained polymer (measuring device: Gemini-30 manufactured by Varian)
0, measurement solvent: chloroform), the integration ratio of isobutylene groups and the integration ratio of allyl groups suggested that an average of 2.1 allyl groups were introduced per molecule of the polymer. Example 2 Instead of 1,9-decadiene, 0.5 mL of isoprene was used.
Example 2 was carried out in the same manner as in Example 1 except that (5.00 mmol, dissolved in a mixed solvent of 6 mL of n-hexane and 4 mL of methylene chloride was added).

GPC analysis of the obtained polymer showed that the isobutylene polymer before addition of styrene had a number average molecular weight Mn of 7
1,000, molecular weight distribution Mw / Mn is 1.15,
Number average molecular weight Mn of block copolymer after styrene polymerization
Was 103,000, and the molecular weight distribution Mw / Mn was 1.25. 1H-NMR spectrum of the obtained polymer,
The integral ratio of the isobutylene group and the integral ratio of the allyl group suggested that an average of 3.5 alkenyl groups were introduced per molecule of the polymer.

[0040]

According to the present invention, the introduction rate of alkenyl groups is high, and the reactivity of introduced alkenyl groups is high.
An isobutylene-based block copolymer can be synthesized by a simple operation.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 23:00)

Claims (8)

[Claims] An isobutylene-based block copolymer in which a monomer containing isobutylene as a main component and a monomer not containing isobutylene as a main component are polymerized in the presence of a compound represented by the following general formula (I). Wherein the cation-polymerizable monomer having a plurality of alkenyl groups is reacted at any stage of the polymerization. Embedded image (Wherein R 1 is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R 2 is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group; X
Is a substituent selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group; n is 1 to 6
Indicates the natural number of. ) 2. A step in which a cationically polymerizable monomer having a plurality of alkenyl groups is converted into a monomer containing isobutylene as a main component and a monomer not containing isobutylene as a main component, when polymerization is substantially completed. The method according to claim 1, wherein the reaction is carried out. 3. The compound represented by the general formula (I) is:
The production method according to claim 1, wherein the production method is 4-bis (1-chloro-1-methylethyl) benzene. 4. The production method according to claim 1, wherein the cationically polymerizable monomer having a plurality of alkenyl groups is a compound represented by the following general formula (II) or (III). Embedded image (Where R3 and R4 are each independently a hydrogen atom or a substituted or unsubstituted organic group;
It represents a single bond, an oxygen atom, a disubstituted silicon atom, or a substituted or unsubstituted divalent organic group. ) (Where R3 and R4 are as defined above; X is
The meaning is as defined above. ) 5. The cationic polymerizable monomer having a plurality of alkenyl groups is divinylbenzene, butadiene, isoprene, 1,5-hexadiene, 1,7-octadiene,
1,9-decadiene, diallyl ether, 2-methyl-
The method according to claim 4, wherein the method is at least one selected from the group consisting of 1,5-hexadiene. 6. The production method according to claim 1, wherein the monomer containing no isobutylene as a main component is a monomer mainly containing an aromatic vinyl monomer. 7. The aromatic vinyl monomer is styrene, α
The method according to claim 6, wherein the method is at least one selected from the group consisting of -methylstyrene, p-methylstyrene, a vinylnaphthalene derivative, and an indene derivative. 8. An alkenyl group-containing isobutylene-based block copolymer obtained by the production method according to claim 1.