JPWO2019070037A1 - Allyl group-terminated styrene-isobutylene block copolymers, their compositions, and methods for producing them. - Google Patents

Abstract

An object of the present invention is to provide an allyl group-terminated styrene-isobutylene block copolymer or the like, which is easy to handle and can provide a composition capable of exhibiting excellent rubber physical properties. In order to achieve the above object, an allyl group-terminated styrene-isobutylene block copolymer having an allyl group at the end of the molecular chain and having more than 2.1 allyl groups and 3.0 or less allyl groups in one molecule is provided.

Description

The present invention relates to styrene-isobutylene block copolymers having an allyl group at the end, compositions thereof, and methods for producing them.

Conventionally, various thermoplastic elastomers have been developed that can utilize general-purpose melt molding techniques such as hot press molding, injection molding, and extrusion molding in the same manner as ordinary thermoplastic resins.

Examples of the thermoplastic elastomer include styrene-butadiene-styrene block copolymer (SBS) and styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylenebutylene-styrene block obtained by hydrogenating them. Styrene-based thermoplastic elastomers such as copolymers (SEBS), styrene-ethylenepropylene-styrene block copolymers (SEPS), and styrene-isobutylene-styrene block copolymers (SIBS) are known. Although all of these thermoplastic elastomers have excellent rubber physical properties, there are cases where the rubber physical properties such as flexibility and compression set are insufficient.

As a technique for solving this problem, Patent Documents 1 to 6 describe a thermoplastic elastomer composition, an alkenyl group-containing styrene-isobutylene block copolymer containing an alkenyl group at the end, or an allyl group-terminated styrene-isobutylene block. Polymers are disclosed.

JP-A-11-222510 Japanese Unexamined Patent Publication No. 2003-26895 WO2003-002654 Japanese Unexamined Patent Publication No. 2004-204108 Japanese Unexamined Patent Publication No. 2004-196970 Japanese Unexamined Patent Publication No. 11-166025

However, in the above-mentioned conventional technique, there is room for further improvement from the viewpoint of ease of handling.

One embodiment of the present invention has been made in view of the above problems, and an object thereof is to provide a composition which is (a) easy to handle and (b) can exhibit excellent rubber properties. It is an object of the present invention to provide a novel allyl group-terminated styrene-isobutylene block copolymer, an allyl group-terminated styrene-isobutylene block copolymer composition containing the copolymer, and a method for producing them.

As a result of diligent studies to solve the above problems, the present inventor has found that the above problems can be solved by a specific allyl group-terminated styrene-isobutylene block copolymer, and has completed the present invention.

According to one embodiment of the present invention, an allyl group-terminated styrene-isobutylene block copolymer capable of providing (a) easy-to-handle and (b) a composition capable of exhibiting excellent rubber properties, the copolymer thereof. Allyl group-terminated styrene-isobutylene block copolymer compositions containing coalescing and methods for producing them are provided.

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments or examples obtained by appropriately combining the technical means disclosed in the different embodiments or examples. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification. Further, unless otherwise specified in the present specification, "A to B" representing a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".

As a result of diligent studies by the present inventor, it has been found that the techniques described in the above-mentioned Prior Art Documents 1 to 6 have room for further improvement as shown below.

In the production of a thermoplastic elastomer composition containing a thermoplastic resin, a thermoplastic resin such as polypropylene, polyethylene, and a styrene-based thermoplastic elastomer is usually used as pellets. Therefore, when an allyl group-terminated styrene-isobutylene block copolymer is used as a raw material for the thermoplastic elastomer composition, the present inventor may also use pellets for the allyl group-terminated styrene-isobutylene block copolymer from the viewpoint of handling. I found it preferable. However, the allyl group-terminated styrene-isobutylene block copolymer having a relatively low molecular weight as described in Patent Documents 2 to 5 described above cannot be pelletized and needs to be handled in a veil shape. Met. The present inventor requires special equipment and a method for charging an allyl group-terminated styrene-isobutylene block copolymer in the production of the thermoplastic elastomer composition in the techniques described in the above-mentioned prior art documents 2 to 5. I found it to be.

In the techniques described in Patent Documents 1 to 5, since a bifunctional polymerization initiator was used in the production of the thermoplastic elastomer composition, the allyl group introduced into the terminal of the styrene-isobutylene block copolymer is one molecule. It was as low as 2 or less per unit. As a result of further studies, the present inventor has difficulty in obtaining a composition having desired rubber properties when the number of allyl groups per copolymer molecule is low, as in the techniques described in Patent Documents 1 to 5. I also found out that it is.

Patent Document 6 discloses an alkenyl group-terminated styrene-isobutylene block copolymer produced by using an alkenyl compound which is cheaper than an allylsilane compound. However, in Patent Document 6, the rubber physical properties of the thermoplastic elastomer composition containing the copolymer have not been studied. In particular, as a result of examination, the present inventor has found that when an alkenyl group-terminated styrene-isobutylene block copolymer is used, the reactivity of the alkenyl group is not sufficient, and therefore, the rubber properties of the dynamic cross-linking composition containing the copolymer. I found that it may be insufficient.

Patent Document 6 also discloses a copolymer obtained by cationically polymerizing isoprene. In such a copolymer, the monomer unit derived from isoprene is basically composed of 1,4-bonds and has a tri-substituted carbon-carbon double bond structure. Such polysubstituted carbon-carbon double bonds are generally not sufficiently reactive. That is, it can be said that such a polysubstituted carbon-carbon double bond has substantially no reactivity. The present inventor states that (a) such a polysubstituted carbon-carbon double bond is also significantly less reactive with the hydrosilylation reaction carried out in one embodiment of the present invention, and (b) such a polysubstituted carbon-carbon double bond. It has been independently found that a composition using a copolymer having a carbon-carbon double bond may not obtain desired rubber physical properties.

Generally, in order to obtain rubber physical properties such as excellent compression set, heat resistance, creep resistance, and solvent resistance, the molecular weight of the copolymer (crosslinkable polymer) used should be reduced, and other crosslinkable compounding agents should be used. A design that increases the crosslink density as much as possible by adding it is preferable. However, in this case, the flexibility and fluidity of the copolymer and the composition containing the copolymer are often impaired. A copolymer having an excellent balance of these physical properties and a composition containing the copolymer have been required.

It is necessary to introduce an allyl group at the end of the copolymer for excellent rubber properties. However, in the prior art, an allyl group could not be introduced at the end of a copolymer having a large molecular weight, and only a copolymer having a low molecular weight could be obtained. On the other hand, as described above, the low molecular weight copolymer cannot be pelletized. That is, it is technically difficult to obtain a copolymer that can be molded into pellets and can provide a composition having excellent rubber physical properties. Here, as a result of diligent studies, the inventor independently found the following (a) and (b) and completed the present invention: (a) By increasing the molecular weight of the copolymer, the copolymer was obtained. By being able to be molded into pellets and (b) performing an allylation reaction before the consumption rate of the monomer (for example, styrene) constituting the end of the copolymer reaches a certain value, An allyl group can be efficiently introduced into the terminal of a copolymer having a large molecular weight.

[1. Allyl group-terminated styrene-isobutylene block copolymer]
The allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention has an allyl group at the end of the molecular chain, and is a polymer block (a) mainly composed of isobutylene and a polymer block mainly composed of styrene. (B), the number average molecular weight (Mn) in terms of standard polystyrene measured by gel permeation chromatography is 30,000 to 130,000 (g / mol), and the molecular weight distribution (Mw / Mn) is , 1.10 to 2.00, the content of the polymer block (a) mainly composed of isobutylene is 50 to 90% by weight, and the molecular chain has a group represented by the following general formula (1). And

（前記一般式（１）中、Ｒ^１およびＲ^２は、水素、または炭素数１〜６の１価の炭化水素基を表す。Ｒ^１およびＲ^２は、同一であっても異なっていてもよい。また、複数存在するＲ^１およびＲ^２は、それぞれが同一の基であっても異なる基であってもよい。）
一分子中にアリル基を２．１個超３．０個以下有する。

(In the general formula (1), R ¹ and R ² represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different. Also, a plurality of R ¹ and R ² may be the same group or different groups, respectively.)
It has more than 2.1 allyl groups and 3.0 or less allyl groups in one molecule.

Since the allyl group-terminated styrene-isobutylene block copolymer according to the embodiment of the present invention has the above-mentioned constitution, it provides (a) easy-to-handle and (b) a composition capable of exhibiting excellent rubber physical properties. It has the advantage of being able to. Here, "easy to handle" means that it can be molded into pellets. Further, in the present specification, the physical properties of rubber are intended to be flexibility, compression set, fluidity, heat resistance, creep resistance, and solvent resistance.

The allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention is hereinafter simply referred to as a copolymer.

The copolymer may have a linear structure or a branched structure as the structure of the polymer chain.

As long as each polymer chain in the copolymer is composed of a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of styrene, the structure thereof is not particularly limited. For example, it can have a linear, branched, star-like structure or the like.

For each polymer chain, any of a diblock copolymer, a triblock copolymer, a multi-block copolymer and the like can be selected.

As a preferable structure of the copolymer, since it is excellent in various physical properties and molding processability, (i) it has a branched structure, and (b) a polymer block (b) mainly composed of styrene is provided at the end of each polymer. A structure having a polymer block main body (a) mainly composed of isobutylene can be mentioned between the branching point and the polymer block (b) mainly composed of styrene.

<1-1. Polymer block mainly composed of isobutylene (a)>
The polymer block (a) mainly composed of isobutylene is also hereinafter referred to as a polymer block (a). The polymer block (a) may be a polymer block composed substantially only of isobutylene, or may contain a monomer unit other than isobutylene as long as the effect of the present invention is not impaired. .. In the present specification, the monomer unit other than isobutylene means a monomer unit obtained by polymerizing a monomer other than isobutylene.

The monomer other than isobutylene is not particularly limited as long as it is a monomer that can be cationically polymerized with isobutylene. For example, aliphatic olefins, aromatic vinyl compounds, dienes, vinyl ethers, silanes, and vinyl carbazoles are used. , Β-Pinene, and monomers such as asenaphthylene. Only one type of these may be used, or two or more types may be used in combination.

The polymer block (a) preferably contains 60% by weight or more of a monomer unit derived from isobutylene, and more preferably 80% by weight or more, because the obtained copolymer has excellent mechanical properties. According to the above configuration, there is an advantage that the gas barrier property of the copolymer does not decrease. In the present specification, the monomer unit derived from isobutylene means a monomer unit obtained by polymerizing an isobutylene monomer.

<1-2. Polymer block mainly composed of styrene (b)>
The polymer block (b) mainly composed of styrene is also hereinafter referred to as the polymer block (b). The polymer block (b) may be a polymer block substantially composed of styrene only, or may contain a monomer unit other than styrene as long as the effect of the present invention is not impaired. .. In the present specification, the monomer unit other than styrene means a unit unit obtained by polymerizing a monomer other than styrene.

Examples of the monomer other than styrene include methylstyrene (which may be o-form, m-form or p-form), 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, t-butylstyrene (o) -Form, m-form or p-form), methoxystyrene (either o-form, m-form or p-form), chloromethylstyrene (o-form, m-form or p-form) (Any form is acceptable), bromomethylstyrene (which may be an o-form, an m-form or a p-form), a styrene derivative substituted with a silyl group, inden, vinylnaphthalene and the like.

Among the monomers other than styrene, methylstyrene (either o-form, m-form or p-form), α-methylstyrene, etc. are excellent in industrial availability, price, and reactivity. Inden and / or a mixture thereof is preferred.

The polymer block (b) mainly composed of styrene preferably contains 60% by weight or more of styrene-derived units, and is preferably 80% by weight, because the obtained copolymer is excellent in various physical properties and reactivity of the monomer. It is more preferable to include% by weight or more. According to the above configuration, a copolymer having low product cost and excellent physical properties can be obtained. In the present specification, the monomer unit derived from styrene means a monomer unit obtained by polymerizing a styrene monomer.

<1-3. Specific structural groups in the copolymer>
As described above, the copolymer has a group represented by the general formula (1). As a result, a highly reactive copolymer can be obtained. A highly reactive copolymer can provide a composition having desired rubber properties.

The method for introducing the group represented by the general formula (1) is not particularly limited, but when the raw material, which is usually called a polymerization initiator and is the starting point of the polymerization reaction, has the structure of the general formula (1), By polymerizing various monomer units in the coexistence of the polymerization initiator, the group represented by the general formula (1) can be introduced into the copolymer. The copolymer having a group represented by the general formula (1) has a branched structure as the structure of the polymer chain.

In the allyl group-terminated styrene-isobutylene block copolymer according to the embodiment of the present invention, the fact that R ¹ and R ² in the general formula (1) are methyl groups determines the availability of raw materials and reactivity. It is preferable because a high copolymer can be obtained.

In order to obtain a copolymer having a group represented by the general formula (1), a compound represented by the following general formula (2) can be used as a polymerization initiator.

（Ｒ^１およびＲ^２は、水素、または炭素数１〜６の１価の炭化水素基を表す。Ｒ^１およびＲ^２は、同一であっても異なっていてもよい。また、複数存在するＲ^１およびＲ^２は、それぞれが同一の基であっても異なる基であってもよい。Ｘは、ハロゲン原子、炭素数１〜６のアルコキシル基および炭素数１〜６のアシロキシル基からなる群より選択される１価の有機基を表す。）
上記ハロゲン原子としては、例えば、塩素、臭素、およびヨウ素等が挙げられる。上記炭素数１〜６のアルコキシル基としては特に限定されず、例えば、メトキシ基、エトキシ基、ｎ−またはイソプロポキシ基等が挙げられる。上記炭素数１〜６のアシロキシ基としては特に限定されず、例えば、アセチルオキシ基、およびプロピオニルオキシ基等が挙げられる。

(R ¹ and R ² represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different, and a plurality of R may be present. ¹ and R ² may be the same group or different groups, respectively. X is from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms and an asyloxyl group having 1 to 6 carbon atoms. Represents the monovalent organic group selected.)
Examples of the halogen atom include chlorine, bromine, iodine and the like. The alkoxyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n- or an isopropoxy group. The asyloxy group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include an acetyloxy group and a propionyloxy group.

Examples of the compound of the general formula (2) used in the present invention include 1,3,5-tris (1-chloro-1-methylethyl) benzene (also known as tricmilk lolide), 1,3,5-tris. (1-Bromo-1-methylethyl) benzene (also known as tricumylbromid), 1,3,5-tris (1-iodo-1-methylethyl) benzene (also known as tricumyliodide), 1,3 Examples thereof include 5-tris (1-methoxy-1-methylethyl) benzene and 1,3,5-tris (1-acetyloxy-1-methylethyl) benzene.

<1-4. Number average molecular weight (Mn)>
The allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention has a number average molecular weight (Mn) of 30,000 to 130,000 (Mn) in standard polystyrene equivalent molecular weight measured by gel permeation chromatography. It is preferably g / mol), and more preferably 40,000 to 120,000 (g / mol). Gel permeation chromatography is also referred to as GPC (Gel permeation chromatography) measurement or SEC (Size exclusion chromatography) measurement.

If the number average molecular weight is less than 30,000 (g / mol), the obtained copolymer may not be molded into pellets. Further, the composition provided by the obtained copolymer may have insufficient rubber physical properties, which may be economically disadvantageous.

On the other hand, when the number average molecular weight exceeds 130,000 (g / mol), the obtained copolymer has a large decrease in fluidity and moldability, and is difficult to handle. Further, in this case, the introduction rate of the allyl group into the copolymer is lowered, and a copolymer having a low allyl group introduction rate can be obtained. Therefore, when the copolymer is used, it is difficult to obtain a composition having desired rubber physical properties. Therefore, it is not preferable that the number average molecular weight is outside the range of 30,000 to 130,000 (g / mol).

<1-5. Molecular weight distribution (Mw / Mn)>
The molecular weight distribution of the allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention (the number represented by the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn) is the melting of the resin. It is preferably 1.10 to 2.00, more preferably 1.10 to 1.90, because it can reduce the viscosity and is easy to handle during molding. According to the above configuration, the uniformity of the molecular weight between the copolymers is high, and the viscosity of the copolymer does not tend to increase when it is molded in a molten state or by using a solvent or the like. Therefore, it has an advantage that workability is good.

<1-6. Percentage of polymer block (a) mainly composed of isobutylene>
Since a copolymer having excellent mechanical properties as a rubber material can be obtained, the content of the polymer block (a) mainly composed of isobutylene is preferably 50 to 90% by weight, preferably 60. It is more preferably ~ 80% by weight. When the content of the polymer block (a) mainly composed of isobutylene is 90% by weight or less, the copolymer does not become veil-like, so that the handleability during processing does not deteriorate and the copolymer weight does not deteriorate. The coalescence can be molded into pellets. Therefore, it becomes easy to handle. When the content of the polymer block (a) mainly composed of isobutylene is 50% by weight or more, the hardness of the copolymer does not become too high and it has flexibility, so that the performance as a rubber material can be sufficiently exhibited. There is an advantage.

<1-7. Allyl group>
The allyl group of the allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention is a functional having a carbon-carbon double bond group that is active in a hydrosilylation reaction with a Si—H group-containing compound. It is also the basis.

As used herein, the allyl group is intended to be a functional group having a structure of main chain −CH ₂ −CH = CH ₂ among functional groups bonded to the main chain. In the present specification, among the functional groups bonded to the main chain, the functional group having the structure of the main chain −CH _2- CH (X) − (CH ₂ ) _m −CH = CH ₂ is an alkenyl group and is referred to as an allyl group. No (X is halogen, m is an integer greater than or equal to 0). When a diene compound is used when introducing a functional group into the copolymer, an alkenyl group is introduced into the main chain. That is, in one embodiment of the present invention, it is preferable not to use a diene compound when introducing a functional group into the copolymer.

The allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention is excellent in heat resistance, creep resistance and solvent resistance, as well as an effect of improving compatibility with other resins and an effect of improving compression set. Therefore, it is preferable to have more than 2.1 allyl groups and 3.0 or less allyl groups in one molecule. The number of allyl groups in one molecule in the copolymer may be the average value of a plurality of copolymers.

In the allyl group-terminated styrene-isobutylene block copolymer according to the embodiment of the present invention, the allyl group introduction rate at the end of the molecular chain is preferably more than 70%, more preferably 80% or more, still more preferably. Is 90% or more.

Here, consider a case where the copolymer does not have the group represented by the general formula (1) and the structure of the copolymer is linear. In this case, when each molecule has two allyl groups, the allyl group introduction rate is 100%. That is, the allyl group introduction rate = the number of allyl groups per molecule / 2 × 100.

Consider a case where the copolymer has a group represented by the general formula (1) and the copolymer has a branched structure. In this case, when each molecule has three allyl groups, the allyl group introduction rate is 100%. That is, the allyl group introduction rate = the number of allyl groups per molecule / 3 × 100.

The method for introducing the allyl group into the styrene-isobutylene block copolymer is not particularly limited, but the following method can be exemplified as a method that can be preferably carried out.

(1) Method of reacting with an allylsilane compound in the presence of a Lewis acid catalyst (2) Method of reacting with an allylphenyl ether compound in the presence of a Lewis acid catalyst (3) Reacting with a phenol compound in the presence of a Lewis acid catalyst Then, a method of stepwise constructing an allylphenyl ether group by introducing a phenol group at the end of the polymer and subsequently reacting with an allyl halide compound.

Among these, in one embodiment of the present invention, a method in which an allylsilane compound is used as an allylating agent and an allyl group is introduced by a substitution reaction between a halogen group at the terminal of the copolymer and the allylsilane compound is an allyl group introduction efficiency. It is preferable because it has excellent reactivity of the introduced allyl group.

In the present specification, the substituent introduced by using the diene compound described in Patent Document 6 is an alkenyl group. That is, Patent Document 6 discloses an alkenyl group-terminated styrene-isobutylene block copolymer. As a result of examination by the present inventor, the alkenyl group-terminated styrene-isobutylene block copolymer disclosed in Patent Document 6 is not preferable because the activity of the obtained copolymer for the cross-linking reaction may be insufficient. Do you get it.

<1-8. Shape>
The allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention is preferably in the form of pellets. In other words, it is preferable that the copolymer can be molded into pellets. The above configuration has the advantage of being easy to handle.

In the present specification, the pellet shape means a solid shape having a substantially constant thickness such as a columnar prism, a spherical prism, an elliptical prism, a polygonal prism (for example, a triangular prism, a square prism, a pentagonal prism, a hexagonal prism, etc.). When the copolymer is a pellet, its cross section is circular, elliptical, polygonal or the like, and is not particularly limited. When the copolymer is pellets, the surface of the copolymer may be uneven.

[2. Method for producing allyl group-terminated styrene-isobutylene block copolymer]
The method for producing an allyl group-terminated styrene-isobutylene block copolymer according to an embodiment of the present invention includes a first step of mixing a styrene monomer and an isobutylene monomer to obtain a styrene-isobutylene block copolymer. It has a second step of mixing the styrene-isobutylene block copolymer and the allylating agent until the consumption rate of the styrene monomer reaches 90%, and in the first step, polymerization is started. As the agent, a compound represented by the following general formula (2) is used.

（Ｒ^１およびＲ^２は、水素、または炭素数１〜６の１価の炭化水素基を表す。Ｒ^１およびＲ^２は、同一であっても異なっていてもよい。また、複数存在するＲ^１およびＲ^２は、それぞれが同一の基であっても異なる基であってもよい。Ｘは、ハロゲン原子、炭素数１〜６のアルコキシル基および炭素数１〜６のアシロキシル基からなる群より選択される１価の有機基を表す。）
当該構成によると、（ａ）取り扱いが容易であり、（ｂ）優れたゴム物性を発現しうる組成物を提供し得る、アリル基末端スチレン−イソブチレンブロック共重合体を得ることができる。

(R ¹ and R ² represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different, and a plurality of R may be present. ¹ and R ² may be the same group or different groups, respectively. X is a group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms and an asyloxyl group having 1 to 6 carbon atoms. Represents the monovalent organic group selected.)
According to this configuration, it is possible to obtain an allyl group-terminated styrene-isobutylene block copolymer capable of (a) being easy to handle and (b) providing a composition capable of exhibiting excellent rubber physical properties.

The method for producing an allyl group-terminated styrene-isobutylene block copolymer according to an embodiment of the present invention is also simply referred to as a method for producing a copolymer. The method for producing the copolymer is described in [1. Allyl group-terminated styrene-isobutylene block copolymer] can be suitably used for obtaining the copolymer described in the section. As an explanation of the physical properties of each component, copolymer, and copolymer in the method for producing a copolymer, [1. Allyl group-terminated styrene-isobutylene block copolymer] can be appropriately incorporated.

The method for producing the allyl group-terminated styrene-isobutylene block copolymer of the present invention is not particularly limited, but for example, in the presence of the compound represented by the general formula (2), (i) isobutylene is the main component. The monomer is polymerized to construct a branched isobutylene-based polymer block (a), and (ii) the styrene-based monomer is then polymerized to form a styrene-based polymer. A method of constructing the block (b) to obtain a copolymer, (iii) finally mixing the copolymer and the allylating agent, and introducing an allyl group at the end of the copolymer is preferably used. The steps (i) and (ii) are the first steps, and since the monomers are polymerized, it can be said to be a step of carrying out a polymerization reaction. The (iii) is the second step.

In the second step, "the styrene-isobutylene block copolymer and the allylating agent are mixed until the consumption rate of the styrene monomer reaches 90%" means that among the added styrene monomers. , The copolymer and the allylating agent are mixed until the amount consumed by the reaction reaches 90% of the input amount (also referred to as the charged amount or the added amount). In addition, "until the consumption rate reaches 90%" means that the consumption rate is less than 90%.

The present inventor can increase the number of allyl groups to more than 2.1 by mixing the styrene-isobutylene block copolymer and the allylating agent until the consumption rate of the styrene monomer reaches 90%. Was found for the first time. In particular, when a compound represented by the general formula (2) was used as the polymerization initiator, the styrene-isobutylene block copolymer and the allylic agent were mixed after the consumption rate of the styrene monomer reached 90% or more. Occasionally, the number of allyl groups was 2.1 or less.

Here, as long as the effect of the present invention is not impaired, in the first step of the method for producing a copolymer, as a polymerization initiator, in addition to the compound represented by the general formula (2), the following general formula ( Another compound shown in 3) may be mixed and used.

(CR ¹ R ² X) nY (3)
In the general formula (3), X represents a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms and an asyloxyl group having 1 to 6 carbon atoms. R ¹ and R ² represent hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms, respectively. R ¹ and R ² may be the same or different. Further, the plurality of R ¹ and R ² existing may be the same or different from each other. Y represents a multi-valent aromatic hydrocarbon group or a multi-valent aliphatic hydrocarbon group capable of having n substituents (CR ¹ R ² X). n represents a natural number of 1-2 or 4-6.

Examples of the halogen atom include chlorine and bromine. Examples of the alkoxyl group having 1 to 6 carbon atoms include a methoxy group and an ethoxy group. Examples of the asyloxy group having 1 to 6 carbon atoms include an acetyloxy group. Examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n- or an isopropyl group and the like.

The compound represented by the general formula (3) is a polymerization initiator, and is considered to generate carbon cations in the presence of Lewis acid or the like and serve as a starting point of a polymerization reaction, that is, cationic polymerization.

Examples of the compound of the general formula (3) include (1-chloro-1-methylethyl) benzene (also known as cumylloride) and 1,4-bis (1-chloro-1-methylethyl) benzene (also known as p). − Dicumyl lolide), 1,3-bis (1-chloro-1-methylethyl) benzene (also known as m-dimethylyl lolide), and 1,3-bis (1-chloro-1-methylethyl)- Examples thereof include 5- (tert-butyl) benzene.

From the viewpoint of availability and reactivity, the compound of the general formula (3) is preferably kmilk lolide, p-dikumilk lolide, or m-dick milk lolide.

The first step (polymerization reaction), that is, the steps (i) and (ii) is generally performed in the coexistence of a Lewis acid catalyst and a polymerization initiator. The Lewis acid catalyst is not particularly limited as long as it can be used for cationic polymerization, and for example, TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ , OEt ₂ , SnCl ₄ , AlCl ₃ , AlBr _3, etc. Metal halides; or metal compounds having both halogen atoms and alkoxide groups on metals such as TiCl ₃ (OiPr), TiCl ₂ (OiPr) ₂ , and TiCl (OiPr) ₃ ; Et ₂ AlCl, Et AlCl ₂ , Me ₂ AlCl, Me AlCl ₂ , Et _1.5 AlCl _1.5 , and organic metal halides such as Me _1.5 AlCl _1.5 .

As the Lewis acid catalyst, TiCl ₄ , BCl ₃ , SnCl ₄ , TiCl ₃ (OiPr), TiCl ₂ (OiPr) ₂ , TiCl (OiPr) ₃ , EtAlCl ₂ , EtAlCl ₂ , because of its excellent catalytic ability and availability. It is preferable to use one or more Lewis acid catalysts selected from the group consisting of Et _1.5 AlCl _1.5 and Et _1.5 AlCl _1.5 .

The amount of the Lewis acid catalyst used is not particularly limited, and can be arbitrarily set in consideration of the polymerization characteristics of the monomer used, the polymerization concentration, the desired polymerization time, the exothermic behavior during the polymerization reaction, and the like. It is preferably used in the range of 0.1 to 200 mol, more preferably 0.2 to 100 mol, with respect to 1 mol of the compound represented by the general formula (2).

In the first step, electron donor components such as pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom are further used, if necessary. You may. The electron donor component is considered to have the effect of stabilizing the carbon cation at the growing chain end and adjusting the Lewis acidity by coordinating with the Lewis acid. Therefore, when the electron donor component is used, a polymer having a narrow molecular weight distribution and a controlled structure can be obtained.

As the electron donor component, a compound having 15 to 60 donors defined as a parameter indicating strength as an electron donor (electron donor) of various compounds can be preferably used. Examples of such compounds include pyridine, 2-methylpyridine, 2,6-dimethylpyridine, N, N-dimethylaminopyridine, diethylamine, trimethylamine, triethylamine, tributylamine, N, N-dimethylformamide, N, N. -Dimethylacetamide, ethyl acetate, butyl acetate, tetrahydrofuran, tetrahydropyridine, hexamethylene oxide, titanium (IV) tetramethoxyde, titanium (IV) tetraisopropoxide, titanium (IV) tetrabutoxide and the like.

As the electron donor component, 2-methylpyridine, 2,6-dimethylpyridine, triethylamine, N, N-dimethylformamide, N, N-dimethylacetamide, and titanium are excellent in terms of addition effect and availability. (IV) One or more compounds selected from the group consisting of tetraisopropoxide can be more preferably used.

The electron donor component can generally be used in an amount of 0.01 to 100 mol per 1 mol of the polymerization initiator. In the method for producing a copolymer, the electron donor component is preferably used in the range of 0.1 to 50 mol with respect to 1 mol of the polymerization initiator.

The first step and the second step can be performed in an organic solvent, if necessary. The organic solvent is not particularly limited as long as it is a solvent generally used in cationic polymerization, and is a solvent composed of halogenated hydrocarbons, non-halogenated solvents such as aliphatic hydrocarbons and aromatic hydrocarbons, or these. A mixture of can be used.

Examples of the halogenated hydrocarbon include methyl chloride, methylene chloride, propyl chloride, butyl chloride, pentyl chloride, and hexyl chloride.

Examples of the aliphatic and / or aromatic hydrocarbon include pentane, hexane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, and toluene.

As the organic solvent, methyl chloride, butyl chloride, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, and toluene are particularly preferably used because of their excellent solubility and economy. Only one type of these may be used, or two or more types may be mixed and used. When two or more kinds are mixed and used, they can be mixed in an arbitrary ratio from the viewpoint of solubility, reactivity and economy.

From the viewpoint of the viscosity of the solution and the ease of heat removal, the solution concentration of the obtained copolymer is preferably set to be 1 to 50% by weight, and is set to be 3 to 35% by weight. Is more preferable.

In the method for producing a copolymer, the temperature at which the polymerization reaction (living cationic polymerization) is carried out is not particularly limited, but for example, each component is mixed at a temperature of −100 ° C. or higher and lower than 50 ° C. to carry out the polymerization reaction. Is preferable. Further, −85 ° C. to 0 ° C. is more preferable because it is excellent in energy cost and stability of the polymerization reaction. When the temperature of the polymerization reaction is (a) -100 ° C or higher, the monomer does not precipitate, and when (b) is less than 50 ° C, the proportion of side reactions decreases and the desired copolymer weight It has the advantage of being easy to coalesce.

Examples of the allylic agent that can be used in the second step include diallyldimethylsilane, allyltrimethylsilane, allyltriethylsilane, diallyldiphenylsilane, triallylmethylsilane, and tetraallylsilane. Among these allylic agents, diallyldimethylsilane and allyltrimethylsilane are more preferable because of their good industrial availability. Only one type of these allylic agents may be used, or two or more types may be used in combination.

[3. Allyl group-terminated styrene-isobutylene block copolymer composition]
The allyl group-terminated styrene-isobutylene block copolymer composition according to one embodiment of the present invention comprises (A) an allyl group-terminated styrene-isobutylene block copolymer and (B) an olefin resin (A) an allyl group. It is contained in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of the terminal styrene-isobutylene block copolymer. Here, (A) the allyl group-terminated styrene-isobutylene block copolymer is [1. Allyl group-terminated styrene-isobutylene block copolymer]. The allyl group-terminated styrene-isobutylene block copolymer. According to the above configuration, the allyl group-terminated styrene-isobutylene block copolymer composition has an advantage that excellent rubber physical properties can be exhibited.

The allyl group-terminated styrene-isobutylene block copolymer composition according to an embodiment of the present invention is also simply referred to as a copolymer composition below. The copolymer composition can also be a thermoplastic elastomer composition.

<3-1. (B) Olefin resin>
When producing the copolymer composition, (B) an olefin resin is used.

The olefin-based resin (B) is not particularly limited, and examples thereof include polyolefin-based resins, styrene-based thermoplastic elastomers, polyvinyl chloride-based resins, and polyacrylic-based resins.

Examples of the polyolefin-based resin include (i) ethylene, (ii) an α-olefin homopolymer or α-olefin copolymer having an α-olefin content of 3 to 20 carbon atoms of 50 to 100 mol%, and an α-olefin copolymer. (Iii) Examples thereof include a homopolymer of a cyclic olefin having a content of a cyclic olefin having 3 to 20 carbon atoms of 50 to 100 mol% or a copolymer of a cyclic olefin.

Specifically, the polyolefin-based resin includes polyethylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, and ethylene-hexene copolymer. (Co) of cyclic olefins such as ethylene-octene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, norbornene, dicyclopentadiene, tricyclopentadiene Examples include polymers, polystyrene, impact resistant polystyrene (high impact polystyrene), poly (α-methylstyrene), and styrene-maleic anhydride copolymers.

Specifically, the styrene-based thermoplastic elastomer comprises hydrogen in (i) styrene-butadiene-styrene block copolymer (SBS) and styrene-isoprene-styrene block copolymer (SIS), (ii) SBS and SIS. The added styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and (iii) styrene-isobutylene-styrene block copolymer (SIBS), etc. Can be mentioned.

Examples of the polyvinyl chloride-based resin include polyvinyl chloride, polyvinylidene chloride, and chlorinated polyvinyl chloride.

Examples of the polyacrylic resin include acrylonitrile-styrene resin (AS), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-butadiene-α-methylstyrene (heat resistant ABS), polymethylmethacrylate, and methylmethacrylate-styrene copolymer weight. Coalescence etc. can be mentioned.

The olefin resin (B) can be used properly according to the required properties. For example, polypropylene and cyclic olefin (co) polymers are preferred when heat resistance is required. Polyethylene is preferable when electrical characteristics such as insulation are required. When polarity such as adhesiveness is required, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and the like are preferable. Further, it is preferable to use a styrene-based thermoplastic elastomer because it is excellent in compatibility, economy, and rubber physical properties.

As the (B) olefin-based resin, polyethylene, polypropylene, a cyclic olefin (co) polymer, and a styrene-based thermoplastic elastomer are preferable because they are excellent in heat resistance, mechanical properties, and economic efficiency. When heat resistance is particularly required among styrene-based thermoplastic elastomers, hydrogenation of styrene-ethylenebutylene-styrene block copolymer (SEBS) and styrene-ethylenepropylene-styrene block copolymer (SEPS) is performed. Styrene-isobutylene-styrene block copolymer (SIBS) is preferred.

The content (blending amount) of the (B) olefin resin in the copolymer composition shall be 5 to 200 parts by weight with respect to 100 parts by weight of the (A) allyl group-terminated styrene-isobutylene block copolymer. Is preferable, and 10 to 150 parts is more preferable. (B) When the content of the olefin resin is (i) 200 parts by weight or less, the flexibility and other rubber physical properties are excellent, and when (ii) 5 parts by weight or more, the obtained copolymer composition is obtained. The product has excellent moldability.

<3-2. (C) Plasticizer>
Since the copolymer composition can improve moldability and flexibility as long as the effects of the present invention are not impaired, it is preferable that the copolymer composition further contains (C) a plasticizer.

The plasticizer (C) is not particularly limited, but a material that is liquid at room temperature is usually preferably used. Also, both hydrophilic and hydrophobic plasticizers can be used. Examples of such a plasticizer include various rubber plasticizers and resin plasticizers. Examples of the (C) plasticizer include mineral oil-based plasticizers, vegetable oil-based plasticizers, and synthetic plasticizers.

Examples of the mineral oil-based plasticizer include paraffin-based oils, naphthen-based oils, and aromatic-based high-boiling petroleum components. A paraffinic oil that does not inhibit the cross-linking reaction is preferable.

Examples of the vegetable oil-based plasticizer include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, wood wax, pine oil, and olive oil.

Examples of the synthetic plasticizer include liquid synthetic oils such as polybutene, hydrogenated polybutene, liquid polybutadiene, hydrogenated liquid polybutadiene, and liquid poly α-olefins, or low molecular weight synthetic oils. Further, dibasic acid dialkyl esters such as dibutyl phthalate, dioctyl phthalate, and dibutyl adipate are also used.

Paraffinic oil is preferable as the (C) plasticizer because it is easy to handle, economical, and has excellent viscosity characteristics. On the other hand, polybutene oil is preferable as the (C) plasticizer because it has excellent compatibility and gas barrier properties. Further, since the extractability is extremely low and the hygiene is excellent, polybutene having a number average molecular weight of 2,000 or more is preferable.

The plasticizer (C) can be used in combination of two or more at any ratio in order to obtain a desired viscosity and physical properties.

In the allyl group-terminated styrene-isobutylene block copolymer composition according to one embodiment of the present invention, the content (blending amount) of (C) the plasticizer is (A) allyl group-terminated styrene-isobutylene block copolymer 100. It is preferably contained in an amount of 1 to 300 parts by weight with respect to parts by weight. (C) When the content of the plasticizer is 300 parts by weight or less, (i) the composition is not significantly tacked, so that it is easy to handle and (ii) a suitable balance of mechanical strength can be maintained. There is an advantage that it can be done.

The (A) allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention may further contain an antioxidant.

<3-3. Physical properties>
Rubber properties of the allyl group-terminated styrene-isobutylene block copolymer composition according to one embodiment of the present invention, specifically, flexibility, compression set, fluidity, heat resistance, creep resistance, and solvent resistance. Will be described.

The flexibility of the copolymer composition can be evaluated using hardness as an index. When the hardness is 10 or more and 70 or less, it means that the copolymer composition is excellent in flexibility.

The compression set of the copolymer composition can be measured according to JIS K 6262. The specific measurement method will be described in detail in the following examples. The compression set of the copolymer composition is preferably 40% or less, more preferably 35% or less, and further preferably 30% or less.

The fluidity of the copolymer composition can be evaluated by the melt flow rate (MFR). The larger the MFR, the higher the liquidity. The higher the fluidity of the copolymer composition, the easier it is to handle. The copolymer composition preferably has an MFR of 0.3 g / 10 minutes or more, more preferably 1 g / 10 minutes or more, further preferably 3 g / 10 minutes or more, and 5 g / 10 minutes. The above is particularly preferable. The specific measurement method of MFR will be described in detail in the following examples.

The heat resistance of the copolymer composition can be evaluated by the retention rate calculated from the storage elastic modulus. The retention rate is the ratio of the storage elastic modulus at 130 ° C. or 140 ° C. to the storage elastic modulus at 23 ° C. The larger the retention rate, the better the heat resistance. The retention rate of the copolymer composition at 130 ° C. is preferably 20% or more under the measurement condition of 100 Hz, preferably 23% or more under the measurement condition of 10 Hz, and 23% or more under the measurement condition of 1 Hz. It is preferable to have. The retention rate of the copolymer composition at 140 ° C. is preferably 12% or more under the measurement condition of 100 Hz, preferably 13% or more under the measurement condition of 10 Hz, and 13% or more under the measurement condition of 1 Hz. It is preferable to have. A specific method for measuring the storage elastic modulus will be described in detail in the following examples.

The creep resistance of the copolymer composition can be evaluated by the creep rate. The lower the creep rate, the better the creep resistance. A specific method for measuring the creep rate will be described in detail in the following examples. The creep rate of the copolymer composition is preferably 200% or less under the measurement condition of 0 minutes (immediately after loading), preferably 225% or less after 50 minutes of the measurement condition, and 100 minutes after the measurement condition. In the case of, it is preferably 260% or less, in the case of 150 minutes after the measurement condition, it is preferably 270% or less, and in the case of 200 minutes after the measurement condition, it is preferably 275% or less. A specific method for measuring the creep rate will be described in detail in the following examples.

The solvent resistance of the copolymer composition can be evaluated by the swelling rate when immersed in toluene for a certain period of time. The smaller the swelling rate, the better the solvent resistance. The copolymer composition preferably has a swelling rate of less than 60% after 30 minutes and / or a swelling rate of less than 145% after 90 minutes. A specific method for measuring the swelling rate will be described in detail in the following examples.

[4. Method for Producing Allyl Group-Terminal Styrene-Isobutylene Block Copolymer Composition]
In the method for producing an allyl group-terminated styrene-isobutylene block copolymer composition according to an embodiment of the present invention, the (A) allyl group-terminated styrene-isobutylene block copolymer and the (B) olefin resin are melted. It has a kneading step, and in the melt-kneading step, the allyl group-terminated styrene-isobutylene block copolymers are dynamically crosslinked with each other. According to the above structure, it is possible to provide an allyl group-terminated styrene-isobutylene block copolymer composition capable of exhibiting excellent rubber physical properties. The method for producing an allyl group-terminated styrene-isobutylene block copolymer composition according to an embodiment of the present invention is also simply referred to as a method for producing a copolymer composition.

The dynamic cross-linking reaction represents a cross-linking reaction of a resin while melt-kneading. By using the melt-kneading method, a composition containing a crosslinked rubber component and having thermoplasticity can be produced. As a result, the thermoplastic elastomer composition having excellent rubber physical properties, moldability and economy can be produced.

(A) As a means for cross-linking the allyl group-terminated styrene-isobutylene block copolymer, a conventionally known method can be used, and there is no particular limitation, but for example, thermal cross-linking by heating and cross-linking with a cross-linking agent are performed. Can be done.

Among these, it is preferable to use a Si—H bond-containing compound as a cross-linking agent in terms of reaction rate and cross-linking efficiency. That is, in the method for producing a copolymer composition, the dynamic cross-linking reaction is preferably a hydrosilylation reaction.

In general, the dynamic cross-linking reactions such as vulcanization and resin cross-linking not only require various auxiliary materials such as a cross-linking agent and a cross-linking catalyst, but also the auxiliary materials elute (bleed) from the rubber material over time. In some cases, there is a problem that the use is restricted in such applications where bleeding is disliked.

On the other hand, the hydrosilylation reaction has the advantage that not only the amount of the cross-linking agent and the cross-linking catalyst is extremely small, but also the amount of bleeding of these components is very small, so that it can be suitably used in the present invention.

The Si—H bond-containing compound that can be used in the present invention is not particularly limited, and in general, a compound called alkylhydrogensilicone can be preferably used. Regarding the alkylhydrogen silicone, the disclosure of Patent Document 4 can be referred to.

When the (A) allyl group-terminated styrene-isobutylene block copolymer of the present invention is subjected to a dynamic cross-linking reaction with the alkylhydrogen silicone, various transition metal catalysts can be preferably used as catalysts. In the transition metal catalyst, a compound having a platinum atom as a central metal is particularly preferable, and a platinum complex in which an olefin compound is coordinated as a ligand is more preferable. Regarding the transition metal catalyst, the disclosure of Patent Document 4 can be referred to.

The method of melt-kneading the thermoplastic elastomer composition in the present invention is not particularly limited. The melt-kneading method may be any method as long as various components such as (A) allyl group-terminated styrene-isobutylene block copolymer, (B) olefin resin, and (C) plasticizer can be uniformly heated and mixed. , Any method known in the art.

The (A) allyl group-terminated styrene-isobutylene block copolymer of the present invention is solid at room temperature and can be treated as pellets, crumbs, powders and the like. Therefore, when the (A) allyl group-terminated styrene-isobutylene block copolymer of the present invention is charged into the extruder, a general supply device can be used.

The method of charging the allyl group-terminated styrene-isobutylene block copolymer of the present invention into the extruder can be preferably carried out by the method exemplified below. For example, when manufactured using a closed or open batch kneader such as a lab plast mill, lavender, Banbury mixer, kneader, roll, etc., all components except the cross-linking agent and cross-linking catalyst are premixed. Melt and knead until uniform. Then, a method of adding a cross-linking agent and a cross-linking catalyst to the cross-linking agent to allow the cross-linking reaction to proceed sufficiently and then stopping the melt-kneading can be adopted.

Further, in the case of manufacturing using a continuous type melt-kneading device such as a single-screw extruder and a twin-screw extruder, all the compositions other than the cross-linking agent and the cross-linking catalyst are uniformly uniformized in advance by the melt-kneading device such as an extruder. After melt-kneading until it becomes, it is molded into pellets. Next, a method in which a cross-linking agent is dry-blended into the pellet-shaped (A) allyl group-terminated styrene-isobutylene block copolymer and then melt-kneaded with a melt-kneading device such as an extruder to dynamically cross-link the composition. There is. Alternatively, all the compositions other than the cross-linking agent and the cross-linking catalyst are melt-kneaded by a melt-kneading device such as an extruder, and the cross-linking agent and the cross-linking catalyst are added thereto from the middle of the cylinder of the extruder, and further melt-kneaded. A method of dynamically cross-linking the composition or the like can be adopted.

The kneading temperature in the above-mentioned melt kneading method is preferably 140 to 250 ° C. According to the above structure, the olefin resin (B) can be sufficiently melted and uniformly kneaded. Further, it has an advantage that the thermal decomposition of (A) allyl group-terminated styrene-isobutylene block copolymer and (B) olefin resin does not proceed.

The thermoplastic elastomer composition of the present invention can be melt-molded using a molding method and a molding apparatus generally adopted for a thermoplastic resin. For example, extrusion molding, injection molding, press molding, blow molding and the like.

Further, since the thermoplastic elastomer composition of the present invention has an excellent balance of rubber properties, it is used for sealing materials such as packing materials, sealing materials, gaskets and stoppers, and vibration damping for dampers, automobiles, vehicles and home appliances. It can be suitably used as a material, a vibration-proof material, an automobile interior material, a cushion material, a daily necessities, an electric part, an electronic part, a sports member, a grip material or a cushioning material, an electric wire covering material, a packaging material, various containers, and a stationery part. ..

[1] Standard polystyrene having an allyl group at the end of the molecular chain, consisting of a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of styrene, and measured by gel permeation chromatography. The converted number average molecular weight (Mn) is 30,000 to 130,000 (g / mol), the molecular weight distribution (Mw / Mn) is 1.10 to 2.00, and the weight mainly composed of isobutylene. The content of the coalesced block (a) is 50 to 90% by weight, and the molecular chain has a group represented by the following general formula (1).

（前記一般式（１）中、Ｒ^１およびＲ^２は、水素、または炭素数１〜６の１価の炭化水素基を表す。Ｒ^１およびＲ^２は、同一であっても異なっていてもよい。また、複数存在するＲ^１およびＲ^２は、それぞれが同一の基であっても異なる基であってもよい。）一分子中にアリル基を２．１個超３．０個以下有することを特徴とするアリル基末端スチレン−イソブチレンブロック共重合体。

(In the general formula (1), R ¹ and R ² represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different. Also, a plurality of R ¹ and R ² existing may be the same group or different groups, respectively.) It has more than 2.1 and 3.0 or less allyl groups in one molecule. An allyl group-terminated styrene-isobutylene block copolymer.

[2] The allyl group-terminated styrene-isobutylene block copolymer according to [1], wherein R ¹ and R ² in the general formula (1) are methyl groups.

[3] The allyl group-terminated styrene-isobutylene block according to [1] or [2], wherein the isobutylene-based polymer block (a) contains 80% by weight or more of a unit derived from isobutylene. Copolymer.

[4] The allyl group according to any one of [1] to [3], wherein the styrene-based polymer block (b) contains 80% by weight or more of styrene-derived units. Terminal styrene-isobutylene block copolymer.

[5] The allyl group-terminated styrene-isobutylene block copolymer according to any one of [1] to [4], wherein the allyl group-terminated styrene-isobutylene block copolymer is in the form of pellets. Combined.

[6] The first step of mixing a styrene monomer and an isobutylene monomer to obtain a styrene-isobutylene block copolymer, and the styrene-by the time the consumption rate of the styrene monomer reaches 90%. It has a second step of mixing the isobutylene block copolymer and the allyrene agent, and in the first step, a compound represented by the following general formula (2) is used as the polymerization initiator [1]. The method for producing an allyl group-terminated styrene-isobutylene block copolymer according to any one of [5].

（Ｒ^１およびＲ^２は、水素、または炭素数１〜６の１価の炭化水素基を表す。Ｒ^１およびＲ^２は、同一であっても異なっていてもよい。また、複数存在するＲ^１およびＲ^２は、それぞれが同一の基であっても異なる基であってもよい。Ｘは、ハロゲン原子、炭素数１〜６のアルコキシル基および炭素数１〜６のアシロキシル基からなる群より選択される１価の有機基を表す。）
〔７〕（Ａ）〔１〕〜〔６〕のいずれか１つに記載のアリル基末端スチレン−イソブチレンブロック共重合体、および、（Ｂ）オレフィン系樹脂を前記（Ａ）アリル基末端スチレン−イソブチレンブロック共重合体１００重量部に対して、５〜２００重量部含有する、ことを特徴とするアリル基末端スチレン−イソブチレンブロック共重合体組成物。

(R ¹ and R ² represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different, and a plurality of R may be present. ¹ and R ² may be the same group or different groups, respectively. X is a group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms and an asyloxyl group having 1 to 6 carbon atoms. Represents the monovalent organic group selected.)
[7] The allyl group-terminated styrene-isobutylene block copolymer according to any one of (A) [1] to [6] and the (B) olefin resin are used as the above-mentioned (A) allyl group-terminated styrene-. An allyl group-terminated styrene-isobutylene block copolymer composition, which is contained in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of the isobutylene block copolymer.

[8] The allyl according to [7], which further contains 1 to 300 parts by weight of (C) a plasticizer with respect to 100 parts by weight of the (A) allyl group-terminated styrene-isobutylene block copolymer. Group-terminal styrene-isobutylene block copolymer composition.

[9] The allyl group-terminated styrene-isobutylene block copolymer has a step of melt-kneading the (B) olefin resin, and in the melt-kneading step, the allyl group-terminated styrene-isobutylene block. The method for producing an allyl group-terminated styrene-isobutylene block copolymer composition according to [7] or [8], which comprises dynamically cross-linking the copolymers with each other.

[10] The method for producing an allyl group-terminated styrene-isobutylene block copolymer composition according to [9], wherein the dynamic cross-linking reaction is a hydrosilylation reaction.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(1. Molecular weight measurement)
In the following examples, "number average molecular weight (Mn)", "weight average molecular weight (Mw)" and "molecular weight distribution (ratio of weight average molecular weight to number average molecular weight, Mw / Mn)" of the obtained copolymer. Was calculated by the standard polystyrene conversion method using gel permeation chromatography (GPC).

As a measuring device, a GPC system manufactured by Waters Corp. was used. The measurement conditions are as follows.
Mobile phase: Chloroform Column temperature: 35 ° C
Polymer concentration of sample solution: 4 mg / mL.

(2. Number of allyl groups introduced)
The obtained copolymer was subjected to a proton NMR spectrum (measuring device: AVANCE series manufactured by Bruker, 400 MHz nuclear magnetic resonance device, measuring solvent: deuterated chloroform), and a polymer block (a) mainly containing isobutylene was used (specifically). The integral value of isobutylene block) and the integral value of allyl group were obtained. The number of allyl groups was determined from the ratio of the obtained integral values. The procedure is shown below.

(I) H _{1.1 ppm} = (number of moles of isobutylene used) / (number of moles of polymerization initiator used) x 6
From the above formula, the value H _{1.1 ppm} to be set as the integral value of the two methyl groups in the monomer unit derived from isobutylene appearing at _{1.1 ppm} was calculated.

(Ii) A peak appearing at 1.1 ppm was detected in the NMR spectrum, and the integrated value of the peak was set to the value H _{1.1 ppm} calculated in (i) above.

(Iii) At this time, two peaks derived from the allyl group appearing at 5.5 ppm and 4.8 ppm were detected in the NMR spectrum, and their integrated values were obtained. _Let H _{5.5 ppm} and H _{4.8 ppm} , respectively.

(Iv) Number of allyl groups = (H _{5.5 ppm} + H _{4.8 ppm} / 2) / 2
The number of allyl groups in one molecule was determined.

(3. Allyl group introduction rate)
The allyl group introduction rate of the obtained copolymer was calculated according to the following formula.
Allyl group introduction rate = (number of allyl groups) / (number of Xs) x 100
However, the number of X is intended to be the number of halogen atoms (X) in the polymerization initiator used in the production of the copolymer. When a compound represented by the general formula (2) (for example, 1,3,5-trikumilk lolide) is used as the polymerization initiator, X is 3. Further, when another compound represented by the general formula (3) (for example, p-dikumilk lolide) is used as the polymerization initiator, X becomes 2.

(4. Tensile strength: Tb)
The tensile strength of the obtained sheet-like composition was determined according to JIS K 6251. A dumbbell piece obtained by punching a 2 mm thick sheet-like composition into a No. 7 type with a dumbbell was used as a test piece, and the test piece was used for measurement. The tensile speed was 500 mm / min.

(5. Tensile elongation: Eb)
The tensile elongation of the obtained sheet-like composition was determined according to JIS K 6251. A dumbbell piece obtained by punching a 2 mm thick sheet-like composition into a No. 7 type with a dumbbell was used as a test piece, and the test piece was used for measurement. The tensile speed was 500 mm / min.

(6. Hardness)
The hardness of the obtained sheet-like composition was measured using a spring type A durometer (manufactured by Polymer Instruments Co., Ltd., model CL-150) in accordance with JIS K 6253. A dumbbell piece obtained by punching a 2 mm thick sheet-like composition into a No. 7 type with a dumbbell was used as a test piece, and the test piece was used for measurement. The value immediately after the measurement was adopted as the hardness.

(7. Compressed permanent distortion)
The measurement was performed under the following conditions in accordance with JIS K 6262. As a test piece, a composition formed into a cylinder having a thickness of 12.0 mm was used.
Temperature: 70 ° C
Time: 22 hours Deformation rate: 25%.

(8. Liquidity)
The MFR (melt flow rate) was measured under the following measurement conditions in accordance with JIS K 7210, A method.
Temperature: 190 ° C
Load: 2.16 kgf.

(9. Heat resistance)
The heat resistance of the obtained sheet-like composition was determined according to JIS K 6394. A 6 mm × 5 mm × 2 mm sample piece was cut out from the sheet-like composition and used as a test piece. Then, the storage elastic modulus at a measurement frequency of 100 Hz, 10 Hz, and 1 Hz was measured at 23 ° C., 130 ° C., and 140 ° C. using a dynamic viscoelasticity measuring device DVA-200 (manufactured by IT Measurement Control Co., Ltd.). Next, the ratio of the storage elastic modulus at 130 ° C. or 140 ° C. to the storage elastic modulus at 23 ° C. was determined, and the ratio was defined as the retention rate (%). The retention rate was used as the standard for heat resistance.

(10. Creep resistance)
A dumbbell piece obtained by punching a 2 mm thick sheet-like composition into a No. 7 shape with a dumbbell was used as a test piece, and two marked lines were drawn at 10 mm intervals on the constricted portion of the dumbbell piece. Next, one of the dumbbell pieces was fixed, a load of 1 kgf was applied to the other piece at 23 ° C. and 50% RH, and the change over time of the distance between the marked lines was measured to evaluate the creep resistance. Here, the creep rate (%) was calculated by the following equation, where Z is the distance between the marked lines at a certain time.
Creep rate (%) = (Z-10) / 10 × 100.

(11. Solvent resistance)
A sample piece of 20 mm × 37 mm × 2 mm was cut out from the sheet-like composition and used as a test piece. The test piece was immersed in about 200 g of toluene at room temperature. After a lapse of a certain period of time, the test piece was taken out, the toluene adhering to the surface was wiped off, and the change in weight of the test piece was measured. Here, the swelling rate (%) was calculated by the following formula, where Y ₁ was the initial weight of the test piece and Y _t was the weight at a certain time. Swelling rate (%) = (Y _t −Y ₁ ) / Y ₁ × 100.

(Example 1) Synthesis of allyl group-terminated styrene-isobutylene block copolymer (A-1)
After nitrogen substitution in a 200 L reactor, 90 kg of butyl chloride and 7.5 kg of hexane were added and the resulting mixture was cooled to about −70 ° C. Next, 19.5 kg (348 mol) of isobutylene, 154 g (0.502 mol) of tricmyllolide and 32.7 g (0.351 mmol) of 2-methylpyridine (also known as α-picoline) were added to the obtained mixture. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 429 g (2.26 mol) of titanium tetrachloride was added to the mixture to initiate polymerization. After stirring for 60 minutes from the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 98.9%.

Specifically, the consumption rate of isobutylene was calculated by the following formula using the results obtained by measuring the amount of isobutylene monomer by GC:
Isobutylene consumption rate (%) = (amount of isobutylene monomer used-amount of unreacted isobutylene monomer measured by GC) / amount of isobutylene monomer used x 100
That is, the consumption rate of isobutylene indicates the ratio of the isobutylene monomer used for producing the polymer among the isobutylene monomers used.

Then, 6.27 kg (60.2 mol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and when 80% of the added amount (charged amount) was consumed, 229 g (2.01 mol) of allyltrimethylsilane and 381 g (2.01 mol) of titanium tetrachloride were added. Was added to the reaction mixture.

Specifically, the styrene consumption rate was calculated by the following formula using the results obtained by measuring the amount of styrene monomer by GC:
Styrene consumption rate (%) = (amount of styrene monomer used-amount of unreacted styrene monomer measured by GC) / amount of styrene monomer used x 100
That is, the styrene consumption rate indicates the ratio of the styrene monomer used for producing the copolymer among the styrene monomers used.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours, and then the reaction was terminated. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, the reaction mixture was poured into a mixture of 75 kg of pure water and 2.32 kg of a 48% aqueous sodium hydroxide solution heated to 50 ° C. Further, the inside of the reactor used for the polymerization was washed with 113 kg of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 72 kg of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (A-1) was obtained.

The number average molecular weight of the obtained copolymer (A-1) was 48,041, and the molecular weight distribution was 1.55. Further, in the copolymer (A-1), the content of the polymer block (a) (specifically, the isobutylene block) mainly composed of isobutylene was 76% by weight. The number of allyl groups introduced into one molecule of the copolymer (A-1) was 2.3, and the rate of introduction of allyl groups into the terminal of the molecular chain was 77%. Table 1 shows the number average molecular weight and the like of the obtained copolymer (A-1).

The obtained copolymer (A-1) was granulated using a granulator 2TR-50A (head temperature 110 ° C.) manufactured by Moriyama Co., Ltd., and it was confirmed that the copolymer could be formed into a pellet shape.

In this way, by appropriately selecting the molecular weight of the copolymer and / or the content of the polymer block mainly composed of isobutylene, the allyl group-terminated styrene-isobutylene block copolymer can be molded into a pellet shape and handled. It can be seen that an easy copolymer can be obtained.

(Example 2) Synthesis of allyl group-terminated styrene-isobutylene block copolymer (A-2)
After nitrogen substitution in the container of the 1 L separable flask, 361 mL of butyl chloride (dried with molecular sieves) and 40 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 137.5 mL (1.46 mol) of isobutylene, 0.645 g (2.10 mmol) of tricmyllolide and 0.126 ml (1.28 mmol) of 2-methylpyridine (also known as α-picoline) were added to the obtained mixture. added. After confirming that the internal temperature of the mixture was −70 ° C. or lower, 0.83 mL (7.55 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. After stirring for 67 minutes from the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 99.8%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 32.1 ml (279 mmol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and when 83% of the added amount (charged amount) was consumed, 1.72 mL (9.43 mmol) of diallyldimethylsilane and 0.83 mL (7) of titanium tetrachloride were used. .55 mmol) was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours, and then the reaction was terminated. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, it was poured into a mixture of 185 mL of pure water and 13.9 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask was washed with 90 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v) and mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 190 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (A-2) was obtained.

The number average molecular weight of the obtained copolymer (A-2) was 63,916, and the molecular weight distribution was 1.36. Further, in the copolymer (A-2), the content of the polymer block (a) (specifically, the isobutylene block) mainly composed of isobutylene was 74% by weight. The number of allyl groups introduced into one molecule of the copolymer (A-2) was 2.5, and the rate of introduction of allyl groups into the terminal of the molecular chain was 83%. Table 1 shows the number average molecular weight and the like of the obtained copolymer (A-2).

(Example 3) Synthesis of allyl group-terminated styrene-isobutylene block copolymer (A-3)
After nitrogen substitution in the container of the 2 L separable flask, 1072 mL of butyl chloride (dried with molecular sieves) and 119 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 300 mL (3.16 mol) of isobutylene, 1.90 g (6.18 mmol) of trikmilk lolide and 0.366 ml (3.71 mmol) of 2-methylpyridine (also known as α-picoline) were added to the obtained mixture. .. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 2.37 mL (21.6 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. When the consumption rate of isobutylene was determined by gas chromatography (GC) 75 minutes after the start of the polymerization, it was confirmed that the consumption rate reached 98.5%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 94.6 ml (821 mmol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and when 82% of the added amount (charged amount) was consumed, 6.75 mL (37.1 mmol) of diallyldimethylsilane and 6.23 mL (56) of titanium tetrachloride were used. .8 mmol) was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours, and then the reaction was terminated. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, the reaction mixture was poured into a mixture of 560 mL of pure water and 45 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask used for the polymerization was washed with 300 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v) and mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 600 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes in the same manner. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (A-3) was obtained.

The number average molecular weight of the obtained copolymer (A-3) was 47,223, and the molecular weight distribution was 1.82. Further, in the copolymer (A-3), the content of the polymer block (a) (specifically, the isobutylene block) mainly composed of isobutylene was 67% by weight. The number of allyl groups introduced into one molecule of the copolymer (A-3) was 2.9, and the rate of introduction of allyl groups into the terminal of the molecular chain was 97%. Table 1 shows the number average molecular weight and the like of the obtained copolymer (A-3).

(Example 4) Synthesis of allyl group-terminated styrene-isobutylene block copolymer (A-4)
After nitrogen substitution in the container of a 500 mL separable flask, 270 mL of butyl chloride (dried with molecular sieves) and 30 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 87.8 mL (0.930 mol) of isobutylene, 0.200 g (0.650 mmol) of tricmyllolide and 0.128 ml (1.30 mmol) of 2-methylpyridine (also known as α-picoline) were added to the obtained mixture. added. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 1.00 mL (9.10 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. 55 minutes after the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 99.6%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 20.2 ml (176 mmol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and when 89% of the added amount (charged amount) was consumed, 0.71 mL (3.90 mmol) of diallyldimethylsilane and 1.00 mL (9) of titanium tetrachloride were used. .10 mmol) was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours, and then the reaction was terminated. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, the reaction mixture was poured into a mixture of 495 mL of pure water and 10 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask used for the polymerization was washed with 412 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 500 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes in the same manner. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation with water was performed two more times (three times in total), and the organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (A-4) was obtained.

The number average molecular weight of the obtained copolymer (A-4) was 103,919, and the molecular weight distribution was 1.39. Further, in the copolymer (A-4), the content of the polymer block (a) (specifically, the isobutylene block) mainly composed of isobutylene was 73% by weight. The number of allyl groups introduced into one molecule of the copolymer (A-4) was 2.2, and the rate of introduction of allyl groups into the terminal of the molecular chain was 73%. Table 1 shows the number average molecular weight and the like of the obtained copolymer (A-4).

(Example 5)
Table 2 shows the copolymer (A-1) obtained in Example 1, an olefin resin (polypropylene “J215W” manufactured by Prime Polymer Co., Ltd.), and a plasticizer (polybutene oil “100R” manufactured by Idemitsu Kosan Co., Ltd.). They were prepared at the ratio of parts by weight shown in (1) and melt-kneaded for 3 minutes using a lab plasticizer (manufactured by Toyo Seiki Co., Ltd.) set at 170 ° C. Next, a cross-linking agent (methyl hydrogen silicone "TSF484" manufactured by Momentive Performance Materials Japan Co., Ltd.) was added to the melt-kneaded product at the ratio shown in Table 2, and further, a cross-linking catalyst ("Pt-" manufactured by N.E. VTSC-3.0X ") was added to the melt kneaded product. Then, kneading was continued at 170 ° C. until the kneading torque reached the maximum value, and dynamic cross-linking was performed. As described above, an allyl group-terminated styrene-isobutylene block copolymer composition was obtained. The obtained composition (dynamic cross-linking composition) could be easily formed into a sheet by a pressure press (manufactured by Kondo Metal Industry Co., Ltd., set temperature 220 ° C.), and thus was a thermoplastic elastomer composition. It was confirmed that. Various physical properties of the obtained sheet-like composition were measured according to the above method. The results are shown in Table 2.

(Example 6)
A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the amount of the plasticizer used was changed, and various physical properties were evaluated. The results are shown in Table 2.

(Example 7)
A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the copolymer (A-2) obtained in Example 2 was used, and various physical properties were evaluated. The results are shown in Table 2.

(Example 8)
A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the copolymer (A-3) obtained in Example 3 was used, and various physical properties were evaluated. The results are shown in Table 2.

(Examples 9 to 16)
A thermoplastic elastomer composition was prepared in the same manner as in Example 8 except that the amounts of the olefin resin, the plasticizer, the cross-linking agent, and / or the cross-linking catalyst were used as shown in Table 2, and various physical properties were evaluated. .. The results are shown in Table 2.

(Example 17)
A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the copolymer (A-4) obtained in Example 4 was used, and various physical properties were evaluated. The results are shown in Table 2.

As shown in Example 1, the styrene-isobutylene block copolymer having an allyl group of the present invention is a polymer that can be treated as pellets, and as shown in Table 2, these block copolymers. It can be seen that the thermoplastic elastomer containing the above is excellent in compression set and flexibility.

(Example 18) Synthesis of allyl group-terminated styrene-isobutylene block copolymer (A-18)
After nitrogen substitution in the container of the 1 L separable flask, 340 mL of butyl chloride (dried with molecular sieves) and 40 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 100 mL (1.06 mol) of isobutylene, 0.66 g (2.15 mmol) of trikmilk lolide and 0.117 ml (1.18 mmol) of 2-methylpyridine (also known as α-picoline) were added to the obtained mixture. .. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 0.75 mL (6.86 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. The consumption rate of isobutylene was measured over time by gas chromatography (GC), and it was confirmed that the consumption rate reached 99.8%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 24.7 ml (215 mmol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and when 80% of the added amount (charged amount) was consumed, 1.70 mL (10.7 mmol) of diallyldimethylsilane and 1.41 mL (12) of titanium tetrachloride were consumed. .9 mmol) was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours, and then the reaction was terminated. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, the reaction mixture was poured into a mixture of 270 mL of pure water and 10.7 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask used for the polymerization was washed with 180 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 250 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes in the same manner. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (A-18) was obtained.

The number average molecular weight of the obtained copolymer (A-18) was 37,000, and the molecular weight distribution was 1.60. Further, in the copolymer (A-18), the content of the polymer block (a) (specifically, the isobutylene block) mainly composed of isobutylene was 76% by weight. The number of allyl groups introduced into one molecule of the copolymer (A-18) was 2.3, and the rate of introduction of allyl groups into the terminal of the molecular chain was 77%. Table 1 shows the number average molecular weight and the like of the obtained copolymer (A-18). A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the obtained copolymer (A-18) was used, and various physical properties were evaluated. The results are shown in Table 2.

（比較例１）アリル基末端スチレン−イソブチレンブロック共重合体の合成（Ｘ−１）
２Ｌのセパラブルフラスコの容器内を窒素置換した後、注射器を用いて塩化ブチル（モレキュラーシーブスで乾燥したもの）６５６ｍＬおよびヘキサン（モレキュラーシーブスで乾燥したもの）４５６ｍＬを加え、得られた混合物を約−７０℃まで冷却した。次に、得られた混合物にイソブチレン２００ｍＬ（２．１３ｍｏｌ）、ｐ−ジクミルクロリド２．６０ｇ（１１．２ｍｍｏｌ）およびＮ，Ｎ−ジメチルアセトアミド１．２２ｇ（１４．０ｍｍｏｌ）を加えた。得られた混合物の内温が−７０℃以下であることを確認した後、当該混合物に四塩化チタン９．９０ｍＬ（９０．３ｍｍｏｌ）を加えて重合を開始した。重合開始から９０分間撹拌を行った後、ガスクロマトグラフィー（ＧＣ）によりイソブチレンの消費率を求めたところ、消費率が９９．８％に達していることを確認した。なお、イソブチレンの消費率は、前記実施例１と同様の方法で測定し、算出した。

(Comparative Example 1) Synthesis of Allyl Group-Terminal Styrene-Isobutylene Block Copolymer (X-1)
After nitrogen substitution in the container of the 2 L separable flask, 656 mL of butyl chloride (dried with molecular sieves) and 456 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 200 mL (2.13 mol) of isobutylene, 2.60 g (11.2 mmol) of p-dicmilk lolide and 1.22 g (14.0 mmol) of N, N-dimethylacetamide were added to the obtained mixture. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 9.90 mL (90.3 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. After stirring for 90 minutes from the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 99.8%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 52 g (499 mmol) of styrene was added to the reaction mixture. The consumption of styrene was measured synchronically by GC, and when 80% of the addition amount (charged amount) was consumed, 12.0 mL (10.0 mmol) of allyltrimethylsilane was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 1 hour, and then 40 ml of methanol was added to terminate the reaction. After distilling off volatile components such as a solvent from the reaction solution, the obtained polymer was dissolved in toluene, and the same washing operation with pure water having the same volume as toluene was repeated twice (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (X-1) was obtained.

The number average molecular weight of the obtained copolymer (X-1) was 15,000, and the molecular weight distribution was 1.50. Further, in the copolymer (X-1), the content of the polymer block (a) (specifically, the isobutylene block) mainly composed of isobutylene was 73% by weight. The number of allyl groups introduced into one molecule of the copolymer (X-1) was 1.53, and the introduction rate of the allyl device to the end of the molecule was 51%. Table 1 shows the number average molecular weight and the like of the obtained copolymer (X-1).

Further, the obtained copolymer (X-1) had a low strength, and when stretched, it broke immediately after plastic deformation. When the broken sample pieces were pressed against each other, they strongly adhered to each other, resulting in a veil-like shape, and it was difficult to form a pellet shape.

As described above, conventionally known block copolymerization is inferior in moldability and may be difficult to handle, and there has been a strong demand for both physical properties of the resin and ease of handling.

(Comparative Example 2) Synthesis of Allyl Group-Terminated Styrene-Isobutylene Block Copolymer (X-2)
After nitrogen substitution in the container of a 500 mL separable flask, 254 mL of butyl chloride (dried with molecular sieves) and 28 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 100 mL (1.06 mol) of isobutylene, 0.470 g (1.53 mmol) of trikmilk lolide and 0.0868 g (0.932 mmol) of 2-methylpyridine (also known as α-picoline) were added to the obtained mixture. .. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 0.60 mL (5.50 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. After stirring for 60 minutes from the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 99.0%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 19.5 ml (170 mmol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and when 85% of the added amount (charged amount) was consumed, 0.42 mL (2.29 mmol) of diallyldimethylsilane was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours, and then the reaction was terminated. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, the reaction mixture was poured into a mixture of 500 mL of pure water and 3.1 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask used for the polymerization was washed with 400 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mechanical stirrer was vigorously stirred for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 500 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes in the same manner. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (X-2) was obtained.

The number average molecular weight of the obtained copolymer (X-2) was 43,806, and the molecular weight distribution was 1.52. Further, in the copolymer (X-2), the content of the polymer block (a) (specifically, the isobutylene block) mainly composed of isobutylene was 77% by weight. The number of allyl groups introduced into one molecule of the copolymer (X-2) was 0.9, and the rate of introduction of allyl groups into the terminal of the molecular chain was 30%. Table 1 shows the number average molecular weight and the like of the obtained copolymer (X-2).

A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the obtained copolymer (X-2) was used, and various physical properties were evaluated. The results are shown in Table 3.

表１〜３より、共重合体（Ｘ−２）を用いて作成された熱可塑性エラストマー組成物は、圧縮永久歪特性に劣ることがわかる。共重合体（Ｘ−２）は、数平均分子量（Ｍｎ）が３０，０００〜１３０，０００（ｇ／ｍｏｌ）であるが、一分子中のアリル基が２．１個以下である。

From Tables 1 to 3, it can be seen that the thermoplastic elastomer composition prepared by using the copolymer (X-2) is inferior in compressive permanent strain characteristics. The copolymer (X-2) has a number average molecular weight (Mn) of 30,000 to 130,000 (g / mol), but has 2.1 or less allyl groups in one molecule.

(Comparative Example 3) Synthesis of Allyl Group-Terminal Styrene-Isobutylene Block Copolymer (X-3)
After nitrogen substitution in the container of the 1 L separable flask, 463 mL of butyl chloride (dried with molecular sieves) and 51 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 100 mL (1.06 mol) of isobutylene, 0.112 g (0.364 mmol) of trikmilk lolide and 0.72 ml (7.28 mmol) of 2-methylpyridine (also known as α-picoline) were added to the resulting mixture. .. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 2.28 mL (20.7 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. After stirring for 60 minutes from the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 99.4%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 21.0 ml (182 mmol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and 0.23 mL (1.46 mmol) of allyltrimethylsilane was added to the reaction mixture when 85.4% of the added amount (charged amount) was consumed. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours to complete the reaction. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, the reaction mixture was poured into a mixture of 800 mL of pure water and 14.0 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask used for the polymerization was washed with 300 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 800 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes in the same manner. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (X-3) was obtained.

The number average molecular weight of the obtained copolymer (X-3) was 135,185, and the molecular weight distribution was 1.36. Further, in the copolymer (X-3), the content of the polymer block (a) (specifically, the isobutylene block) mainly composed of isobutylene was 76% by weight. The number of allyl groups introduced into one molecule of the copolymer (X-3) was 0.7, and the rate of introduction of allyl groups into the terminal of the molecular chain was 23%. Table 1 shows the number average molecular weight and the like of the obtained copolymer (X-3).

When the number average molecular weight of the copolymer, such as the copolymer (X-3), is large, the concentration of the reaction point is lowered, and it may be difficult to introduce the allyl group.

A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the obtained copolymer (X-3) was used, and various physical properties were evaluated. The results are shown in Table 3.

As shown in Tables 1 to 3, the thermoplastic elastomer composition prepared by using the copolymer (X-3) having 2.1 or less allyl groups in one molecule due to its large number average molecular weight It can be seen that it is inferior in compression set characteristics.

(Comparative Example 4) Synthesis of alkenyl group-terminated styrene-isobutylene block copolymer (X-4)
After nitrogen substitution in the container of a 500 mL separable flask, 260 mL of butyl chloride (dried with molecular sieves) and 29 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 100 mL (1.06 mol) of isobutylene, 0.470 g (1.53 mmol) of trikmilk lolide and 0.0868 g (0.932 mmol) of 2-methylpyridine (also known as α-picoline) were added to the resulting mixture. .. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 0.60 mL (5.50 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. After stirring for 67 minutes from the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 99.9%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 19.5 ml (170 mmol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and when 78% of the added amount (charged amount) was consumed, 3.46 mL (22.9 mmol) of 1,7-octadiene was added, followed by titanium tetrachloride. 0.60 mL (5.50 mmol) was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours to complete the reaction. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, the reaction mixture was poured into a mixture of 500 mL of pure water and 5.7 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask used for the polymerization was washed with 400 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 500 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes in the same manner. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an alkenyl group-terminated styrene-isobutylene block copolymer (X-4) was obtained.

The number average molecular weight of the obtained copolymer (X-4) was 45,833, and the molecular weight distribution was 1.62. The content of the polymer block (a) (specifically, isobutylene block) mainly composed of isobutylene in the copolymer (X-4) was 77% by weight. The number of alkenyl groups introduced into one molecule of the copolymer (X-4) was 2.5. Table 1 shows the number average molecular weight and the like of the obtained copolymer (X-4).

A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the obtained copolymer (X-4) was used, and various physical properties were evaluated. The results are shown in Table 3.

As shown in Table 3, the compressive permanent strain of the thermoplastic elastomer composition obtained in Comparative Example 4 was 45%, which was an insufficient result. Although the copolymer (X-4) has 2.5 allyl groups in one molecule, the compression permanent strain property is insufficient because the structure near the end of the polymer affects the cross-linking reaction. It is possible that there is. Although this mechanism is not always clear, the alkenyl group introduction reaction using the diene compound proceeds by the addition reaction to the olefin, so that the chlorine atom at the polymer terminal remains on the olefin carbon. It is presumed that the residual chlorine atom acts to inhibit the cross-linking reaction in some way, thereby impairing the rubbery properties of the obtained thermoplastic elastomer composition.

On the other hand, since the allyl group-terminated block copolymer of the present invention does not have a halogen atom in the vicinity of the allyl group, it is considered that an efficient cross-linking reaction proceeds.

(Comparative Example 5) Synthesis of Allyl Group-Terminated Styrene-Isobutylene Block Copolymer (X-5)
After nitrogen substitution in a 200 L reactor, 90 kg of butyl chloride and 7.5 kg of hexane were added and the resulting mixture was cooled to about −70 ° C. Next, 19.5 kg (348 mol) of isobutylene, 154 g (0.502 mol) of trikmilk lolide and 32.7 g (0.351 mmol) of 2-methylpyridine (also known as α-picoline) were added to the resulting mixture. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 429 g (2.26 mol) of titanium tetrachloride was added to the mixture to initiate polymerization. After stirring for 60 minutes from the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 98.9%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then, 6.27 kg (60.2 mol) of styrene was added to the reaction mixture. The consumption of styrene was measured over time by GC, and when 95% of the added amount (charged amount) was consumed, 229 g (2.01 mol) of allyltrimethylsilane and 381 g (2.01 mol) of titanium tetrachloride were added. Was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours, and then the reaction was terminated. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, the reaction mixture was poured into a mixture of 75 kg of pure water and 2.32 kg of a 48% aqueous sodium hydroxide solution heated to 50 ° C. Further, the inside of the reactor used for the polymerization was washed with 113 kg of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 72 kg of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an allyl group-terminated styrene-isobutylene block copolymer (X-5) was obtained.

The number average molecular weight of the obtained copolymer (X-5) was 49,172, and the molecular weight distribution was 1.54. Further, in the copolymer (X-5), the content of the polymer block (a) (specifically, isobutylene block) mainly composed of isobutylene is 76% by weight, and the number of allyl groups introduced is 1.5. The rate of introduction of allyl groups into the terminal of the molecular chain was 50%. Table 3 shows these physical properties of the obtained copolymer (X-5). Table 1 shows the number average molecular weight and the like of the obtained copolymer (X-5).

It was confirmed that the block copolymer (X-5) could be molded into a pellet shape in the same manner as in Example 1.

A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the obtained copolymer (X-5) was used, and various physical properties were evaluated. The results are shown in Table 3. As shown in Table 3, the compressive permanent strain of the thermoplastic elastomer composition obtained in Comparative Example 5 was 45%, which was an unsatisfactory result. It is considered that this result is due to the use of a copolymer (X-5) having a low number of allyl groups in one molecule of 1.5 in the production of the thermoplastic elastomer composition.

(Comparative Example 6) Synthesis of Allyl Group-Terminal Styrene-Isobutylene Block Copolymer (X-6)
After nitrogen substitution in the container of a 500 mL separable flask, 210 mL of butyl chloride (dried with molecular sieves) and 18 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, to the mixture obtained 85 mL (0.904 mol) of isobutylene, 0.142 g (0.61 mmol) of p-dicmilk lolide and 0.117 g (1.25 mmol) of 2-methylpyridine (also known as α-picoline). added. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 0.96 mL (8.76 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. When the consumption rate of isobutylene was determined by gas chromatography (GC), it was confirmed that the consumption rate reached 99.9%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then, 13.2 ml (114 mmol) of styrene was added to the reaction mixture, and after reacting for 40 minutes, 0.39 mL (2.46 mmol) of allyltrimethylsilane was added. After an additional 1 minute, 1.50 mL (13.7 mmol) of titanium tetrachloride was added to the reaction mixture.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 4 hours to complete the reaction. Next, the reaction mixture was poured into a mixture of 300 mL of pure water and 11 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask used for the polymerization was washed with 100 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the above reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 300 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes in the same manner. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, an alkenyl group-terminated styrene-isobutylene block copolymer (X-6) was obtained.

The number average molecular weight of the obtained copolymer (X-6) was 96,594, and the molecular weight distribution was 1.31. The content of the polymer block (a) (specifically, isobutylene block) mainly composed of isobutylene in the copolymer (X-6) was 80% by weight. The number of allyl groups introduced into one molecule of the copolymer (X-6) was 1.10. Table 1 shows the number average molecular weight and the like of the obtained copolymer (X-6).

A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the obtained copolymer (X-6) was used, and various physical properties were evaluated. The results are shown in Table 3.

As shown in Table 3, the compressive permanent strain of the thermoplastic elastomer composition obtained in Comparative Example 6 was 53%, which was an insufficient result. As described above, in the production of the copolymer (X-6), despite the fact that 4.0 equivalents of the allylic agent (allyltrimethylsilane) were used with respect to 1 equivalent of the polymerization initiator (dicumylloride). The number of allyl groups in one molecule of the obtained copolymer was insufficient. Therefore, the compression set of the obtained thermoplastic elastomer composition was also insufficient.

(Comparative Example 7) Synthesis of Allyl Group-Terminated Styrene-Isobutylene Block Copolymer (X-7)
Allyl group-terminated styrene-isobutylene in the same manner as in Comparative Example 6 (X-6) except that 0.39 mol (2.46 mmol) of allyltrimethylsilane in Comparative Example 6 was changed to 0.98 mol (6.14 mmol). A block copolymer (X-7) was obtained.

The number average molecular weight of the obtained copolymer (X-7) was 95,637, and the molecular weight distribution was 1.33. The content of the polymer block (a) (specifically, isobutylene block) mainly composed of isobutylene in the copolymer (X-7) was 80% by weight. The number of allyl groups introduced into one molecule of the copolymer (X-7) was 1.30. Table 1 shows the number average molecular weight and the like of the obtained copolymer (X-7).

A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the obtained copolymer (X-7) was used, and various physical properties were evaluated. The results are shown in Table 3.

As shown in Table 3, the compressive permanent strain of the thermoplastic elastomer composition obtained in Comparative Example 7 was 52%, which was an insufficient result.

From Comparative Examples 6 and 7, a thermoplastic elastomer composition prepared by using a copolymer having 2.1 or less allyl groups in one molecule even if the number average molecular weight is within the range of the present invention is It can be seen that the rubber properties are inferior.

(Comparative Example 8) Synthesis of Allyl Group-Terminal Styrene-Isobutylene Block Copolymer (X-8)
After nitrogen substitution in the container of a 500 mL separable flask, 224 mL of butyl chloride (dried with molecular sieves) and 25 mL of hexane (dried with molecular sieves) were added using a syringe, and the obtained mixture was about-. It was cooled to 70 ° C. Next, 85 mL (0.901 mol) of isobutylene, 0.300 g (1.30 mmol) of dicumyl lolide and 0.0726 g (0.779 mmol) of 2-methylpyridine (also known as α-picoline) were added to the obtained mixture. .. After confirming that the internal temperature of the obtained mixture was −70 ° C. or lower, 0.50 mL (4.57 mmol) of titanium tetrachloride was added to the mixture to initiate polymerization. After stirring for 67 minutes from the start of the polymerization, the consumption rate of isobutylene was determined by gas chromatography (GC), and it was confirmed that the consumption rate reached 99.4%. The consumption rate of isobutylene was measured and calculated by the same method as in Example 1 above.

Then 19.9 ml (173 mmol) of styrene was added to the reaction mixture. The amount of styrene consumed was measured over time by GC, and when 80% of the added amount (charged amount) was consumed, 0.710 mL (3.89 mmol) of diallyldimethylsilane and 0.50 mL (4) of titanium tetrachloride were used. .57 mmol) was added to the reaction mixture. The styrene consumption rate was measured and calculated in the same manner as in Example 1.

Then, while keeping the reaction mixture at −70 ° C. or lower, stirring was continued for another 3 hours, and then the reaction was terminated. At this time, it was confirmed by GC that the entire amount of styrene was consumed. Next, it was poured into a mixture of 500 mL of pure water and 20.0 g of a 48% aqueous sodium hydroxide solution heated to 55 ° C. Further, the separable flask used for the polymerization was washed with 400 g of a mixed solvent of butyl chloride and hexane (mixing ratio 9: 1, v / v), and this washing liquid was also mixed with the reaction mixture. It was confirmed that the internal temperature of the obtained reaction mixture reached 50 ° C. Then, the mixture was vigorously stirred with a mechanical stirrer for 60 minutes. After stirring for 60 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. Next, 500 mL of pure water was added to the organic phase, and the organic phase was washed with water by vigorously stirring at 55 ° C. for 30 minutes in the same manner. After stirring for 30 minutes, the stirring was stopped, the organic phase and the aqueous phase were separated, and the separated aqueous phase was discharged. The same washing operation was repeated twice more (three times in total). The organic phase thus obtained was separated, and volatile components such as a solvent in the organic phase were distilled off under a heating vacuum and dried. As described above, a linear allyl group-terminated styrene-isobutylene block copolymer (X-8) was obtained.

The number average molecular weight of the obtained copolymer (X-8) was 47,917, and the molecular weight distribution was 1.67. Further, in the copolymer (X-8), the content of the polymer block (a) (specifically, isobutylene block) mainly composed of isobutylene was 74% by weight. The number of allyl groups introduced into one molecule of the copolymer (X-8) was 1.7, and the rate of introduction of allyl groups into the terminal of the molecular chain was 85%. Moreover, the obtained copolymer (X-8) could be molded into a pellet shape. Table 1 shows the number average molecular weight and the like of the obtained copolymer (X-8).

A thermoplastic elastomer composition was prepared in the same manner as in Example 5 except that the obtained copolymer (X-8) was used, and various physical properties were evaluated. Table 3 shows these physical properties of the obtained copolymer (X-8). As shown in Tables 1 to 3, even in the case of a copolymer having no group represented by the general formula (1), the rubber property is impaired unless the number of allyl groups introduced exceeds 2.1. You can see that.

Next, with respect to the copolymer having a group represented by the general formula (1) (Example 5) and the copolymer having no group represented by the general formula (1) (Comparative Example 8). Furthermore, the physical properties of rubber were examined.

The copolymer used in Example 5 (the copolymer obtained in Example 1 and the copolymer (A-1)) and the copolymer used in Comparative Example 8 (X-8). As a result of measuring the MFR of), the MFR of the copolymer (A-1) was 5.37 g / 10 min, and the MFR of the copolymer (X-8) was 0.275 g / 10 min.

Although the copolymer (A-1) and the copolymer (X-8) have similar number average molecular weights and molecular weight distributions to each other, there is a very large difference in the value of MFR. There was found. It is considered that this difference is derived from the group represented by the general formula (1) possessed by the copolymer (A-1) of the present invention. From this, it can be seen that the copolymer having a group represented by the general formula (1) is a polymer having excellent handleability.

Next, the heat resistance was evaluated using the thermoplastic elastomer compositions obtained in Example 5 and Comparative Example 8. The results are shown in Table 4.

表４より、本発明の一実施形態に係る熱可塑性エラストマー組成物は、耐熱性に優れることが分かる。一般に動的架橋組成物中のゴム成分はマトリックス樹脂中に微分散していることが知られており、熱可塑性エラストマー組成物のマクロな熱的特性はマトリックス樹脂に異存すると考えられる。

From Table 4, it can be seen that the thermoplastic elastomer composition according to the embodiment of the present invention has excellent heat resistance. It is generally known that the rubber component in the dynamic cross-linking composition is finely dispersed in the matrix resin, and it is considered that the macrothermal properties of the thermoplastic elastomer composition are different from the matrix resin.

However, it has been found that the heat resistance of the thermoplastic elastomer composition itself can be improved by using the polymer into which the branched structure of the present invention is introduced.
Next, the creep resistance was evaluated using the thermoplastic elastomer compositions obtained in Example 5 and Comparative Example 8. The results are shown in Table 5.

表１〜５に示す結果から、本発明の熱可塑性エラストマー組成物は、低モジュラスでありながら、優れた耐クリープ性を示すことがわかる。

From the results shown in Tables 1 to 5, it can be seen that the thermoplastic elastomer composition of the present invention exhibits excellent creep resistance while having low modulus.

Generally, the restoring force against deformation is expected to depend on the modulus of the rubber material, and it was common to design a highly modulus composition in order to improve the creep resistance. However, according to the thermoplastic elastomer composition of the present invention, it can be seen that the flexibility and creep resistance of the rubber material can be compatible with each other.

Next, the solvent resistance was evaluated using the thermoplastic elastomer compositions obtained in Example 5 and Comparative Example 8. The results are shown in Table 6.

表６に示すように、一般式（１）で示される基を有する共重合体を含む組成物は耐溶剤性に優れることがわかる。

As shown in Table 6, it can be seen that the composition containing the copolymer having the group represented by the general formula (1) is excellent in solvent resistance.

From the above, the allyl group-terminated styrene-isobutylene block copolymer of the present invention is excellent in flexibility, compression set, fluidity, heat resistance, creep resistance, and solvent resistance as compared with conventionally known ones. It can be seen that a thermoplastic elastomer composition can be provided.

The allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention is easy to handle, has desired rubber physical properties, and can be pelletized. Therefore, the allyl group-terminated styrene-isobutylene block copolymer according to one embodiment of the present invention is a sealing material such as a packing material, a sealing material, a gasket, and a stopper; a damper; a control for automobiles, vehicles, and home appliances. Vibration materials and anti-vibration materials; Automotive interior materials; Cushion materials; Daily necessities, electrical parts, electronic parts, sports parts, etc., grip materials, cushioning materials, and packaging materials; Electric wire coating materials such as electrical parts; Various containers; Stationery It can be suitably used for parts and the like.

Claims (10)

It has an allyl group at the end of the molecular chain
It is composed of a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of styrene.
The number average molecular weight (Mn) in terms of standard polystyrene measured by gel permeation chromatography is 30,000 to 130,000 (g / mol).
The molecular weight distribution (Mw / Mn) is 1.10 to 2.00.
The content of the polymer block (a) mainly composed of isobutylene is 50 to 90% by weight.
It has a group represented by the following general formula (1) in the molecular chain.

(In the general formula (1), R ¹ and R ² represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different. Also, a plurality of R ¹ and R ² may be the same group or different groups, respectively.)
An allyl group-terminated styrene-isobutylene block copolymer characterized by having more than 2.1 allyl groups and 3.0 or less allyl groups in one molecule. The allyl group-terminated styrene-isobutylene block copolymer according to claim 1, wherein R ¹ and R ² in the general formula (1) are methyl groups. The allyl group-terminated styrene-isobutylene block copolymer according to claim 1 or 2, wherein the isobutylene-based polymer block (a) contains 80% by weight or more of a unit derived from isobutylene. The allyl group-terminated styrene-isobutylene block according to any one of claims 1 to 3, wherein the styrene-based polymer block (b) contains 80% by weight or more of styrene-derived units. Copolymer. The allyl group-terminated styrene-isobutylene block copolymer according to any one of claims 1 to 4, wherein the allyl group-terminated styrene-isobutylene block copolymer is in the form of pellets. The first step of mixing a styrene monomer and an isobutylene monomer to obtain a styrene-isobutylene block copolymer, and
It has a second step of mixing the styrene-isobutylene block copolymer and the allylic agent until the consumption rate of the styrene monomer reaches 90%.
The allyl group-terminated styrene-isobutylene block copolymer according to any one of claims 1 to 5, wherein a compound represented by the following general formula (2) is used as the polymerization initiator in the first step. Production method.

(R ¹ and R ² represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different, and a plurality of R may be present. ¹ and R ² may be the same group or different groups, respectively. X is a group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms and an asyloxyl group having 1 to 6 carbon atoms. Represents the monovalent organic group selected.) (A) The allyl group-terminated styrene-isobutylene block copolymer according to any one of claims 1 to 6, and
The olefin resin (B) is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the (A) allyl group-terminated styrene-isobutylene block copolymer.
An allyl group-terminated styrene-isobutylene block copolymer composition. The allyl group-terminated styrene according to claim 7, wherein 1 to 300 parts by weight of (C) a plasticizer is further contained with respect to 100 parts by weight of the (A) allyl group-terminated styrene-isobutylene block copolymer. -Isobutylene block copolymer composition. It has a step of melt-kneading the (A) allyl group-terminated styrene-isobutylene block copolymer and the (B) olefin resin.
The allyl group-terminated styrene-isobutylene block copolymer composition according to claim 7 or 8, wherein in the melt-kneading step, the allyl group-terminated styrene-isobutylene block copolymers are subjected to a dynamic cross-linking reaction. Manufacturing method. The method for producing an allyl group-terminated styrene-isobutylene block copolymer composition according to claim 9, wherein the dynamic cross-linking reaction is a hydrosilylation reaction.