WO2019013298A1 - Brominated polyisobutylene polymer and method for producing same - Google Patents

Abstract

To provide a brominated polyisobutylene-based polymer which exhibits (a) excellent vulcanization reactivity and (b) an excellent balance between rubber strength and gas barrier properties. This is achieved by a brominated polyisobutylene-based polymer characterized by containing a specific amount of a non-brominated methylstyrene group and a brominated methylstyrene group as constituent units.

Description

Brominated polyisobutylene polymer and method for producing the same

The present invention relates to a brominated polyisobutylene-based polymer and a method for producing the same.

Polyisobutylene-based polymers containing isobutylene as a main component have excellent flexibility and gas barrier properties. Therefore, polyisobutylene polymers are widely used as various seal members. As polyisobutylene polymers, for example, isobutylene-isoprene polymers, halogenated isobutylene-isoprene polymers, isobutylene-methylstyrene polymers, and halogenated isobutylene-methylstyrene polymers are known.

In general, a polymer having a chlorine group and / or a bromine group is more likely to have a higher vulcanization reactivity than a polymer having no halogen group, and as a result, the productivity is improved. In addition, a polymer having a bromine group tends to have a higher vulcanizability than a polymer having a chlorine group, and as a result, the productivity is improved. Therefore, polymers having a chlorine group and / or a bromine group, particularly polymers having a bromine group, are suitably used as various rubber members.

Patent documents 1 to 3 disclose a method for brominating isobutylene-methylstyrene polymer, a brominated isobutylene-methylstyrene polymer, and use of the brominated isobutylene-methylstyrene polymer.

An isobutylene-styrene block copolymer is known as another isobutylene polymer. The isobutylene-isoprene polymer and the isobutylene-methylstyrene polymer described above exhibit plastic deformation when they are not crosslinked (low green strength). On the other hand, the isobutylene-styrene block copolymer itself has appropriate strength, and the isobutylene-styrene block copolymer is provided in the form of pellets. Therefore, isobutylene-styrene block copolymers have the advantage of being easier to handle than isobutylene-isoprene polymers and isobutylene-methylstyrene polymers.

Patent Document 4 discloses an isobutylene-styrene-based block copolymer produced using chloromethylstyrene.

Patent Document 5 discloses a styrene-isobutylene block copolymer containing a brominated methylstyrene group in an isobutylene segment.

JP-A-2-150408 Japanese Patent Publication No. 2010-531386 Japanese Patent Application Publication No. 2002-544357 JP, 2012-087201, A WO 2000-040631

However, the prior art as described above provides a brominated polyisobutylene-based polymer that exhibits (a) excellent vulcanization reactivity and (b) an excellent balance between rubber strength and gas barrier properties. From the point of view, it was not enough and there was room for further improvement.

One embodiment of the present invention is made in view of the above-mentioned subject, and the object is (a) showing the outstanding vulcanization reactivity, and excellent in the balance of (b) rubber strength and gas barrier property. Another object is to provide a novel brominated polyisobutylene-based polymer.

As a result of intensive studies to solve the above problems, the present inventor (a) has an excellent vulcanization reaction by containing a specific amount of a methylstyrene group which is not brominated and a brominated methylstyrene group as constituent units. It has been found that it is possible to provide a brominated polyisobutylene-based polymer which exhibits good properties and is excellent in the balance between (b) rubber strength and gas barrier property, and the present invention has been completed.

That is, in one embodiment of the present invention, a total of 100 moles of a methylbrominated methylstyrene group and a brominated methylstyrene group which are not brominated and a total of 100 mols of the non-brominated methylstyrene group and the brominated methylstyrene group as constituent units. Bromine characterized in that it contains 65 mol% or more of the brominated methylstyrene group with respect to%, and contains 1.00 mol% or more of the brominated methylstyrene group with respect to 100 mol% of the total of the constituent units. A polyisobutylene-based polymer.

According to one embodiment of the present invention, it is possible to provide a brominated polyisobutylene-based polymer that exhibits (a) excellent vulcanization reactivity and (b) an excellent balance between rubber strength and gas barrier properties. Play an effect.

Although one embodiment of the present invention is described below, the present invention is not limited to this. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. Further, embodiments or examples obtained by appropriately combining the technical means respectively disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the academic literature and patent documents described in the present specification are incorporated herein by reference. Also, unless otherwise specified herein, “A to B” representing a numerical range intends “more than A (including A and greater than A) B or less (including B and less than B)”.

As a result of intensive studies by the inventor, the inventors have found that the techniques described in the above-mentioned prior art documents 1 to 5 have the following problems or room for improvement.

Patent Documents 1 to 3 disclose, as mentioned above, brominated isobutylene-methylstyrene polymer and the like. However, known butyl rubbers, halogenated butyl rubbers, and halogenated isobutylene-alkylstyrene copolymers have the problem of low green strength because (a) they themselves do not have a crosslinking point, and (b ) There is a problem that handling is difficult because it is provided in a bale shape. All the polymers disclosed in Patent Documents 1 to 3 do not have a polystyrene block, and therefore are not thermoplastic elastomers. In addition, "green strength" means the strength of the compounded rubber in an unvulcanized state. High green strength or excellent green strength means that the unvulcanized rubber blend can be easily processed or molded.

Patent Document 4 discloses an isobutylene-styrene-based block copolymer produced using chloromethylstyrene. The technology described in Patent Document 4 can solve the problem that isobutylene-styrene block copolymer having no functional group does not exhibit vulcanization reactivity and may not satisfy various physical properties required as a rubber member. It was a thing. The present inventors noticed that chloromethylstyrene used in the technology described in Patent Document 4 is a difficult-to-handle raw material. That is, the inventor has found that the technology described in Patent Document 4 has room for improvement in terms of the handleability of the raw material.

The styrene-isobutylene block copolymer disclosed in Patent Document 5 is insufficient in terms of the properties as a rubber member.

The inventor of the present invention has thoroughly studied to solve the above-mentioned problems and points of improvement, and as a result, it is brominated which shows (a) excellent vulcanization reactivity and (b) excellent balance between rubber strength and gas barrier properties. It has been found that a polyisobutylene-based polymer can be provided. Such a brominated polyisobutylene-based polymer can be achieved by the brominated polyisobutylene-based polymer including a specific amount of a non-brominated methylstyrene group and a brominated methylstyrene group as constituent units. In addition, in patent document 4, it is not specifically examined about introduction | transduction of a bromine containing functional group. Furthermore, in Patent Document 4, (a) relationship between the amount of bromine-containing functional group and vulcanization reactivity, and (b) a method for producing an isobutylene-based block copolymer in which a large amount of bromine-containing functional group is introduced. Also, is not disclosed.

[2. Brominated polyisobutylene polymer]
A brominated polyisobutylene-based polymer according to an embodiment of the present invention includes, as constituent units, a non-brominated methylstyrene group and a brominated methylstyrene group, and the non-brominated methylstyrene group and the above-mentioned bromine The brominated methylstyrene group is contained in an amount of 65 mol% or more based on 100 mol% of the total amount of methylated methyl styrene groups, and 1.00 mol% of the brominated methylstyrene group based on 100 mol% of the total amount of the constituent units It is characterized by including the above.

The brominated polyisobutylene-based polymer according to one embodiment of the present invention has (a) excellent vulcanization reactivity and (b) excellent balance between the rubber strength and the gas barrier property because it has the above-mentioned configuration. It has the advantage of being

The brominated polyisobutylene-based polymer can be obtained by brominating a polymer containing methylstyrene groups. Here, in order to introduce a large amount of brominated methylstyrene groups, the inventors of the present invention inhibit polymerization when a large amount of methylstyrene is used for producing a polymer, and a polymer having a sufficiently high molecular weight can not be obtained. I found that for the first time. As a result of intensive investigations, the inventors of the present invention have found that (a) a polymer of high molecular weight can be obtained by using a suitable amount of methylstyrene to produce a polymer, and (b) a weight containing a methylstyrene group. In the coalescence, a polymer containing a large amount of brominated methylstyrene groups can be obtained by brominating 65 mol% or more of the methylstyrene groups with respect to the total 100 mol% of methylstyrene groups in the polymer. I found it for the first time. As a result, the inventors have come to provide a polymer excellent in both strength and vulcanization reactivity, that is, a brominated polyisobutylene-based polymer according to an embodiment of the present invention.

In the present specification, the "brominated polyisobutylene polymer according to one embodiment of the present invention" is also referred to as "the present brominated polyisobutylene polymer". In the present specification, a non-brominated methylstyrene group as a constitutional unit may also be referred to as a "non-brominated methylstyrene unit", and a brominated methylstyrene group as a constitutional unit is It may be called "styrene unit".

The brominated polyisobutylene-based polymer may further contain an isobutylene group as a structural unit. In the present specification, an isobutylene group as a constituent unit may be referred to as an "isobutylene unit". The polymer composition of the brominated polyisobutylene-based polymer is not particularly limited as long as the brominated polyisobutylene-based polymer contains a non-brominated methylstyrene group and a brominated methylstyrene group as constituent units. The present brominated polyisobutylene-based polymer preferably contains 50% by weight or more of isobutylene group as a constituent unit with respect to 100% by weight of the brominated polyisobutylene-based polymer. If it is the said structure, a brominated polyisobutylene type | system | group polymer has the advantage that favorable gas barrier property, a softness | flexibility, and heat resistance can be expressed.

The structure of the brominated polyisobutylene polymer may be either a random copolymer or a block copolymer, but a block copolymer is preferable because it can produce a thermoplastic elastomer excellent in green strength. Is preferred.

When the structure of the brominated polyisobutylene-based polymer is a block copolymer, the brominated polyisobutylene-based polymer can not only exhibit rubber elasticity but also be pelletized without undergoing a crosslinking step. . Therefore, it is easy to handle with an extruder or the like, and since it is a material that can be reworked even after molding, it has the advantage of low environmental impact.

Brominated polyisobutylene block copolymer
The brominated polyisobutylene polymer is a brominated polyisobutylene block copolymer comprising a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of an aromatic vinyl compound It is preferably a block copolymer comprising a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of an aromatic vinyl compound. If it is the said structure, a brominated polyisobutylene type polymer can express rubber elasticity, without passing through a bridge | crosslinking process, and it can be made not only excellent in green strength but pellet shape. Therefore, it is easy to handle with an extruder or the like, and since it is a material that can be reworked even after molding, it has the advantage of low environmental impact.

A brominated polyisobutylene block copolymer according to one embodiment of the present invention is composed of a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of an aromatic vinyl compound. There are no particular restrictions on the structure of the For example, a block copolymer having a linear, branched or star-like structure, a diblock copolymer, a triblock copolymer, a multiblock copolymer, and any group selected from these groups Any mixture of two or more structures can be selected.

As a preferable structure from the viewpoint of balance of physical properties and molding processability, a polymer block (b) mainly composed of an aromatic vinyl compound is provided at both ends, and a polymer block mainly composed of isobutylene is interposed therebetween. (A) (b)-(a)-(b) type triblock copolymer, a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of isobutylene (a)-(b) Type diblock copolymers can be mentioned.

The content of the polymer block (a) mainly composed of isobutylene in the total weight (100% by weight) of the brominated polyisobutylene block copolymer is preferably 20 to 95% by weight, more preferably 50 It is ̃90% by weight. If the content of the polymer block (a) mainly composed of isobutylene in the total weight (100% by weight) of the brominated polyisobutylene block copolymer exceeds 95% by weight, handling as pellets becomes difficult, The copolymer becomes baled. Therefore, the handleability at the time of processing deteriorates. In addition, when the content of the polymer block (a) mainly composed of isobutylene in the total weight (100% by weight) of the brominated polyisobutylene block copolymer is less than 20%, the hardness of the copolymer becomes high. It's going to be too soft. Therefore, the performance as an elastomer material can not be exhibited sufficiently.

The number average molecular weight of the brominated polyisobutylene polymer is not particularly limited, but is preferably 5,000 to 1,000,000, and 10,000 to 500,000 in terms of polystyrene equivalent as measured by gel permeation chromatography. Is particularly preferred. When the number average molecular weight of the brominated polyisobutylene-based polymer is less than 5,000, mechanical properties may not be sufficiently expressed, and as a result, the performance as an elastomeric material may be inferior. When the number average molecular weight of the brominated polyisobutylene-based polymer exceeds 1,000,000, the decrease in fluidity, processability and moldability becomes remarkable, and as a result, the handling at the time of production becomes difficult There is a case.

The molecular weight distribution (the numerical value represented by the ratio of weight average molecular weight Mw to number average molecular weight Mn (Mw / Mn)) of the brominated polyisobutylene polymer is preferably 1.0 to 3.0, and 1.0 Those in the range of -2.0 are more preferred. According to the above configuration, there is an advantage that the melt viscosity of the resin can be lowered while maintaining an appropriate viscosity. When the molecular weight distribution of the brominated polyisobutylene-based polymer exceeds 3.0, the uniformity of the molecular weight is low, and the viscosity in the molten state may be too low or too high. Therefore, it is not preferable in terms of processing stability, and the workability may be deteriorated.

The gas barrier properties of the brominated polyisobutylene-based polymer can be evaluated by the oxygen permeation coefficient. The brominated polyisobutylene-based polymer preferably has an oxygen permeability coefficient of 0.0 to 10.0 × 10 ⁻¹⁶ (mol · m / (m ² · sec · Pa)). According to the above configuration, the brominated polyisobutylene-based polymer can be expected to have the same gas barrier property as that of a known butyl rubber. The oxygen permeability coefficient is a value measured according to the method described in JIS K-7126.

The rubber strength of the brominated polyisobutylene-based polymer is evaluated by tensile strength. That is, in the present specification, "rubber strength" is also referred to as "tensile strength", and the terms "rubber strength" and the term "tensile strength" are mutually interchangeable. The brominated polyisobutylene polymer preferably has a tensile strength of 5.00 to 30.00 MPa. According to the above configuration, since the green strength is sufficient, there is an advantage that the productivity is not reduced. Moreover, according to the said structure, the melt viscosity at the time of shaping | molding does not become too high, but it becomes appropriate melt viscosity. Therefore, there is an advantage that no unevenness is observed on the surface of the molded product, the surface of the molded product becomes beautiful, and the designability is increased. The tensile strength is a value measured in accordance with the method described in JIS K-6251.

The brominated polyisobutylene-based polymer preferably has a vulcanization reactivity of 70 to 300 N / 25 mm, more preferably 70 to 200 N / 25 mm, and 70 to 180 N / 25 mm, as evaluated by the method described later. Being particularly preferred. According to the above configuration, there is an advantage that appropriate vulcanization reactivity and productivity can be maintained in a well-balanced manner.

<Polymer block mainly composed of isobutylene (a)>
A polymer block containing isobutylene as a main component is composed of 50% by weight or more, preferably 80% by weight or more of units derived from isobutylene because the mechanical properties of the resulting copolymer as an elastomer are excellent. It is preferably a polymer block. When the unit derived from isobutylene is less than 50% by weight, a polymer block mainly composed of isobutylene is not preferable because it may have poor gas barrier properties.

In addition, it may be a polymer block essentially consisting only of isobutylene, or may contain a constitutional unit derived from a monomer other than isobutylene as long as the effects according to one embodiment of the present invention are not impaired. It is also good.

The monomer other than isobutylene is not particularly limited as long as it is a monomer which can be cationically polymerized with isobutylene, but, for example, aliphatic olefins, aromatic vinyl compounds, dienes, vinyl ethers, silanes, vinylcarbazole, β-pinene And monomers such as acenaphthylene. These may be used alone or in combination of two or more.

<Polymer block mainly composed of aromatic vinyl compound (b)>
The polymer block mainly composed of the aromatic vinyl compound is preferably a polymer block composed of 60% by weight or more, preferably 80% by weight or more of a unit derived from the aromatic vinyl compound.

Examples of the aromatic vinyl compounds include styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o -Methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2 , 4,6-Trimethylstyrene, α-Methyl-2,6-dimethylstyrene, α-Methyl-2,4-dimethylstyrene, β-Methyl-2,6-dimethylstyrene, β-Methyl-2,4-dimethyl Styrene, o-, m- or p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m -Chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α -Chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-, m- or p -T-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-bromomethylstyrene, silyl-substituted styrene derivatives, Examples thereof include indene and vinyl naphthalene. Among these, styrene, methylstyrene (o-isomer, m-isomer or p-isomer), α-methylstyrene, indene, or a mixture thereof from the viewpoint of industrial availability, price, and glass transition temperature Is preferred, and styrene is particularly preferred in view of good availability.

Moreover, as for any of the above-mentioned polymer blocks, mutual monomers can be used as a copolymerization component, and other cationically polymerizable monomer components can be used. Examples of such monomer components include monomers such as aliphatic olefins, dienes, vinyl ethers, silanes, vinyl carbazole and acenaphthylene. These can be used alone or in combination of two or more.

In the brominated polyisobutylene-based polymer, a methylstyrene group that is not brominated is a p-methylstyrene (4-methylstyrene) group, and a brominated methylstyrene group is a p-bromomethylstyrene (4 It is preferable that it is -bromomethylstyrene) group. With this configuration, the brominated polyisobutylene polymer is excellent in vulcanization reactivity, reactivity with different rubber members, flexibility, flex fatigue, low temperature characteristics, rubber physical properties, mechanical properties and the like. Have an advantage.

<Methylstyrene>
Examples of methylstyrenes which can be used when producing the brominated polyisobutylene polymer include o-methylstyrene, m-methylstyrene and p-methylstyrene, and the availability and reactivity of p-methylstyrene, And preferred in view of rubber physical properties.

<Bromomethylstyrene group>
The present brominated polyisobutylene-based polymer can be obtained by brominating an isobutylene-based polymer having a structure of the following general formula (1).

　一般式（１）のメチル基（－ＣＨ_３）の位置はオルト（ｏ）位、メタ（ｍ）位、パラ（ｐ）位のいずれでも構わないが、原料の入手性や反応性の点から、メタ位かまたはパラ位に置換基を有することが好ましい。

The position of methyl group (-CH ₃ ) in the general formula (1) may be any of ortho (o) position, meta (m) position and para (p) position, but from the viewpoint of availability and reactivity of raw materials It is preferable to have a substituent at the meta or para position.

Depending on the copolymerization conditions with a monomer mainly composed of isobutylene, p-methylstyrene has higher copolymerizability than m-methylstyrene, and a polymer having excellent mechanical properties may be obtained. Therefore, it is most preferable to use p-methylstyrene as a raw material.

The structure represented by the general formula (1) is preferably 1.0 to 50.0% by mole, based on 100.0% by mole of all the structural units constituting the isobutylene polymer, and 1.5 to 30%. It is more preferable that the content be 0.2 mol%. If the amount is less than 1.0 mol%, the content of the bromomethylstyrene group is reduced, and the vulcanization reactivity and the reactivity with different rubber members may not be sufficient. If it exceeds 50.0 mol%, the flexibility, bending fatigue resistance, low temperature properties and the like of the brominated polyisobutylene polymer are impaired, and the advantage may be reduced economically, which is not preferable.

The brominated polyisobutylene-based polymer in one embodiment of the present invention is obtained by brominating an isobutylene-based polymer having the structure of the general formula (1). The bromination method is not particularly limited, but it is preferable to obtain a brominated polyisobutylene-based polymer having the following general formula (2) by reacting with bromine under light irradiation of a specific wavelength. That is, the brominated polyisobutylene-based polymer in one embodiment of the present invention has the following [3. Production Method of Brominated Polyisobutylene-Based Polymer] It is preferable that the production is carried out using the production method described in the section above.

　特許文献１、２に開示されている重合体は、その主鎖中に導入されたメチルスチレン基のうち６０モル％以下が臭素化されたものである。一方、本発明における臭素化ポリイソブチレン系重合体は、導入されたメチルスチレンユニットのうち、６５モル％以上がブロモメチルスチレン基へと置換された構造を有する。６５モル％未満の変換効率の場合、加硫反応性や異種ゴム部材に対する反応性が所望の水準に達しない場合があるため好ましくない。さらには、臭素化ポリイソブチレン系重合体の構成単位（構成モノマー単位とも称する）に占めるブロモメチルスチレン基の割合が１．００モル％以上であることが好ましい。

The polymers disclosed in Patent Documents 1 and 2 are those in which 60 mol% or less of the methylstyrene group introduced in the main chain is brominated. On the other hand, the brominated polyisobutylene-based polymer in the present invention has a structure in which 65 mol% or more of the introduced methylstyrene units is substituted with a bromomethylstyrene group. If the conversion efficiency is less than 65% by mole, it is not preferable because the vulcanization reactivity and the reactivity to different rubber members may not reach desired levels. Furthermore, it is preferable that the ratio of the bromomethylstyrene group to the constituent unit (also referred to as constituent monomer unit) of the brominated polyisobutylene-based polymer is 1.00 mol% or more.

As a method of increasing the content of the bromomethylstyrene group, for example, it is conceivable to introduce a large number of methylstyrene groups. However, this method is not preferable because the glass transition temperature of the polymer becomes high, and the excellent flexibility, bending fatigue property, low temperature characteristics and the like as a rubber member are impaired. Thus, there is a need for a method to increase the efficiency of converting methylstyrene groups to bromomethylstyrene groups.

The bromination method disclosed in Patent Document 5 is bromination with a high-power lamp, in which 32% of paramethylstyrene groups are brominated. In this case, the remaining para-methylstyrene group is not preferable because it has no activity for vulcanization and may cause the above-mentioned problems.

The structure represented by the general formula (2) is preferably 1.00 mol% or more and 50.00 mol% or less with respect to 100 mol% of all constituent units constituting the brominated polyisobutylene polymer, and 1 The content is more preferably not less than 0.00 mol% and not more than 30.00 mol%, and particularly preferably not less than 1.00 mol% and not more than 10.00 mol%. If it is less than 1.00 mol%, it is not preferable because the vulcanization reactivity and the reactivity with different rubber members may be poor.

A brominated polyisobutylene-based polymer produced in one embodiment of the present invention comprises a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of an aromatic vinyl compound In the case of an isobutylene-based block copolymer, the positions at which the structures represented by the general formula (1) and the general formula (2) are introduced are introduced into the polymer block (a) mainly composed of isobutylene It may be introduced into the polymer block (b) mainly composed of an aromatic vinyl compound or may be introduced into both of the blocks.

The total amount of the structures represented by the general formulas (1) and (2) in the brominated polyisobutylene polymer is set to 100% in order to express satisfactory vulcanization reactivity and reactivity to different rubber members. It is preferable that at least 50% by weight of the structure represented by the general formulas (1) and (2) be introduced into the polymer block (a) mainly composed of isobutylene, and 70% by weight or more is introduced. It is more preferable that 90% by weight or more is introduced. That is, in the present brominated polyisobutylene polymer, the block (a) composed mainly of isobutylene is the total amount of unbrominated methylstyrene groups and brominated methylstyrene groups in the brominated polyisobutylene polymer. It is preferable to contain 50% by weight or more of non-brominated methylstyrene groups and brominated methylstyrene groups, in terms of% by weight. With the above configuration, the brominated polyisobutylene-based polymer can have excellent and satisfactory vulcanization reactivity and reactivity to different rubber members.

[3. Method for producing brominated polyisobutylene polymer]
The brominated polyisobutylene block copolymer according to one embodiment of the present invention is obtained by obtaining a copolymer of isobutylene and an alkylstyrene and / or another monomer, and specifying the obtained copolymer in the next step It is obtained by reacting with bromine under light irradiation of a wavelength. That is, in the method for producing a brominated polyisobutylene polymer according to one embodiment of the present invention, a reaction mixture is obtained by mixing an isobutylene polymer containing one or more methylstyrene groups as a constituent unit and a compound containing bromine. Preparing a reaction mixture, and irradiating the reaction mixture with light using an irradiation apparatus to convert one or more of the methylstyrene groups into a brominated methylstyrene group; Wherein the light contains (a) light of a wavelength of 350 nm to 600 nm, and (b) when the total intensity of the light is 100%, the light intensity of a wavelength of 300 nm or less is It is characterized by being 5% or less. If it is the above-mentioned constitution, it contains methylstyrene group and brominated methylstyrene group which is not brominated as a constitutional unit, and it is 100 mol% to a total of 100 mol% of the methylstyrene group which is not brominated and the brominated methylstyrene group. To obtain a brominated polyisobutylene-based polymer containing at least 65 mol% of the brominated methylstyrene group and containing at least 1.00 mol% of the brominated methylstyrene group relative to 100 mol% of the total of the constituent units. be able to. The brominated polyisobutylene block copolymer according to one embodiment of the present invention is as described above [2. Brominated Polyisobutylene-Based Polymer] The brominated polyisobutylene-based polymer described in the section can be suitably used. In the present specification, the method for producing a brominated polyisobutylene-based polymer is also referred to simply as a method for producing.

<Polymerization process>
The method for producing a brominated polyisobutylene-based polymer according to an embodiment of the present invention may further include a polymerization step for obtaining an isobutylene-based polymer containing one or more methylstyrene groups. A polymerization method for producing a brominated polyisobutylene block copolymer according to an embodiment of the present invention, that is, a polymerization method for obtaining an isobutylene polymer containing one or more methylstyrene groups is particularly limited. And, for example, a method of copolymerizing a monomer component containing isobutylene as a main component and a monomer component not containing isobutylene as a main component in the presence of a compound represented by the following general formula (3). .

(CR ¹ R ² X) n Y-General formula (3)
In the formula, X represents a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms and an acyloxyl group having 1 to 6 carbon atoms. R ¹ and R ² each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹ and R ² may be the same or different. Moreover, two or more R < ¹ > and R < ² > may be same or different, respectively. Y represents a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group which can have n substituents (CR ¹ R ² X). n represents a natural number of 1 to 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 acyloxy group having 1 to 6 carbon atoms include acetyloxy group. Examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n- or isopropyl group and the like.

The compound represented by the general formula (3) is to be a polymerization initiator, and is considered to form a carbon cation in the presence of a Lewis acid or the like and to be a starting point of cationic polymerization.

The following compounds etc. are mentioned as an example of a compound of General formula (3) used in one embodiment of the present invention. (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, 1,3-bis (1-chloro-1-methylethyl) benzene, 1,3, 5-tris (1-chloro-1-methylethyl) benzene and 1,3-bis (1-chloro-1-methylethyl) -5- (tert-butyl) benzene. In addition, (1-chloro-1-methylethyl) benzene is also called α-chloroisopropylbenzene, 2-chloro-2-propylbenzene, or cumyl chloride. 1,4-bis (1-chloro-1-methylethyl) benzene is 1,4-bis (α-chloroisopropyl) benzene, 1,4-bis (2-chloro-2-propyl) benzene or p- It is also called dicumyl chloride. 1,3,5-tris (1-chloro-1-methylethyl) benzene is 1,3,5-tris (α-chloroisopropyl) benzene, 1,3,5-tris (2-chloro-2-propyl) ) Also called benzene or tricumyl chloride.

Among these, more preferable are (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, and 1,3,5-tris (1- Chlor-1-methylethyl) benzene.

When a compound represented by the general formula (3) is used in the polymerization step, a Lewis acid catalyst is generally used in combination. Such a Lewis acid catalyst is not particularly limited as long as it can be used for cationic polymerization, and, for example, TiCl ₄ (titanium tetrachloride), TiBr ₄ , BCl ₃ , BF ₃ , BF ₃ · OEt ₂ , SnCl ₄ , Metal halides such as AlCl ₃ and AlBr ₃ ; or metal compounds having both a halogen atom and an alkoxide group on metals such as TiCl ₃ (OiPr), TiCl ₂ (OiPr) ₂ , TiCl (OiPr) ₃ ; Et ₂ Organometallic halides such as AlCl, EtAlCl ₂ , Me ₂ AlCl, MeAlCl ₂ , Et _1.5 AlCl _1.5 , Me _1.5 AlCl _{1.5 and the} like can be mentioned.

Among them, TiCl ₄ , BCl ₃ , SnCl ₄ , TiCl ₃ (OiPr), TiCl ₂ (OiPr) ₂ , and TiCl (OiPr) ₃ are preferable in view of catalytic ability and availability.

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 monomers to be used, the polymerization concentration, the desired polymerization time, the heat generation behavior in the system, and the like. Preferably, it is used in the range of 0.1 to 200-fold mol, more preferably 0.2 to 100-fold mol, with respect to the compound represented by the general formula (3).

In the polymerization step, if necessary, electron donor components such as pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom can also be used in combination. The electron donor component is considered to have the effect of stabilizing the carbon cation at the growth end or adjusting the Lewis acidity by coordinating to the Lewis acid, and the molecular weight distribution is narrow and the structure is controlled. The obtained polymer can be obtained.

As the electron donor component, for example, 2,6-dimethylpyridine, as the one having a donor number of 15 to 60 defined as a parameter representing the strength of various compounds as an electron donor (electron donor), 2-Methylpyridine, pyridine, diethylamine, trimethylamine, triethylamine, tributylamine, N, N-dimethylaminopyridine, N, N-dimethylformamide, N, N-dimethyacetamide, ethyl acetate, titanium (IV) tetramethoxide, titanium (IV) Tetraisopropoxide, titanium (IV) butoxide and the like can be used.

Among these, 2,6-dimethylpyridine, 2-methylpyridine, triethylamine, N, N-dimethylformamide, N, N-dimethylacetamide, and titanium (IV) isopropoxide are preferable in terms of addition effect and availability. It can be used suitably.

The electron donor component is usually used in an amount of 0.01 to 100 times by mole to that of the polymerization initiator, and preferably in a range of 0.1 to 50 times by mole.

The polymerization step can be carried out in an organic solvent, if necessary. Such a polymerization solvent is not particularly limited as long as it is a solvent generally used in cationic polymerization, and a solvent comprising a halogenated hydrocarbon, a nonhalogen solvent such as an aliphatic hydrocarbon or an aromatic hydrocarbon, etc. Or these mixtures can be used.

Examples of the halogenated hydrocarbon include methyl chloride, chloroethane, 1-chlorobutane, 1-chloropentane, 1-chlorohexane and the like.

Examples of the aliphatic and / or aromatic hydrocarbons include hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and the like.

These can be used alone or in combination of two or more, but from the viewpoint of solubility and economy, the combination of 1-chlorobutane with hexane, cyclohexane, methylcyclohexane and ethylcyclohexane is solubility, economy and reactivity It can be suitably used in view of the ease of distillation in the post-treatment step.

In consideration of the viscosity of the solution and the ease of heat removal, the solution concentration of the obtained polymer is preferably set to 1 to 50% by weight, more preferably 3 to 35% by weight.

In the polymerization step, for example, the respective components are mixed at a temperature of −100 ° C. or more and less than 0 ° C. to carry out polymerization. A more preferable temperature range is −80 ° C. to −30 ° C. because of energy cost and stability of polymerization reaction.

In the case of producing an isobutylene copolymer in one embodiment of the present invention, the method and order of addition of the Lewis acid, the polymerization initiator, the electron donor component, the monomer component and the like are not particularly limited. However, preferred examples include the following.

When copolymerizing methylstyrene into a polymer block (a) based on isobutylene;
(1) A polymerization initiator, an electron donor, isobutylene and methylstyrene are previously added to a reaction vessel, and polymerization is initiated by adding a Lewis acid component at a predetermined temperature. The polymerization reaction is continued until each monomer component reaches a predetermined conversion rate to obtain isobutylene-methylstyrene copolymer; or (2) polymerization initiator, electron donor, isobutylene is previously added to the reaction vessel The polymerization is initiated by adding the Lewis acid component at a predetermined temperature. After the polymerization reaction is started, continuous addition of methylstyrene is started, or methylstyrene is added collectively at a predetermined time, and polymerization is performed until each monomer component reaches a predetermined conversion rate. A method for obtaining isobutylene-methylstyrene copolymer by continuing the reaction.

In the reaction examples (1) and (2), a monomer component mainly composed of isobutylene and a monomer component mainly composed of, for example, an aromatic vinyl compound after methyl styrene is consumed are further added. By additionally continuing the polymerization reaction, it is possible to obtain an isobutylene-aromatic vinyl compound block copolymer in which methylstyrene is introduced into a polyisobutylene block.

When methylstyrene is copolymerized with an aromatic vinyl compound block of isobutylene-aromatic vinyl compound block copolymer;
(3) A polymerization initiator, an electron donor, and isobutylene are previously added to a reaction vessel, and polymerization is initiated by adding a Lewis acid component at a predetermined temperature. At the end of the polymerization reaction of isobutylene, the vinyl aromatic compound component and methylstyrene are simultaneously added to carry out the polymerization reaction until the desired conversion is reached, or the vinyl aromatic compound component is added first, and then Start the continuous addition of methylstyrene to the mixture, or add methylstyrene in one batch, and continue the polymerization reaction until each monomer component reaches a predetermined conversion rate to obtain isobutylene-methylstyrene copolymer How to get united.

Bromination reaction
The present brominated polyisobutylene polymer can be produced by performing a reaction mixture preparation step and an irradiation step after obtaining an isobutylene polymer. These steps are collectively referred to as bromination reaction.

The bromination reaction of polymers has conventionally been carried out by reacting the polymer, bromine, a thermal radical initiator, an optical radical initiator, and a chemical radical initiator in a solution. Alternatively, the bromination reaction of a polymer has been carried out by irradiating a mixture of the polymer and bromine with light using a high pressure mercury lamp or a tungsten lamp as an irradiation device. Although it is possible to use these bromination techniques, in one embodiment of the present invention, it was found that the bromination rate can be further increased by irradiating light of a specific wavelength in the coexistence of a bromine source. . That is, in the method for producing a brominated polyisobutylene polymer according to one embodiment of the present invention, one or more of the methylstyrene styrene groups of the isobutylene polymer are made into a brominated methylstyrene group by the above-mentioned irradiation step. Is preferred. In the irradiation step, it is presumed that the reaction is moderated by irradiating the long wavelength light of 350 nm to 600 nm necessary for the bromination, and as a result, the selectivity of the bromination is enhanced. Therefore, it is preferable that it is a light emitting diode (LED) as an irradiation apparatus. On the other hand, bromination by radical generating agents such as azobisisobutyronitrile (AIBN) or bromination by light irradiation using an irradiation apparatus including many wavelengths of 300 nm or less such as a high pressure mercury lamp causes a reaction to occur violently. It is thought that it is losing selectivity.

When one or more of the methylstyrene groups are brominated methylstyrene groups by irradiating light of a specific wavelength using an irradiation apparatus, that is, in the irradiation step according to one embodiment of the present invention, the radical initiator is required And not. Therefore, the bromination reaction can be performed under milder conditions than conventionally known radical bromination techniques.

As a compound containing bromine (also referred to as a bromine source), bromine molecules (Br ₂ ), N-bromosuccinimide and the like can be suitably used, but bromine molecules (Br ₂ ) in terms of availability, economy and easy handling Is preferred.

When bromine molecules (Br ₂ ) are used in the irradiation step, the amount of bromine molecules is preferably 0.65 to 50 equivalents relative to the number of moles of methylstyrene in the isobutylene-based copolymer, and 0. It is more preferably 70 to 20 equivalents, and most preferably 0.70 to 5 equivalents. Use of more than 50 equivalents is not preferable because it is not only uneconomical because surplus bromine remains, but also the subsequent purification may become difficult. Moreover, when it is less than 0.65 equivalent, since the high bromination rate which is one of the effects concerning one embodiment of the present invention may not be achieved, it is unpreferable.

When using the irradiation step with molecular bromine (Br _2), as a method of input molecular bromine (Br _2), to the molecular bromine (Br ₂₎ or directly it is introduced into the system, a solvent or the like to be used for bromination The solution may be diluted to any concentration and then added.

The irradiation process according to an embodiment of the present invention can be carried out in bulk or in solution, but isobutylene-methylstyrene copolymer is an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, or a halogenated hydrocarbon. It is preferable to dissolve in a system solution and carry out in a solution.

Preferred hydrocarbon solvents include butane, pentane, hexane, heptane, octane, nonane, decane, 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, 2,2,5-trimethylhexane, cyclohexane And methylcyclohexane, ethylcyclohexane, paraffin oil, benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene and the like.

Preferred halogenated hydrocarbon solvents include methyl chloride, methylene chloride, chloroethane, dichloroethane, 1-chloropropane, 1-chloro-2-methylpropane, 1-chlorobutane, 1-chloro-2-methylbutane, 1-chloro-3 -Methylbutane, 1-chloro-2,2-dimethylbutane, 1-chloro-3,3-dimethylbutane, 1-chloro-2,3-dimethylbutane, 1-chloropentane, 1-chloro-2-methylpentane, 1-chloro-3-methylpentane, 1-chloro-4-methylpentane, 1-chlorohexane, 1-chloro-2-methylhexane, 1-chloro-3-methylhexane, 1-chloro-4-methylhexane, 1-Chloro-5-methylhexane, 1-chloroheptane, 1-chlorooctane, 2-chloropropane, 2-chloropropane Rorobutan, 2-chloro-pentane, 2-chloro-hexane, 2-chloro-heptane, 2-chloro octane, chlorobenzene, and the like. These can be used 1 type or in combination of 2 or more types.

In the irradiation step according to one embodiment of the present invention, one or more solvents selected from the group consisting of 1-chloropropane, 1-chlorobutane, 1-chloropentane and pentane, hexane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane A combination of one or more solvents selected from the group consisting of: is most suitable in terms of solubility, economy, reactivity, and ease of distillation in the post-treatment step. Among these, it is preferable to use again the solvent used at the time of polymerization also in the irradiation step.

The concentration of the organic solvent is preferably set to 1 to 50% by weight, more preferably 3 to 35% by weight, in consideration of viscosity at the time of bromination reaction and ease of heat removal. .

The temperature of the reaction mixture in the irradiation step according to one embodiment of the present invention is adjusted in view of the reaction efficiency, the stability of the polymer, the boiling point of the solvent, and the like. In order to realize an efficient bromination reaction, it is preferable to carry out at 0 ° C. to 100 ° C., and it is more preferable to maintain between 10 ° C. and 80 ° C. If the temperature is lower than 0 ° C., cooling may be required, which is not preferable economically. If the temperature is higher than 100 ° C., heating is required, which is not preferable economically.

In the irradiation step according to one embodiment of the present invention, it is preferable to irradiate the reaction mixture with light satisfying the following (a) and (b) using an irradiation device: (a) 350 nm to 600 nm And (b) when the total intensity of the light is 100%, the intensity of the light having a wavelength of 300 nm or less is 5% or less. It is more preferable that the light used for light irradiation further satisfy (c) in addition to the above (a) and (b): (c) Contain light with a wavelength of 375 nm to 600 nm.

Among light having a wavelength of 350 nm or less, light having a wavelength of 300 nm or less in particular may cause side reactions such as decomposition of a polymer skeleton by causing an undesired radical reaction. Therefore, in order to efficiently obtain a desired polymer, the intensity of light with a wavelength of 300 nm or less is preferably 5% or less, and 1% or less, when the total intensity of light is 100%. More preferable. Light with a wavelength longer than 600 nm also can not efficiently advance the bromination reaction. Therefore, the light irradiated to the reaction mixture in the irradiation step preferably has a light intensity of 5% or less at a wavelength longer than 600 nm, when the total light intensity is 100%.

In one embodiment of the present invention, it is considered that bromine radical molecules can be efficiently generated by irradiating light having a wavelength in the above-described range, and thus, the bromination efficiency is enhanced.

In the irradiation step according to one embodiment of the present invention, it is preferable that the light irradiation is performed under substantially no or minimal conditions of styrene and the metal halide compound.

In the method for producing a brominated polyisobutylene-based polymer according to one embodiment of the present invention, (a) the reaction mixture contains substantially no styrene, or (b) the reaction mixture further contains styrene, and The ratio of the number of moles of styrene to the number of moles of bromine in the reaction mixture (value represented by (number of moles of styrene) / (number of moles of bromine)) is preferably less than 0.35. The ratio of the number of moles of styrene to the number of moles of bromine in the reaction mixture is more preferably less than 0.1, still more preferably less than 0.0001, and the reaction mixture is substantially free of styrene. Is particularly preferred. This configuration has the advantage that the formation of by-products and the consumption of bromine due to unwanted reactions do not occur. This is considered to be because, when styrene is present in the reaction mixture, a reaction of adding bromine to styrene proceeds in a later irradiation step. In addition, conditions larger than 0.35 are not preferable because the bromine molecules consumed in the bromination reaction increase, which decreases the amount of bromine available for the forward reaction and increases the amount of impurities remaining in the resin.

In the method for producing a brominated polyisobutylene-based polymer according to one embodiment of the present invention, (a) the reaction mixture is substantially free of a metal halide compound, or (b) the reaction mixture further contains a metal halide. The ratio of the number of moles of the metal halide compound to the number of moles of bromine in the reaction mixture containing the compound (value represented by (number of moles of metal halide compound) / (number of moles of bromine)) is Preferably it is less than 1.5. The ratio of the number of moles of metal halide compound to the number of moles of bromine in the reaction mixture is more preferably less than 0.1, still more preferably less than 0.01, and the reaction mixture is a metal halide compound. It is particularly preferred to be substantially free of If it is the said structure, it has the advantage that a bromination reaction advances appropriately, without delaying, without the bromination reaction activity falling. The present inventors have found that when the reaction mixture contains a metal halide compound, the bromination reaction activity is reduced in the subsequent irradiation step. On the other hand, conditions larger than 1.5 are not preferable because the progress of the bromination reaction becomes extremely slow.

After the irradiation step, as is known in the prior art, brominated polyisobutylene-based weight obtained by neutralization with dilute aqueous caustic solution, washing with pure water, reductive treatment of residual bromine, removal of solvent by steam stripping The coalescing can be recovered and, if necessary, the brominated polyisobutylene-based polymer is then further dried.

<Resin composition>
Furthermore, if it is a range which does not impair the effect concerning one embodiment of the present invention, a filler and a reinforcing material can be blended with this brominated polyisobutylene type polymer from physical property improvement or an economic advantage. The composition comprising the brominated polyisobutylene-based polymer and the other substance is referred to as a brominated polyisobutylene-based polymer composition, or simply a resin composition. Brominated polyisobutylene-based polymer compositions are also an embodiment of the present invention.

Suitable fillers and reinforcing materials include organic or inorganic hollow fillers, various foaming agents, various types of clay, diatomaceous earth, silica sand, pumice powder, slate powder, dry or wet silica, amorphous silica, wollastonite, synthetic or synthetic Natural zeolite, talc, barium sulfate, lithopone, light or heavy calcium carbonate, magnesium carbonate, calcium sulfate, aluminum sulfate, molybdenum disulfide, magnesium hydroxide, calcium silicate, alumina, titanium oxide, other metal oxides, mica , Scale-like inorganic fillers such as graphite and aluminum hydroxide, various metal powders, wood chips, glass powders, ceramic powders, carbon black, granular to powdery solid fillers such as granular or powder polymers, and various other natural substances Or artificial short fibers, long fibers and the like.

Any filler may be used as long as it does not impair the effects according to the embodiment of the present invention, and two or more of these fillers may be used in combination.

The compounding amount of the filler is 0 to 500 parts by weight with respect to 100 parts by weight of the brominated polyisobutylene polymer. If it exceeds 500 parts by weight, the physical properties of the resulting resin composition may be significantly reduced, which is not preferable. Preferably, it is 0 to 100 parts by weight.

The brominated polyisobutylene polymer composition according to an embodiment of the present invention may be a hindered phenol-based or phosphoric acid ester, if necessary, so long as the effects according to the embodiment of the present invention are not impaired. A system, an amine, an antioxidant such as sulfur, and / or an ultraviolet absorber such as a benzodiazole, a benzotriazole, a benzophenone, and a light stabilizer can be blended.

The recommended blending amount of the above-mentioned antioxidant, UV absorber and light stabilizer is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, with respect to 100 parts by weight of the brominated polyisobutylene polymer It is.

A plasticizer and a softener can be added to the brominated polyisobutylene polymer composition according to an embodiment of the present invention as long as the effects of the invention are not impaired.

Examples of plasticizers and softeners include phthalic acid esters, adipic acid esters, phosphoric acid esters, trimellitic acid esters, epoxy compounds, paraffinic oils, naphthenic oils, and aromatic high boiling point petroleum components, castor oil , Cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, wax, pine oil, olive oil, olive oil, polybutene, hydrogenated polybutene, liquid polybutadiene, hydrogenated liquid polybutadiene, liquid poly α-olefins Etc.

These plasticizers and softeners may be used in combination of two or more, but among them, polybutene oil or hydrogenated polybutene oil is preferable in terms of compatibility and gas barrier properties. In particular, use of polybutene or hydrogenated polybutene oil having a number average molecular weight of 20000 or more is preferable because the bleed out is extremely low.

The blending amount of these plasticizers and softeners is preferably 1 to 300 parts by weight with respect to 100 parts by weight of the brominated polyisobutylene polymer. If the amount is more than 300 parts by weight, stickiness tends to occur and mechanical strength tends to decrease.

A tackifying resin can be added to the brominated polyisobutylene polymer composition according to an embodiment of the present invention as long as the effects of the invention are not impaired. As tackifying resins, alicyclic petroleum resins and their hydrides, aliphatic petroleum resins, hydrides of aromatic petroleum resins, polyterpene resins, rosin resins and the like can be mentioned. These may be used alone or in combination of two or more.

The compounding amount of the tackifier is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the brominated polyisobutylene polymer. If the amount is less than 1 part by weight, the tackifying effect may not be obtained in some cases, and if it exceeds 100 parts by weight, the hardness of the composition may be too high.

Other additives include flame retardants, antibacterial agents, colorants, fluidity improvers, lubricants, antiblocking agents, antistatic agents, crosslinking agents, crosslinking aids, modifiers, pigments, dyes, conductive fillers, and various other additives. Chemical blowing agents, physical blowing agents and the like can be added, and these can be used singly or in combination of two or more.

The brominated polyisobutylene polymer composition according to one embodiment of the present invention may further contain an ethylene-vinyl alcohol copolymer from the viewpoint of improving the gas barrier properties. The ethylene-vinyl alcohol copolymer preferably has an ethylene content of 20 to 70 mol%. If the ethylene content is less than 20 mol%, there is a possibility that the composition may be inferior in moisture barrier properties and flexibility and inferior in flex resistance, and also inferior in thermoformability. If it exceeds 70 mol%, the gas barrier properties may be insufficient.

The blending amount of the ethylene-vinyl alcohol copolymer in the brominated polyisobutylene polymer composition according to one embodiment of the present invention is 1 to 400 parts by weight with respect to 100 parts by weight of the brominated polyisobutylene polymer. Is preferable, and 10 to 400 parts by weight is more preferable. If the blending amount of ethylene-vinyl alcohol copolymer exceeds 400 parts by weight, the flexibility may be lost and the bending fatigue property in the long term may be inferior.

A crosslinking agent and a crosslinking assistant may be further added to the brominated polyisobutylene polymer composition according to one embodiment of the present invention. The crosslinking agent is exemplified by sulfur S ₈ , tetramethylthiuram disulfide, 4,4-dithiobismorpholine, organic peroxide, phenolformaldehyde resin, halomethylphenol. Among these, elemental sulfur, tetramethylthiuram disulfide, and 4,4-dithiobismorpholine are preferable. Examples of crosslinking aids include metal oxides such as sulfenamide, benzothiazole, guanidine, dithiocarbamic acid and zinc oxide, fatty acids such as stearic acid, nitrogen-containing compounds, triallyl isocyanurate, ethylene glycol dimethacrylate, and trimethylolpropane methacrylate Can be mentioned. Among these, metal oxides such as sulfenamide, benzothiazole, guanidine, dithiocarbamic acid and zinc oxide, and fatty acids such as stearic acid are preferable.

The blending amount of the crosslinking agent and the crosslinking aid is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the brominated polyisobutylene polymer.

The brominated polyisobutylene polymer composition according to an embodiment of the present invention can be produced by the method exemplified below. For example, in the case of manufacturing using a closed type or open type batch type kneading apparatus such as Labo Plastomill, Brabender, Banbury mixer, kneader, roll, etc., all the components other than the cross-linking agent mixed in advance are kneaded. The method is to stop the melt-kneading after the crosslinking reaction proceeds sufficiently by adding a crosslinking agent if necessary.

Moreover, it can also manufacture using a continuous-type melt-kneading apparatus like a single-screw extruder, a twin-screw extruder, etc.

In melt-kneading, a temperature range of 100 to 270 ° C. is preferable, and a temperature range of 130 to 230 ° C. is more preferable. If the melt-kneading temperature is lower than 100 ° C., the resin component may not melt and mixing may not be sufficient. If higher than 270 ° C., the brominated polyisobutylene-based polymer is decomposed, variously. It is not preferable because it may lead to a decrease in the physical properties of

The brominated polyisobutylene-based polymer according to one embodiment of the present invention is excellent in flexibility, gas barrier property and vulcanization reactivity, and reactivity with different rubber members, and therefore, can be suitably used for the following applications.

(1) Sealing materials: gaskets, gaskets for construction, stoppers, glass sealing materials for double glazing, packaging materials, sheets, multilayer sheets, containers, gas barrier materials such as multilayer containers, multilayer laminates, civil engineering sheets, waterproof sheets , Packaging transport materials, sealants, medical medicine stoppers, syringe gaskets, etc.

(3) Tubes: Medical tubes, ink tubes, food tubes, etc.

(4) Others: Resin or asphalt modifiers (impact modifiers for thermoplastic or thermosetting resins, damping modifiers, gas barrier modifiers, for roads, for bridge floor slabs or tarpaulins Asphalt modifiers), adhesives or adhesives (hot melt adhesives, water-based adhesives, solvent adhesives, adhesives), viscosity modifiers, paint base resins, damping materials, vibration control materials, buffer materials Materials, soundproofing materials, sound absorbing materials, foams, PVC alternatives, etc.

One embodiment of the present invention may be configured as follows.

[1] The structural unit includes a methylstyrene group which is not brominated and a methylstyrene group which is not brominated, and the above-mentioned methylstyrene group which is not brominated and a total of 100 mol% of the brominated methylstyrene group A brominated polyisobutylene polymer comprising 65 mol% or more of a brominated methylstyrene group, and containing 1.00 mol% or more of the brominated methylstyrene group with respect to 100 mol% of the total amount of the constituent units. .

[2] The non-brominated methylstyrene group is p-methylstyrene (4-methylstyrene) group, and the brominated methylstyrene group is p-bromomethylstyrene (4-bromomethylstyrene) The brominated polyisobutylene-based polymer according to [1], which is a group.

[3] The brominated polyisobutylene-based polymer is a block copolymer comprising a polymer block (a) composed mainly of isobutylene and a polymer block (b) composed mainly of an aromatic vinyl compound The brominated polyisobutylene-type polymer as described in [1] or [2] characterized by these.

[4] The polymer block (a) mainly composed of isobutylene is 100% by weight of the total amount of the non-brominated methylstyrene group and the brominated methylstyrene group in the brominated polyisobutylene-based polymer And a brominated polyisobutylene-based polymer according to [3], which contains 50% by weight or more of the non-brominated methylstyrene group and the brominated methylstyrene group.

[5] The oxygen permeability coefficient is 0.0 to 10.0 × 10 ⁻¹⁶ (mol · m / (m ² · second · Pa)), and the tensile strength is 5.00 to 30.00 MPa, where The oxygen permeability coefficient is a value measured according to the method described in JIS K-7126, and the tensile strength is a value measured according to the method described in JIS K-6251 The brominated polyisobutylene-based polymer according to any one of [1] to [4].

[6] A reaction mixture preparation step of preparing a reaction mixture by mixing an isobutylene polymer containing one or more methylstyrene groups as a constitutional unit, and a compound containing bromine, and an irradiation device for the reaction mixture Irradiating one or more of the methylstyrene groups with brominated methylstyrene groups by irradiating with light using a light source, wherein the light has a wavelength of (a) 350 nm to 600 nm Any of [1] to [5] characterized in that it contains light, and (b) the intensity of light with a wavelength of 300 nm or less is 5% or less when the total intensity of the light is 100%. The manufacturing method of the brominated polyisobutylene type polymer as described in any one.

[7] The method for producing a brominated polyisobutylene-based polymer according to [6], wherein the irradiation device is a light emitting diode (LED).

[8] (a) The reaction mixture contains substantially no styrene, or (b) the reaction mixture further contains styrene, and the number of moles of styrene and the number of moles of bromine in the reaction mixture Brominated polyisobutylene as described in [6] or [7], having a ratio of ((number of moles of styrene) / (number of moles of bromine)) of less than 0.35. Method for producing a base polymer.

[9] (a) the reaction mixture is substantially free of a metal halide compound, or (b) the reaction mixture further contains a metal halide compound, and the metal halide in the reaction mixture A ratio of the number of moles of the compound to the number of moles of bromine (a value represented by (number of moles of metal halide compound) / (number of moles of bromine)) is less than 1.5 [6 ] The manufacturing method of the brominated polyisobutylene type-polymer as described in any one of -8.

[10] The method for producing a brominated polyisobutylene-based polymer according to any one of [6] to [9], wherein the compound containing bromine is a bromine molecule (Br ₂ ).

One embodiment of the present invention may also be configured as follows.

[1] A brominated polyisobutylene-based polymer comprising a monomer unit in which a methylstyrene group is brominated, wherein 65 mol% or more of the methylstyrene group is brominated, and the bromo occupied in the constituting monomer unit A brominated polyisobutylene-based polymer, wherein the proportion of methylstyrene groups is 1.0 mol% or more.

[2] The brominated polyisobutylene-based polymer according to [1], wherein the methylstyrene group is a p-methylstyrene (4-methylstyrene) group.

[3] The brominated polyisobutylene polymer is a block copolymer comprising a block (a) composed mainly of isobutylene and a block (b) composed mainly of an aromatic vinyl compound The brominated polyisobutylene-based polymer according to [1] or [2].

[4] 50% by weight or more of methylstyrene copolymerized in the block copolymer consisting of the block (a) mainly composed of isobutylene and the block (b) mainly composed of an aromatic vinyl compound The brominated polyisobutylene-based polymer according to any one of [1] to [3], which is contained in the block (a) mainly composed of isobutylene.

[5] The oxygen permeation coefficient measured according to JIS K-7126 is 0 to 10.0 × 10 ⁻¹⁶ (mol · m / (m ² · sec · Pa)), and the tension measured according to JIS K-6251 The brominated polyisobutylene-based polymer according to any one of [1] to [4], which has a strength of 5.0 to 30.0 MPa.

[6] A light having a wavelength of 350 nm to 600 nm and containing no light of a wavelength of 300 nm or less in a reaction mixture comprising an isobutylene polymer containing monomer units having a methylstyrene group and bromine (Br ₂ ) The method for producing a brominated polyisobutylene-based polymer according to any one of [1] to [5], which comprises brominating a methylstyrene site by irradiating with.

[7] The method for producing a brominated polyisobutylene-based polymer according to [6], wherein the light source of light is an LED (light emitting diode).

[8] The reaction mixture is characterized in that the ratio of the number of moles of styrene and bromine remaining in the solution (value represented by the number of moles of styrene) / (the number of moles of bromine) is smaller than 0.35. The manufacturing method of the brominated polyisobutylene-type polymer as described in [6] or [7] to be taken.

[9] In the reaction mixture, the ratio of the number of moles of halogenated metal compound and bromine present in the solution ((the number of moles of halogenated metal compound) / (the number of moles of bromine)) is 1. A method for producing a brominated polyisobutylene-based polymer according to any one of [6] to [8], which is smaller than 5.

EXAMPLES Hereinafter, one embodiment of the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

(Measurement of molecular weight)
In the following examples, “number average molecular weight”, “weight average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” refer to gel permeation chromatography (Gel Permeation Chromatography; GPC) (size exclusion chromatography) Calculated by the standard polystyrene conversion method using Size Exclusion Chromatography (also referred to as SEC) As a measuring apparatus, using chloroform as a mobile phase using a 510 type GPC system manufactured by Waters, conditions of column temperature 35 ° C. The concentration was measured by injecting a sample solution having a polymer concentration of 4 mg / ml into GPC, and polystyrene was used as a standard sample.

Production Example 1 Preparation of Brominated Polyisobutylene Polymer Test Pieces For 40 g of brominated polyisobutylene polymer, 0.08 g of an antiaging agent (product name: AO-50, manufactured by Adeka Co., Ltd.), and inorganic Measure 0.2 g of a salt acid acceptor (product name: Alkamizer 1, manufactured by Kyowa Chemical Industry Co., Ltd.) and knead it for 9 minutes with a Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 170 degrees and 50 rpm for 9 minutes Degassed at 170 degrees / vacuum for 1 minute. Thereafter, the obtained resin composition was sandwiched by release paper and pressed at 170 ° C. for 8 minutes to obtain a sheet-like sample having a thickness of 0.5 mm or 2.0 mm.

(Measurement of oxygen permeability coefficient)
The oxygen permeation coefficient was measured by a differential pressure method using a press sheet 0.5 mm thick according to JIS K-7126.

(Measurement of tensile strength)
In accordance with JIS K 6251, a 2.0 mm thick sheet was punched into a No. 3 type with a dumbbell as a test piece, and this was used for measurement. The tensile speed was 200 mm / min.

(Vulcanization reactivity)
In order to verify the vulcanization reactivity, the reactivity with isoprene rubber was evaluated as follows. That is, a test piece of a brominated polyisobutylene copolymer pressed to a thickness of 2.0 mm shown in (Production Example 1), a support layer shown in (Production Example 2), and an isoprene rubber shown in (Production Example 3) It bonded so that it might be pinched | interposed with a test piece, and after performing heating pressurization vulcanization for 40 minutes at 150 degreeC and 50 MPa, it cut out in width 2.5 cm x 6 cm. Then, the stress at the time of conducting a 180 degree peeling test was measured. The test speed was 200 mm / min, and the average value of the test stress measured three times was adopted.

Production Example 2 Preparation of Support Layer This support layer is prepared to prevent the brominated polyisobutylene layer from being broken during the vulcanization reaction test to make accurate evaluation difficult. Styrene-isobutylene block copolymer: 40 g of pellets of SIBSTAR 102T (manufactured by Kaneka Co., Ltd.) were pressed at 200 ° C. for 8 minutes to obtain a 2 mm thick test piece. Next, a nylon mesh was placed on this sample piece, and pressed again at 200 degrees for 8 minutes to prepare a support layer test piece in which the nylon mesh and SIBSTAR 102T were crimped.

Production Example 3 Preparation of Polyisoprene Rubber Test Pieces 1 L kneader (stock) with 400 g of polyisoprene rubber (trade name “IR2200” manufactured by JSR Corporation) and 200 g of carbon black (Asahi Carbon Asahi # 50) set at 40 ° C. Company's Moriyama Co., Ltd.) and knead at 50 rpm for 5 minutes, then 6 g of sulfur, 8 g of N-tert-butyl-2-benzothiazolesulfenamide, 8 g of zinc oxide and 8 g of stearic acid and knead for 2 minutes It discharged | emitted and the test piece of 2 mm thickness was shape | molded by the heating press (made by a Shinto metal company) at 80 degreeC.

Production Example 4 Production of Butyl Rubber Test Piece Butyl 268 (manufactured by JSR Corporation, 100 parts by weight), sulfur (manufactured by Wako Pure Chemical Industries, 2 parts by weight), Noxceler DM-P (manufactured by Ouchi Shinko Chemical Co., Ltd., 0. 5 parts by weight), Noxceler TT-P (made by Ouchi Shinko Chemical Co., Ltd., 1 part by weight), zinc oxide (made by Wako Pure Chemical Industries, 5 parts by weight), stearic acid (made by Wako Pure Chemical Industries, 1 part by weight) At this rate, it is put into a 1 L kneader (made by Moriyama Co., Ltd.) set to 40 ° C., kneaded at 50 rpm for 2 minutes and then discharged, and a sheet of 0.5 mm thickness is heated at 150 ° C. with a heat press (made by Shinto Metal Co.) Molded into a shape. Next, the oxygen permeability coefficient was measured, and it was 3.4 × 10 ⁻¹⁶ (mol · m / (m ² · second · Pa)).

Comparative Example 1 Synthesis of Brominated Polyisobutylene Polymer P-1 The inside of the container of a 500 mL separable flask was purged with nitrogen, and then 247 mL of butyl chloride (dried with molecular sieves) and hexane (using molecular syringes) using a syringe. 27.4 mL of dried (by molecular sieves) was added. The polymerization vessel was immersed in a dry ice / acetone bath at −80 ° C. and cooled, and then 85 mL (0.899 mol) of isobutylene monomer was added. Next, 0.1412 g (0.61 mmol) of p-dicumyl chloride and 0.12 mL (1.25 mmol) of α-picoline were added. The system was cooled to -70 ° C. Polymerization was initiated by adding 0.96 mL (0.0087 mol) of titanium tetrachloride. The polymerization was followed by measuring the amount of residual isobutylene monomer by gas chromatography, and it was judged that the polymerization of isobutylene was completed when 99.5% of the isobutylene was consumed, and then 9.8 mL of styrene (0 .085 mol) was added. After 2 minutes, 2.80 mL (0.0213 mol) of paramethylstyrene was added. Thereafter, the polymerization was traced while measuring the amount of residual styrene monomer by gas chromatography, and the polymerization of styrene was terminated when 80% of the styrene monomer was consumed. At this time, 95% of paramethylstyrene was consumed. Next, the reaction mixture obtained was poured into 1 L of pure water heated to 70 ° C., and polymerization was stopped by vigorously stirring for 60 minutes using a mechanical stirrer. Next, washing was repeated three times with 1 L of pure water. Thereafter, volatile components such as a solvent were distilled off under heating, and drying was performed to obtain isobutylene-methylstyrene copolymer R-1.

The number average molecular weight of the obtained isobutylene-methylstyrene copolymer R-1 was 91,805, and the molecular weight distribution was 1.17. ^{According to 1} H NMR, the number of methylstyrene groups introduced into one polymer molecule was 33.

Next, 1 g of the obtained isobutylene-methylstyrene copolymer R-1, 18.5 μL of bromine (Br ₂ ), and 0.0022 g of azoisobutyronitrile (AIBN) are dissolved in 5 mL of carbon tetrachloride, and the reaction is carried out for 1 hour. Refluxed. Thereafter, the reaction mixture was reprecipitated from acetone to obtain a brominated polyisobutylene polymer P-1. ^{From 1} H NMR, the bromomethyl group was 0.68 mol%, and the reaction rate was 33 mol%.

Comparative Example 2 Synthesis of Brominated Polyisobutylene Polymer P-2 A brominated polyisobutylene polymer P-2 was synthesized in the same manner as Comparative Example 1 except that 37 μL of bromine (Br ₂ ) was used. . ^{According to 1} H NMR, the bromomethyl group was 0.61 mol%, and the reaction rate was 30 mol%.

Comparative Example 3 Synthesis of Brominated Polyisobutylene Polymer P-3 A brominated polyisobutylene polymer P was prepared in the same manner as Comparative Example 1 except that 0.0043 g of azoisobutyronitrile (AIBN) was used. -3 was synthesized. ^{From 1} H NMR, the bromomethyl group was 0.55 mol%, and the reaction rate was 27 mol%.

Comparative Example 4 Synthesis of Brominated Polyisobutylene Polymer P-4 Brominated poly was prepared in the same manner as Comparative Example 1 except that 0.128 g of N-bromosuccinimide was used instead of bromine (Br ₂ ). An isobutylene polymer P-4 was synthesized. ^{From 1} H NMR, the bromomethyl group was 0.80 mol%, and the conversion was 39 mol%.

Comparative Example 5 Synthesis of Brominated Polyisobutylene Polymer P-5 Comparative Example 4 except that 0.064 g of N-bromosuccinimide was used instead of bromine (Br ₂ ) and the reaction time was 3 hours. A brominated polyisobutylene polymer P-5 was synthesized in the same manner as in. ^{From 1} H NMR, the bromomethyl group was 0.74 mol%, and the reaction rate was 36 mol%.

Comparative Example 6 Synthesis of Brominated Polyisobutylene Polymer P-6 The inside of a container of a 2 L separable flask was purged with nitrogen, and then 944 mL of butyl chloride (dried with molecular sieves) and hexane (using molecular syringes) using a syringe. 404 mL dried (by molecular sieves) was added. The polymerization vessel was immersed in a dry ice / acetone bath at −80 ° C. and cooled, and then 331 mL (3.50 mol) of isobutylene monomer was added. Next, 0.550 g (2.38 mmol) of p-dicumyl chloride and 0.71 mL (7.14 mmol) of α-picoline were added. The system was cooled to -70 ° C. 9.13 mL (0.0833 mol) of titanium tetrachloride was added to initiate polymerization. After 3 minutes, 12.5 mL (0.0952 mol) of paramethylstyrene was added dropwise, and the entire amount was dropped over 28 minutes. Thereafter, the polymerization was traced while measuring the amount of residual isobutylene monomer by gas chromatography, and it was judged that the polymerization of isobutylene was completed when 99.5% of the isobutylene was consumed. At that time, 99.9% of para-methylstyrene was consumed. Then 47.7 mL (0.414 mol) of styrene was added. Thereafter, the polymerization was traced while measuring the amount of residual styrene monomer by gas chromatography, and the polymerization of styrene was terminated when 80% of the styrene monomer was consumed. The reaction mixture was poured into 3 L of pure water heated to 70 ° C., and polymerization was stopped by vigorously stirring for 60 minutes using a mechanical stirrer. Next, washing was repeated three times with 3 liters of pure water. Thereafter, volatile components such as a solvent were distilled off under heating, and drying was performed to obtain isobutylene-methylstyrene copolymer R-2.

The number average molecular weight of the obtained isobutylene-methylstyrene copolymer R-2 was 96,890, and the molecular weight distribution was 1.24. ^{From 1} H NMR, the number of methylstyrene groups introduced into one polymer molecule was 40.

Next, 100 g of the obtained isobutylene-methylstyrene copolymer R-2, 6.6 g of bromine (Br ₂ ) and 0.020 g of azoisobutyro nitrile (AIBN) are dissolved in 500 mL of carbon tetrachloride, and the reaction time is 1 hour Refluxed. Thereafter, the reaction mixture was reprecipitated from acetone to obtain a brominated polyisobutylene polymer P-6. ^{From 1} H NMR, the bromomethyl group was 0.92 mol%, and the reaction rate was 38 mol%.

(Example 1) Synthesis of brominated polyisobutylene polymer Q-1 After purging the inside of the container of an 8 L separable flask with nitrogen, using a syringe, 3774 mL of butyl chloride (dried with molecular sieves) and hexane ( 1618 mL of dried (by molecular sieves) was added. The polymerization vessel was immersed in a −80 ° C. dry ice / acetone bath and cooled, and then 1322 mL (14.0 mol) of isobutylene monomer was added. Next, 2.20 g (9.52 mmol) of p-dicumyl chloride and 3.98 mL (0.0286 mol) of triethylamine were added. The system was cooled to -70 ° C. After 24.2 mL (0.0816 mol) of titanium (IV) isopropoxide was added and stirred for 5 minutes, 62.6 mL (0.571 mol) of titanium tetrachloride was added to initiate polymerization. After 3 minutes, 50.2 mL (0.381 mol) of paramethylstyrene was added dropwise, and the entire amount was dropped over 37 minutes. Thereafter, the polymerization was followed while measuring the amount of residual isobutylene monomer by gas chromatography, and it was judged that the polymerization of isobutylene was completed when it was confirmed that 99.0% of isobutylene was consumed. At that time, 99.3% of para-methylstyrene was consumed. Next, 191 mL (1.66 mol) of styrene was added. Thereafter, the polymerization was traced while measuring the amount of residual styrene monomer by gas chromatography, and 30 ml of titanium tetrachloride was added at a stage where 41% of the styrene monomer was consumed 15 minutes after the addition of styrene. Then, after 15 minutes, it was confirmed that the consumption rate of styrene monomer reached 81%, and the polymerization of styrene was completed. The reaction mixture was poured into 15 liters of pure water heated to 70 ° C., and polymerization was stopped by vigorously stirring for 60 minutes using a mechanical stirrer. Next, washing was repeated three times with 15 liters of pure water. Thereafter, volatile components such as a solvent were distilled off under heating, and drying was carried out to obtain isobutylene-methylstyrene copolymer R-3.

The number average molecular weight of the obtained isobutylene-methylstyrene copolymer R-3 was 103,065, and the molecular weight distribution was 1.31. ^{From 1} H NMR, the number of methylstyrene groups introduced into one polymer molecule was 39.

Next, the obtained isobutylene-methylstyrene copolymer R-3 (40 g) and 0.8 mL of bromine (Br ₂ ) were dissolved in a mixed solvent of 180 mL of butyl chloride and 20 mL of n-hexane at room temperature. Next, the reaction mixture was irradiated for 90 minutes at room temperature with a single-wavelength LED light source (LDA10DGZ60W manufactured by Panasonic Corporation) having a wavelength of 395 nm. Thereafter, it was judged that the reaction was completed because the dark brown peculiar to bromine became faint and orange from the reaction mixture. The reaction mixture was reprecipitated from acetone to obtain a brominated polyisobutylene polymer Q-1. ^{From 1} H NMR, the bromomethyl group was 1.67 mol%, and the conversion was 69 mol%.

The vulcanization reactivity of the brominated polyisobutylene polymer Q-1 with respect to polyisoprene rubber was evaluated to be 94 N / 25 mm. In addition, the oxygen permeability coefficient was measured and found to be 3.2 × 10 ⁻¹⁶ (mol · m / (m ² · second · Pa)). Furthermore, the tensile strength was 7.00 MPa.

(Example 2) Synthesis of brominated polyisobutylene polymer Q-2 By preparing in the same manner as in Example 1 except that 1.6 mL of bromine (Br ₂ ) was used, a brominated polyisobutylene polymer Q was prepared. I got -2. ^{From 1} H NMR, the bromomethyl group was 1.67 mol%, and the conversion was 69 mol%.

(Example 3) Synthesis of brominated polyisobutylene polymer Q-3 After nitrogen-substituting the inside of the container of a 1 L separable flask, using a syringe, butyl chloride (dried with molecular sieves) 1211 mL and hexane (hexane) 519 mL of dried with molecular sieves was added. The polymerization vessel was immersed in a −80 ° C. dry ice / equine bath and cooled, and then 423 mL (4.48 mol) of isobutylene monomer was added. Next, 0.704 g (3.05 mmol) of p-dicumyl chloride and 4.25 mL (0.0305 mol) of triethylamine were added. The system was cooled to -70 ° C. After adding 9.02 mL (0.0305 mol) of titanium (IV) isopropoxide and stirring for 5 minutes, 23.4 mL (0.213 mol) of titanium tetrachloride was added to initiate polymerization. After 5 minutes, add dropwise a mixed solution of 8.03 mL (0.0609 mol) of paramethylstyrene, 5.62 mL of butyl chloride (dried with molecular sieves), and 2.41 mL of hexane (dried with molecular sieves) After starting, the whole amount was dropped over 30 minutes. Thereafter, the polymerization was followed while measuring the amount of residual isobutylene monomer by gas chromatography, and it was judged that the polymerization of isobutylene was completed when it was confirmed that 99.1% of the isobutylene was consumed. At that time, 99.5% of para-methylstyrene was consumed. Next, 61.1 mL (0.531 mol) of styrene was added. Thereafter, the polymerization was traced by gas chromatography while measuring the amount of the remaining styrene monomer, and at a stage where 42% of the styrene monomer was consumed 15 minutes after the addition of styrene, 7.80 mL of titanium tetrachloride was added. Thereafter, after 80 minutes, it was confirmed that the consumption rate of styrene monomer reached 82%, and the polymerization of styrene was finished. The reaction mixture obtained was poured into 1.3 L of a 3 wt% aqueous sodium hydroxide solution heated to 50 ° C., and 542 g of a mixed solvent in which butyl chloride and hexane were mixed at a volume ratio of 9: 1 was used to co The polymerization was terminated by pouring the mixed solvent after washing and co-washing into the aqueous sodium hydroxide solution and vigorously stirring for 60 minutes using a mechanical stirrer. Next, washing was repeated twice with 1.2 L of pure water. Thereafter, volatile components such as a solvent were distilled off under heating, and drying was carried out to obtain isobutylene-methylstyrene copolymer R-5.

The number average molecular weight of the obtained isobutylene-methylstyrene copolymer R-5 was 104, 106, and the molecular weight distribution was 1.36. ^{From 1} H NMR, the number of methylstyrene groups introduced into one polymer molecule was 20.

Using isobutylene-methylstyrene copolymer R-5 (307 g) instead of isobutylene-methylstyrene copolymer R-3, except that 5.9 mL of bromine (Br ₂ ), 1386 mL of butyl chloride and 594 mL of hexane were used The product was produced in the same manner as in Example 1 to obtain a brominated polyisobutylene polymer Q-3. ^{From 1} H NMR, the bromomethyl group was 1.09 mol%, and the reaction rate was 89 mol%.

The vulcanization reactivity of the brominated polyisobutylene polymer Q-3 with respect to polyisoprene rubber was evaluated to be 82 N / 25 mm. Furthermore, the tensile strength was 5.04 MPa.

(Example 4) Synthesis of brominated polyisobutylene polymer Q-4 After purging the inside of the container of a 1 L separable flask with nitrogen, using a syringe, butyl chloride (dried with molecular sieves) 1211 mL and hexane (hexane) 519 mL of dried with molecular sieves was added. The polymerization vessel was immersed in a −80 ° C. dry ice / equine bath and cooled, and then 423 mL (4.48 mol) of isobutylene monomer was added. Next, 0.528 g (2.28 mmol) of p-dicumyl chloride and 4.25 mL (0.0305 mol) of triethylamine were added. The system was cooled to -70 ° C. After adding 9.02 mL (0.0305 mol) of titanium (IV) isopropoxide and stirring for 5 minutes, 23.4 mL (0.213 mol) of titanium tetrachloride was added to initiate polymerization. After 5 minutes, add dropwise a mixed solution of 8.03 mL (0.0609 mol) of paramethylstyrene, 5.62 mL of butyl chloride (dried with molecular sieves), and 2.41 mL of hexane (dried with molecular sieves) After starting, the whole amount was dropped over 30 minutes. Thereafter, the polymerization was followed while measuring the amount of residual isobutylene monomer by gas chromatography, and it was judged that the polymerization of isobutylene was completed when it was confirmed that 98.2% of isobutylene was consumed. At that time, 99.8% of para-methylstyrene was consumed. Next, 61.1 mL (0.531 mol) of styrene was added. Thereafter, the polymerization was followed while measuring the amount of the remaining styrene monomer by gas chromatography, and at a stage where 41% of the styrene monomer was consumed 15 minutes after the addition of styrene, 7.80 mL of titanium tetrachloride was added. Thereafter, after 130 minutes, it was confirmed that the consumption rate of styrene monomer reached 86%, and the polymerization of styrene was completed. The reaction mixture obtained was poured into 1.3 L of a 3 wt% aqueous sodium hydroxide solution heated to 50 ° C., and 542 g of a mixed solvent in which butyl chloride and hexane were mixed at a volume ratio of 9: 1 was used to co The polymerization was terminated by pouring the mixed solvent after washing and co-washing into the aqueous sodium hydroxide solution and vigorously stirring for 60 minutes using a mechanical stirrer. Next, washing was repeated twice with 1.2 L of pure water. Thereafter, volatile components such as a solvent were distilled off under heating, and drying was performed to obtain isobutylene-methylstyrene copolymer R-6.

The number average molecular weight of the obtained isobutylene-methylstyrene copolymer R-6 was 136, 385, and the molecular weight distribution was 1.31. ^{From 1} H NMR, the number of methylstyrene groups introduced into one polymer molecule was 27.

Instead of isobutylene-methylstyrene copolymer R-3, use isobutylene-methylstyrene copolymer R-6 (356 g) and use 5.51 mL of bromine (Br ₂ ), 2276 mL of butyl chloride, and 975 mL of hexane By manufacturing in the same manner as in Example 1 except for the above, a brominated polyisobutylene-based polymer Q-4 was obtained. ^{From 1} H NMR, the bromomethyl group was 1.12 mol%, and the conversion was 92 mol%.

The vulcanization reactivity of the brominated polyisobutylene-based polymer Q-4 with respect to polyisoprene rubber was evaluated to be 91 N / 25 mm. Furthermore, the tensile strength was 5.13 MPa.

(Example 5) Synthesis of brominated polyisobutylene polymer Q-5 After replacing the inside of the container of a 1 L separable flask with nitrogen, butyl chloride and hexane are mixed at a volume ratio of 9: 1 using a syringe 499 mL of the mixed solvent (dried over molecular sieves) was added. The polymerization vessel was immersed in a dry ice / equine bath at −80 ° C. and cooled, and then 38.0 mL (0.402 mol) of isobutylene monomer was added. Next, 0.936 g (0.607 mmol) of a 15% by weight solution of p-dicumyl chloride in butyl chloride, 0.516 mL (3.70 mmol) of triethylamine, and 2.13 mL (16.2 mmol) of paramethylstyrene were added. The system was cooled to -70 ° C. Polymerization was initiated by adding 2.13 mL (19.4 mmol) of titanium tetrachloride. During the reaction, the polymerization solution was withdrawn at any time, and the consumption rates of isobutylene and paramethylstyrene were measured by gas chromatography. After 21 minutes from the introduction of titanium tetrachloride, 88.7 mL (0.939 mol) of isobutylene was added. It was confirmed that 93% of the initially charged isobutylene and 92% of paramethylstyrene were consumed just before this addition of isobutylene. It was confirmed that after 98 minutes of charging titanium tetrachloride, 98.1% of isobutylene and 98.4% of paramethylstyrene were consumed. Next, 17.2 mL (0.150 mol) of styrene was charged. It was confirmed by gas chromatography that 78% of the charged styrene was consumed 78 minutes after the charging of styrene. The reaction mixture obtained was poured into 0.35 L of a 0.4 wt% aqueous sodium hydroxide solution heated to 50 ° C., and mixed with 370 g of a mixed solvent of butyl chloride and hexane at a volume ratio of 9: 1 in a polymerization vessel The co-washing was washed, the mixed solvent after co-washing was poured into the aqueous sodium hydroxide solution, and polymerization was terminated by vigorously stirring for 60 minutes using a mechanical stirrer. Next, it was washed with pure water 0.9 L. Thereafter, volatile components such as a solvent were distilled off under heating, and drying was carried out to obtain isobutylene-methylstyrene copolymer R-7.

The number average molecular weight of the obtained isobutylene-methylstyrene copolymer R-7 was 114,500, and the molecular weight distribution was 1.32. ^{From 1} H NMR, the number of methylstyrene groups introduced into one polymer molecule was 27.

Instead of isobutylene-methylstyrene copolymer R-3, isobutylene-methylstyrene copolymer R-7 (45.6 g) was used, and 0.835 mL of bromine (Br ₂ ), 239 mL of butyl chloride and 27 mL of hexane were used. By manufacturing in the same manner as in Example 1 except for the above, a brominated polyisobutylene-based polymer Q-5 was obtained. ^{From 1} H NMR, the bromomethyl group was 1.00 mol%, and the conversion was 92 mol%.

The vulcanization reactivity of the brominated polyisobutylene-based polymer Q-5 with respect to polyisoprene rubber was evaluated to be 80 N / 25 mm. Furthermore, the tensile strength was 5.09 MPa.

(Example 6) Synthesis of brominated polyisobutylene polymer Q-6 After replacing the inside of a 1 L separable flask with nitrogen, using a syringe, butyl chloride (dried with molecular sieves) 1211 mL and hexane (hexane) 519 mL of dried with molecular sieves was added. The polymerization vessel was immersed in a −80 ° C. dry ice / equine bath and cooled, and then 423 mL (4.48 mol) of isobutylene monomer was added. Next, 0.704 g (3.05 mmol) of p-dicumyl chloride and 4.25 mL (0.0305 mol) of triethylamine were added. The system was cooled to -70 ° C. After adding 11.60 mL (0.0392 mol) of titanium (IV) isopropoxide and stirring for 5 minutes, 30.1 mL (0.274 mol) of titanium tetrachloride was added to initiate polymerization. After 5 minutes, add dropwise a mixed solution of 8.03 mL (0.0609 mol) of paramethylstyrene, 5.62 mL of butyl chloride (dried with molecular sieves), and 2.41 mL of hexane (dried with molecular sieves) After starting, the whole amount was dropped over 30 minutes. Thereafter, the polymerization was followed while measuring the amount of residual isobutylene monomer by gas chromatography, and it was judged that the polymerization of isobutylene was completed when it was confirmed that 98.8% of the isobutylene was consumed. At that time, 99.6% of para-methylstyrene was consumed. Next, 61.1 mL (0.531 mol) of styrene was added. Thereafter, the polymerization was followed while measuring the amount of the remaining styrene monomer by gas chromatography, and at a stage where 44% of the styrene monomer was consumed 15 minutes after the addition of styrene, 6.01 mL of titanium tetrachloride was added. Then, after 141 minutes, it confirmed that the consumption rate of a styrene monomer reached 82%, and complete | finished the superposition | polymerization of styrene. The reaction mixture obtained was poured into 1.3 L of a 3 wt% aqueous sodium hydroxide solution heated to 50 ° C., and 528 g of a mixed solvent in which butyl chloride and hexane were mixed at a volume ratio of 9: 1 was used to co The polymerization was terminated by pouring the mixed solvent after washing and co-washing into the aqueous sodium hydroxide solution and vigorously stirring for 60 minutes using a mechanical stirrer. Next, washing was repeated twice with 1.2 L of pure water. Thereafter, volatile components such as a solvent were distilled off under heating, and drying was carried out to obtain isobutylene-methylstyrene copolymer R-8.

The number average molecular weight of the obtained isobutylene-methylstyrene copolymer R-8 was 180,002, and the molecular weight distribution was 1.17. ^{From 1} H NMR, the number of methylstyrene groups introduced into one polymer molecule was 40.

Using isobutylene-methylstyrene copolymer R-8 (302 g) instead of isobutylene-methylstyrene copolymer R-3, except using 6.22 mL of bromine (Br ₂ ), 1931 mL of butyl chloride, and 828 mL of hexane The same procedure was carried out as in Example 1 to obtain a brominated polyisobutylene polymer Q-6. ^{From 1} H NMR, the bromomethyl group was 1.19 mol%, and the reaction rate was 97 mol%.

The vulcanization reactivity of the brominated polyisobutylene-based polymer Q-6 with respect to polyisoprene rubber was evaluated to be 122 N / 25 mm. Furthermore, the tensile strength was 4.04 MPa.

Comparative Example 7 Synthesis of Brominated Polyisobutylene Polymer P-7 The isobutylene-methylstyrene copolymer R-3 (134 g) obtained in Example 1 and 3.4 mL of bromine (Br ₂ ) were chlorinated. It was dissolved in a mixed solvent of 600 mL of butyl and 66.6 mL of n-hexane at room temperature. Next, 0.178 g of azoisobutyronitrile (AIBN) was added and refluxed for 15 minutes. After that, since the dark brown color of bromine in the solution disappeared, it was judged that the reaction was completed. The resulting reaction mixture was reprecipitated from acetone to obtain a brominated polyisobutylene polymer P-7. ^{From 1} H NMR, the bromomethyl group was 0.92 mol%, and the reaction rate was 38 mol%.

The vulcanization reactivity of the brominated polyisobutylene polymer P-7 to polyisoprene rubber was evaluated to be 63 N / 25 mm.

Comparative Example 8 Synthesis of Brominated Polyisobutylene Polymer P-8 The isobutylene-methylstyrene copolymer R-3 (40 g) obtained in Example 1 and 1.0 mL of bromine (Br ₂ ) in 180 mL of butyl chloride And n-hexane were dissolved in a mixed solvent at room temperature. Next, the reaction mixture was irradiated for 90 minutes at room temperature with a high pressure mercury lamp light source having a maximum wavelength at a wavelength of 365 nm. Next, the reaction mixture was reprecipitated from acetone to obtain a brominated polyisobutylene polymer P-8. ^{From 1} H NMR, the bromomethyl group was 0.87 mol%, and the conversion was 36 mol%.

The vulcanization reactivity of the brominated polyisobutylene copolymer P-8 to the polyisoprene rubber was evaluated to be 62 N / 25 mm.

Comparative Example 9 Synthesis of Brominated Polyisobutylene Polymer P-9 The inside of a 500 mL separable flask was purged with nitrogen, and then 247 mL of butyl chloride (dried with molecular sieves) and hexane (using molecular syringes) using a syringe. 27 mL of dried (by molecular sieves) was added. The polymerization vessel was immersed in a dry ice / acetone bath at −80 ° C. and cooled, and then 85 mL (0.899 mol) of isobutylene monomer was added. Next, 0.1412 g (0.61 mmol) of p-dicumyl chloride and 0.12 mL (1.25 mmol) of α-picoline were added. The system was cooled to -70 ° C. Polymerization was initiated by adding 0.96 mL (0.0087 mol) of titanium tetrachloride. The polymerization was followed by measuring the amount of residual isobutylene monomer by gas chromatography, and it was judged that the polymerization of isobutylene was completed when 99.8% of isobutylene was consumed, and then 9.8 mL of styrene (0 .085 mol) was added. After 2 minutes, 3.22 mL (0.0244 mol) of paramethylstyrene was added. Thereafter, the polymerization was traced while measuring the amount of residual styrene monomer by gas chromatography, and the polymerization of styrene was terminated when 85% of the styrene monomer was consumed. At this time, 95% of paramethylstyrene was consumed.

Next, the reaction mixture obtained was poured into 1 L of pure water heated to 70 ° C., and polymerization was stopped by vigorously stirring for 60 minutes using a mechanical stirrer. Next, washing was repeated three times with 1 L of pure water. Thereafter, volatile components such as a solvent were distilled off under heating, and drying was carried out to obtain isobutylene-methylstyrene copolymer R-4.

The number average molecular weight of the obtained isobutylene-methylstyrene copolymer R-4 was 91,005, and the molecular weight distribution was 1.15. ^{From 1} H NMR, the number of methylstyrene groups introduced into one molecule of polymer was 38.

Next, the obtained isobutylene-methylstyrene copolymer R-4 (40 g) and 0.8 mL of bromine (Br ₂ ) were dissolved in a mixed solvent of 180 mL of butyl chloride and 20 mL of n-hexane at room temperature. Next, the reaction mixture was irradiated with a single wavelength LED light source having a wavelength of 395 nm for 90 minutes at room temperature. Thereafter, it was judged that the reaction was completed because the dark brown peculiar to bromine became faint and orange from the reaction mixture. The reaction mixture was reprecipitated from acetone to obtain a brominated polyisobutylene polymer P-9. ^{From 1} H NMR, the bromomethyl group was 1.40 mol%, and the reaction rate was 60 mol%.

The vulcanization reactivity of the brominated polyisobutylene polymer P-9 to the polyisoprene rubber was evaluated to be 41 N / 25 mm.

From the above results, as compared with the brominated polyisobutylene-based polymer having a low bromination rate of methylstyrene group and a low proportion of bromomethylstyrene group in constituent monomer units as Comparative Examples 7 and 8, It is understood that the brominated polyisobutylene-based polymer is excellent in the vulcanization reactivity with different rubber members such as polyisoprene rubber.

Further, according to Comparative Example 9, it is understood that when the bromination rate is less than 65 mol%, the vulcanization reactivity to the rubber member tends to decrease.

Further, as shown in Example 1, the oxygen permeability coefficient shows a good value as in the general-purpose butyl rubber shown in Production Example 4, and a brominated polyisobutylene-based polymer according to an embodiment of the present invention It has been found that has good gas barrier properties.

Furthermore, the brominated polyisobutylene-based polymer obtained in Example 1 had a tensile strength of 7.00 MPa and exhibited elastic deformation. From this feature, it is found that the green strength is excellent, and the moldability to various shapes is excellent.

This is also suggested from the result that the oxygen permeability in Example 1 is good, and it can be seen that even when molded into a thin film, pinholes and breakage are less likely to occur.

Next, the influence of monomer species present in the reaction system during the bromination reaction was examined. Here, conditions under which the value represented by (mole number of styrene) / (mole number of bromine) is 0.896 were examined.

Comparative Example 10 Bromination Reaction in the Presence of Styrene Monomer The isobutylene-methylstyrene copolymer R-3 (40 g) obtained in Example 1, 0.8 mL (0.0155 mol) of bromine (Br ₂ ), styrene 1.6 mL (0.0134 mol) of the monomer was dissolved in a mixed solvent of 180 mL of butyl chloride and 20 mL of n-hexane at room temperature. The reaction mixture was irradiated for 90 minutes at room temperature with a single wavelength LED light source at a wavelength of 395 nm. The reaction mixture was reprecipitated from acetone to obtain a brominated polyisobutylene polymer P-10. ^{From 1} H NMR, the bromomethyl group was 0.19 mol%, and the reaction rate was 8 mol%.

In addition, from the ¹ H NMR of the reaction mixture, a peak derived from the residual styrene monomer could not be confirmed, and instead, new peaks could be confirmed around 4.2 ppm and 5.3 ppm. As considered from the reaction mode, these two peaks are attributed to styrene dibromide (brominated adduct of styrene). From this result, it can be seen that the addition reaction of bromine molecules to styrene proceeds very rapidly and quantitatively. In the present invention, this is a side reaction to be limited, and in order to obtain a bromination rate of 65 mol% or more, the value represented by (mole number of styrene) / (mole number of bromine) is from 0.35 The size is preferably small, and from the viewpoint of reducing the impurities remaining in the resin, the condition is preferably smaller than 0.1.

Next, the influence of the catalyst species present in the reaction system during the bromination reaction was examined. Here, conditions under which the value represented by (the number of moles of metal halide compound) / (the number of moles of bromine) is 1.6 were examined.

(Comparative Example 11) Bromination reaction in the coexistence of a metal halide compound catalyst The methylstyrene-isobutylene copolymer R-3 (4 g) obtained in Example 1, 0.1 mL (0.0194 mol) of bromine (Br ₂ ) ), 0.634 g (0.00314 mol) of TiCl _3.5 (OiPr) _0.5 was dissolved in a mixed solvent of 18 mL of butyl chloride and 2 mL of n-hexane at room temperature. The reaction mixture was irradiated with a single-wavelength LED light source at a wavelength of 395 nm for 60 minutes at room temperature, and the reaction mixture continued to react for another 2 hours because it had a dark brown color of bromine. Thereafter, the reaction mixture was reprecipitated from acetone to obtain a brominated polyisobutylene polymer P-11.

^{From 1} H NMR, the bromomethyl group was 0.44 mol%, and the reaction rate was 18 mol%. In comparison to Example 1, it is clear that the metal halide compounds inhibit the bromination reaction. Although the detailed reaction mechanism is unknown, it is suggested that the coexistence of metal halide compounds prevents the generation of radical species from bromine (Br ₂ ) by light irradiation, thereby slowing the reaction rate it is conceivable that.

Physical properties of isobutylene-methylstyrene copolymer, proportion of brominated methylstyrene group in brominated polyisobutylene-based polymer, bromination ratio, and physical properties of Examples 1 to 6 and Comparative Examples 1 to 11 Reactivity, oxygen permeability coefficient and tensile strength are described in Tables 1 and 2.

The brominated polyisobutylene-based polymer according to one embodiment of the present invention exhibits (a) excellent vulcanization reactivity and (b) excellent balance between the rubber strength and the gas barrier properties. Therefore, the brominated polyisobutylene-based polymer according to one embodiment of the present invention includes various seal members, tubes, resins or asphalt modifiers, adhesives or adhesives, viscosity modifiers, paint base resins, and damping materials. It can be suitably used as a vibration-proof material, shock-absorbing material, sound-proof material, sound-absorbing material, foam, and PVC alternative material.

Claims (10)

Containing a methylstyrene group which is not brominated and a brominated methylstyrene group as constituent units,
65 mol% or more of the brominated methylstyrene groups with respect to a total amount of 100 mol% of the non-brominated methylstyrene groups and the brominated methylstyrene groups,
A brominated polyisobutylene-based polymer comprising 1.00 mol% or more of the brominated methylstyrene group with respect to 100 mol% of the total of the constituent units. The non-brominated methylstyrene group is p-methylstyrene (4-methylstyrene) group, and the brominated methylstyrene group is p-bromomethylstyrene (4-bromomethylstyrene) group The brominated polyisobutylene-based polymer according to claim 1, which is characterized in that The brominated polyisobutylene-based polymer is a block copolymer comprising a polymer block (a) composed mainly of isobutylene and a polymer block (b) composed mainly of an aromatic vinyl compound. The brominated polyisobutylene-based polymer according to claim 1 or 2. The polymer block (a) composed mainly of the isobutylene is defined in the case where the total amount of the non-brominated methylstyrene group and the brominated methylstyrene group in the brominated polyisobutylene polymer is 100% by weight. The brominated polyisobutylene-based polymer according to claim 3, comprising 50% by weight or more of the non-brominated methylstyrene group and the brominated methylstyrene group. The oxygen permeability coefficient is 0.0 to 10.0 × 10 ⁻¹⁶ (mol · m / (m ² · second · Pa)), and the tensile strength is 5.00 to 30.00 MPa,
Here, the oxygen permeability coefficient is a value measured in accordance with the method described in JIS K-7126, and the tensile strength is a value measured in accordance with the method described in JIS K-6251. The brominated polyisobutylene-based polymer according to any one of claims 1 to 4, characterized in that A reaction mixture preparation step of preparing a reaction mixture by mixing an isobutylene polymer containing one or more methylstyrene groups as a constitutional unit, and a compound containing bromine;
Irradiating the reaction mixture with light using an irradiation apparatus to convert one or more of the methylstyrene groups into a brominated methylstyrene group;
Here, the light contains (a) light with a wavelength of 350 nm to 600 nm, and (b) when the total intensity of the light is 100%, the intensity of light with a wavelength of 300 nm or less is 5% or less The method for producing a brominated polyisobutylene-based polymer according to any one of claims 1 to 5, characterized in that The method for producing a brominated polyisobutylene-based polymer according to claim 6, wherein the irradiation device is a light emitting diode (LED). (A) the reaction mixture is substantially free of styrene, or (b) the reaction mixture further contains styrene, and the ratio of the number of moles of styrene to the number of moles of bromine in the reaction mixture 8. The method for producing a brominated polyisobutylene-based polymer according to claim 6, wherein ((number of moles of styrene) / (number of moles of bromine)) is less than 0.35. Method. (A) the reaction mixture is substantially free of a metal halide compound, or (b) the reaction mixture further contains a metal halide compound, and the mole of the metal halide compound in the reaction mixture 9. The method according to claim 6, wherein the ratio of the number to the number of moles of bromine (the value represented by (number of moles of metal halide compound) / (number of moles of bromine)) is less than 1.5. The manufacturing method of the brominated polyisobutylene type | system | group polymer as described in any one of these. The method for producing a brominated polyisobutylene-based polymer according to any one of claims 6 to 9, wherein the compound containing bromine is a bromine molecule (Br ₂ ).