WO2007046344A1

WO2007046344A1 - Process for producing isobutylene block copolymer

Info

Publication number: WO2007046344A1
Application number: PCT/JP2006/320600
Authority: WO
Inventors: Ryuji Fukuda
Original assignee: Kaneka Corporation
Priority date: 2005-10-17
Filing date: 2006-10-16
Publication date: 2007-04-26
Also published as: JPWO2007046344A1

Abstract

A process for producing an isobutylene block copolymer comprising a polymer block formed from one or more monomers comprising isobutylene as the main ingredient and a polymer block formed from one or more monomers in which isobutylene is not the main ingredient. The block copolymer stably has excellent mechanical properties and is stably flowable in a molten state. A monomer ingredient (a) comprising isobutylene as the main component is reacted with a monomer ingredient (b) in which isobutylene is not the main component, in the presence of a polymerization initiator having a given structure while keeping the amount of water at up to 75 weight ppm of the total amount of the reaction solvent and the monomer ingredients.

Description

Specification

Method for producing isobutylene block copolymer

Technical field

The present invention relates to a method for producing an isobutylene block copolymer. More specifically, the present invention relates to a process for producing an isobutylene block copolymer comprising a polymer block having isobutylene as a main component of monomer and excellent polymer characteristics and a polymer block having no isoprene as a main component of monomer.

Background art

[0002] By isotopylene and aromatic vinyl monomers such as styrene by cationic polymerization, a polymer block composed of isoprene and an isobutylene block copolymer composed of a polymer block composed of an aromatic vinyl monomer It is known that coalescence can be produced. For example, Patent Document 1 discloses a method for producing an isobutylene block copolymer in a mixed solvent in which methyl chloride and methylcyclohexane are combined. Patent Document 2 also discloses a method for producing a block copolymer of isoprene and styrene force in a mixed solvent composed of methylene chloride and hexane.

[0003] A polymer block composed mainly of an aromatic vinyl monomer composed of a polymer block composed of isoprene and a polymer block composed of an aromatic vinyl monomer by the methods described in these patent documents. —Polymer block mainly composed of isobutylene—When a triblock copolymer formed from a polymer block composed mainly of an aromatic butyl monomer is produced, the raw material handling method and polymerization during the production Depending on the polymerization operation, the mechanical properties represented by the tensile strength of the obtained triblock copolymer are not constant and may be significantly reduced, or the melt viscosity that affects the molding processing characteristics may be reduced. It was.

Patent Document 1: US Patent No. 4946899 Specification

Patent Document 2: Japanese Patent Publication No. 7-59601

Disclosure of the invention

Problems to be solved by the invention

[0004] In view of the above-mentioned problems of the prior art, an object of the present invention is to stably provide excellent mechanical properties. The isobutylene block copolymer consisting of a polymer block containing isobutylene as the main monomer component and a polymer block not containing isobutylene as the main monomer component and having stable fluidity when melted It is intended to provide a method.

Means for solving the problem

[0005] As a result of extensive research, the present inventor performs the polymerization reaction of the isobutylene block copolymer under the condition that the water content is maintained at 75 pmm or less with respect to the total weight of the reaction solvent and the monomer component. As a result, the inventors have found that the above problems can be solved, and have reached the present invention.

[0006] That is, the present invention is a method in which the water content relative to the total weight of the reaction solvent and the monomer component is maintained at 75 ppm or less in the presence of a polymerization initiator represented by the following general formula (1). A polymer comprising isobutylene as a main monomer component, comprising reacting a monomer component (a) containing sobutylene as a main component with a monomer component (b) not containing isobutylene as a main component. The present invention relates to a method for producing an isobutylene-based block copolymer having a polymer block power that does not contain block and isobutylene as monomer main components.

[0007] [Chemical 2]

(In the formula, a plurality of R ^{1 s} are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group having carbon number:! To 6; R ² represents a monovalent or polyvalent aromatic carbonization. Represents a hydrogen group or a monovalent or polyvalent aliphatic hydrocarbon group, X represents a halogen atom, an alkoxyl group having from 6 to 6 carbon atoms, or an alkoxyl group having from 1 to 6 carbon atoms, n is And represents an integer of 1 to 6. When a plurality of Xs are present, they may be the same or different.

It is preferable to keep the water content with respect to the total weight of the reaction solvent and the monomer component at 50 ppm or less, more preferably 20 ppm or less. [0009] In a preferred embodiment, the present invention relates to the above production method, wherein the polymerization reaction is carried out in the presence of a Lewis acid.

[0010] A further preferred embodiment relates to the above-described production method using titanium tetrachloride as norelic acid.

In a preferred embodiment, the polymerization initiator represented by the general formula (1) is bis (1-chloro-1-1-methylethyl) benzene [CH (C (CH) C1)] or (1-chloro-one). 1-methylethyl) benzene [CHC (CH 3) C1] The above production method is at least one selected from the group.

[0012] As a preferred embodiment, the monomer component (b) not containing isobutylene as a main component relates to the production method described above, which is a monomer component containing an aromatic vinyl monomer as a main component.

[0013] In a more preferred embodiment, the aromatic bur monomer is related to the above production method, which is at least one selected from the group consisting of styrene, p-methylol styrene, monomethyl styrene and indene.

[0014] As a preferred embodiment, the isobutylene block copolymer is a polymer block mainly composed of an aromatic butyl monomer. A polymer block mainly composed of an isobutylene is an aromatic butyl monomer. A triblock copolymer formed from a polymer block as a component, a polymer block mainly composed of isobutylene, a polymer block mainly composed of an aromatic butyl monomer, and a polymer block mainly composed of isobutylene Selected from the group consisting of a triblock copolymer formed from a diblock copolymer formed from a polymer block mainly composed of an aromatic butyl monomer and a polymer block composed mainly of a sobutylene It is related with the said manufacturing method which is at least 1 sort.

As a preferred embodiment, a monohalogenated hydrocarbon solvent comprising a primary monohalogenated hydrocarbon having 3 to 8 carbon atoms and Z or a secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms, and In addition, the present invention relates to the above production method, wherein the polymerization is carried out in a mixed solvent with a non-halogen hydrocarbon solvent comprising an aliphatic hydrocarbon and / or an aromatic hydrocarbon.

In a preferred embodiment, the monohalogenated hydrocarbon solvent is at least one selected from the group consisting of 1_chloropropane and 1_chlorobutane. About.

[0017] In a preferred embodiment, the non-halogenated hydrocarbon solvent is at least one selected from the group consisting of hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane. About.

The invention's effect

[0018] According to the production method of the present invention, a polymer block comprising isobutylene as a main component of monomer and isobutylene as a monomer, which stably exhibits excellent mechanical properties and has a stable fluidity upon melting. An isobutylene block copolymer composed of a polymer block which is not a main component is obtained. For this reason, a molded product can be obtained in which the processing characteristics without any significant change in the properties of the polymer each time the polymerization is performed and the properties after molding are not varied.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

[0020] The present invention mainly comprises isobutylene in the presence of a polymerization initiator represented by the following general formula (1) in a state where the water content relative to the total weight of the reaction solvent and the monomer component is maintained at 75 ppm or less. A polymer block containing isobutylene as a main component of a monomer and an isobutylene, characterized by reacting the monomer component (a) as a main component with a monomer component (b) containing no isobutylene as a main component. The present invention relates to a method for producing an isobutylene block copolymer comprising a polymer block containing no main component of ethylene.

[0021] [Chemical 3]

(In the formula, a plurality of R ^{1 s} are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group having from 6 to 6 carbon atoms. R ² represents a monovalent or polyvalent aromatic hydrocarbon group or Monovalent or polyvalent fat Represents a group hydrocarbon group. X represents a halogen atom, an alkoxyl group having from 6 to 6 carbon atoms, or a alkoxyl group having from 1 to 6 carbon atoms. n represents an integer of 1 to 6. When there are a plurality of X, they may be the same or different.

[0023] The above-mentioned monomer component (b) containing isobutylene as a main component is preferably a monomer component having an isoprene content of 30% by weight or less, preferably 10% by weight or less. More preferably, it is more preferably 3% by weight or less. This is because when the content of isoprene is 30% or more, excellent mechanical strength is not exhibited.

[0024] The monomer other than isobutylene in the monomer component (b) not containing isobutylene as the main component of the present invention is not particularly limited as long as it is a monomer capable of cationic polymerization, but aliphatic olefins. And monomers such as aromatic burs, gens, bur ethers, silanes, burcarbazonoles, β-pinene, and acenaphthylene. These can be used alone or in combination of two or more.

[0025] The aliphatic olefin-based monomer is not particularly limited. For example, ethylene, propylene, 1-butene, 2-methyl 1-butene, 3-methyl 1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexene, otaten, norbornene and the like.

[0026] The aromatic bur monomer is not particularly limited. For example, styrene, ο-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2, 6 dimethylstyrene, 2, 4 Dimethylstyrene, α-methyl-ο-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, -methyl-ο-methylstyrene, β-methyl-m-methylstyrene, β-methyl-ρ-methylstyrene, 2, 4, 6 trimethylstyrene , 1 methylolene 2, 6 _ dimethyl styrene, 1 methyl _ 2, 4-dimethyl styrene, β-methyl 1, 2, 6 dimethyl styrene, β-methyl _ 2, 4 _ dimethyl styrene, o _, m Or ρ-Chlorostyrene, 2,6-Dichlorostyrene, 2,4-Dichlorostyrene, Single _o _Chlorostyrene, Single _m Rollostyrene, one black mouth p-chlorostyrene, one black mouth _o_chlorostyrene, / 3 _ black mouth _m-chlorostyrene, —black mouth _ρ-chlorostyrene, 2, 4, 6 _trichlorostyrene, one black Mouth _ 2, 6-Dichlorostyrene, Hokukuro 1, 2, 4-Dichlorostyrene,; 3-Chloro 1, 2, 6-Dichloro Mouth Styrene, β-chloro-2,4-dichlorostyrene, ο—, m—or p-t butinoresylene, o—, m—or p-methoxystyrene, o—, m or p chloromethylstyrene, o—, m—or p Bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, urnaphthalene and the like.

[0027] The gen-based monomer is not particularly limited, and examples thereof include butadiene, isoprene, cyclopentagen, cyclohexagen, dicyclopentagen, dibutenebenzene, and ethylidene norbornene.

[0028] The butyl ether monomer is not particularly limited, and examples thereof include methyl butyl ether, ethyl vinyl ether, ( _n- , iso) propyl butyl ether, ( _n- , sec-, tert-, iso) butino. Revinino reetenore, methino lepropenole ethenore, ethino lepropenole eleter and the like.

[0029] The silanic compound is not particularly limited, and examples thereof include butyltrichlorosilane, butylmethyrene resin chlorosilane, vinyldimethylchlorosilane, butyldimethylmethoxysilane, vinyltrimethylsilane, dibutydichlorosilane, dibutydimethoxysilane, and dibutymethylenosilane. 1,3-Divininole 1,1,3,3-Tetramethylenoresisiloxane, Trivininoremethinoresilane, γ-methacryloyloxyprovir trimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, etc. .

[0030] The monomer component (b) not containing isobutylene as a main component of the present invention may be a monomer component containing an aromatic vinyl monomer as a main component from the balance of physical properties and polymerization characteristics. I like it. The monomer component mainly composed of the aromatic bulle monomer of the present invention is a monomer component having an aromatic bule monomer content of 60% by weight or more, preferably 80% by weight or more. Show. Here, it is preferable to use at least one monomer selected from the group consisting of styrene, monomethylstyrene, p-methylstyrene, and indene as the aromatic bule monomer, and in terms of cost. It is particularly preferable to use styrene, monomethylstyrene, p-methylstyrene or a mixture of these.

[0031] The monomer component (a) containing isobutylene as a main component may or may not contain a monomer other than isobutylene as a monomer component. The monomer component contains 60% by weight or more, preferably 80% by weight or more of isobutylene. The above isobutyle There are no particular restrictions on the monomers other than styrene, as long as they are cationically polymerizable monomers. For example, aliphatic olefins, aromatic vinyls, gens, vinyl ethers, silanes, vinyl carbazole, β- Examples thereof include monomers such as binene and acenaphthylene. These may be used alone or in combination of two or more.

[0032] The ratio of the polymer block mainly composed of isobutylene and the polymer block composed of a monomer component mainly composed of aromatic butyl is not particularly limited, but from the viewpoint of various physical properties, isobutylene is mainly used. It is preferable that the polymer block comprising 40 to 95% by weight of the polymer block and the polymer block comprising the monomer component mainly composed of aromatic bur are 5 to 60% by weight. It is particularly preferable that the polymer block is 50 to 85% by weight and the polymer block composed of a monomer component mainly composed of aromatic bur is 15 to 50% by weight.

[0033] In addition, the number average molecular weight of the isobutylene block copolymer is not particularly limited, but the surface strength such as fluid life, Kaloe life, and life time is 30,000 to 500,000. The power that is between 50000 and 400000 S, especially preferred. If the number average molecular weight of the isobutylene block copolymer is lower than the above range, mechanical properties tend not to be sufficiently expressed. On the other hand, if the number exceeds the above range, the flowability and processability are poor. It is disadvantageous. The above-mentioned number average molecular weight is obtained by Waters Gel Permeation Chromatography (GPC) system (column: Showa Denko Shodex K-804, K 802.5 (polystyrene gel), mobile phase: black mouth form). It is the value measured using.

[0034] The preferred block copolymer of the isobutylene block copolymer (a) is a polymer block isobutylene containing an aromatic vinyl monomer as a main component from the viewpoint of physical balance. A polymer block having an aromatic vinyl monomer as a main component, a triblock copolymer having a polymer block having an aromatic vinyl monomer as a main component, and a polymer block having an aromatic vinyl monomer as a main component. Polymer block strength as the main component

And a star block copolymer having three or more arms each composed of a polymer block mainly composed of an aromatic bur monomer and a polymer block mainly composed of isobutylene. These can be used alone or in combination of two or more in order to obtain the desired physical properties and moldability. Among these, the triblock structure is particularly preferred from the viewpoint of processability and cost. A styrene isobutylene styrene block copolymer and a styrene isobutylene block copolymer having a diblock structure are preferred.

[0035] The compound represented by the general formula (1) serves as an initiator and serves as a starting point for cationic polymerization. In the formula, a plurality of R ^{1 s} are the same or different and represent a hydrogen atom or a monovalent hydrocarbon group having 6 to 6 carbon atoms. R ² represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group. X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or a alkoxyl group having 1 to 6 carbon atoms. n represents an integer of 1 to 6. When a plurality of X are present, they may be the same or different.

[0036] Examples of the compound of the general formula (1) used in the present invention include the following compounds.

(1-chloro- 1-methylethyl) benzene [CHC (CH) Cl], 1,4_bis (1-chloroethyl_1-methylethyl) benzene [1, 4-CKCH) CC HC (CH) CI], 1, 3_ screw

(1-chloro-1- 1-methylethyl) benzene [1, 3-Cl (CH) CC H C (CH) Cl], 1

, 3, 5—Tris (1—chloro—1-methylethyl) benzene [1, 3, 5— (CIC (CH)) C

H], 1,3-bis (1 chloro 1 methylethyl) 1-5- (tert butyl) benzene [1,

3— (C (CH) C1) 5— (C (CH)) CH]

[0037] Among these, (1 chloro 1-methylethyl) benzene [C H C] is particularly preferable.

(CH) Cl], bis (1-chloro-1- 1-methylethyl) benzene [CH (C (CH) CI)], tris (1-chloro-1-methylethyl) benzene [(C1C (CH)) 〇 ^ 1 ] N- (1-chloro-1-methylethyl) benzene is also referred to as (cyclochloroisopropyl) benzene, (2-chloro-2-propyl) benzene or tammyl chloride, and bis (1-chloro-1-methylenoethyl) benzene is bis Also known as (one black mouth isopropylene) benzene, bis (2-chloro mouth _ 2_propyl) benzene or dicmilk mouth ride, tris (1 chloro one 1-methinore ethinore) benzene is tris (one head mouth isopropylene). Nore) benzene, tris (2-chloropropyl) benzene or tritamilk chloride.

[0038] When the isobutylene block copolymer is produced, a Lewis acid catalyst may be allowed to coexist. Such Lewis acid may be any one that can be used for cationic polymerization. TiCl, TiBr, BC1, BF, BF-OEt, SnCl, SbCl, SbF, WC1, TaCl, VC1 Metal halides such as FeCl, ZnBr, A1C1, and AlBr; Organometallic halides such as EtA1C1 and EtAlCl can be preferably used (Et represents an ethyl group). Of these, TiCl, BC1, and SnCl are preferred when considering the ability as a catalyst and industrial availability. The amount of norelic acid used is not particularly limited, but can be set in view of the polymerization characteristics or polymerization concentration of the monomer used. Usually, 0.1 to 100 molar equivalents can be used with respect to the compound represented by the general formula (1), preferably in the range of 1 to 50 molar equivalents.

[0039] When the isobutylene block copolymer is produced, an electron donor component may be further present if necessary. This electron donor component is believed to have the effect of stabilizing the growing carbon cation during cationic polymerization, and the addition of an electron donor produces a polymer with a controlled molecular weight distribution structure. Can do. The electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom. it can.

[0040] Examples of the electron donor component include those having 15 to 60 donors defined as one parameter representing the strength of various compounds as electron donors (electron donors). 2,6-di-t-butylpyridine, 2-t-butylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylviridine, 2-methinolepyridine, pyridine, jetylamine, trimethylamine, triethylamine , Tributylamine, N, N-dimethylaniline, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-jetylacetamide, dimethyl sulfoxide, jetyl ether, methyl acetate, acetic acid Ethyl, trimethyl phosphate, hexamethyl phosphate triamide, titanium (III) methoxide, titanium (IV) methoxide, titanium (IV) isopropoxide, Titanium (IV) butoxide and other titanium alkoxides; aluminum triethoxide and aluminum tributoxide and other aluminum alkoxides can be used. Preferred examples include 2,6-di_t_butylpyridine, 2,6_dimethylpyridine, 2-Methylenopyridine, pyridine, cetylamine, trimethinoleamine, triethylamine, N, N-dimethylolenolemamide, N, N-dimethylacetamide, dimethyl sulfoxide, titanium (IV) isopropoxide, titanium (IV) Examples include butoxide. To the number of donors of the above various substances About "Donor and Acceptor", by Dardman, Otsuki, Okada translation, Academic Publishing Center

(1983). Among these, 2-methylpyridine, N, N-dimethylacetamide, which has a remarkable effect of addition, and titanium (IV) isopropoxide that makes the reaction system uniform are particularly preferable.

[0041] The electron donor component is used in an amount of 0.01 to 10 moles relative to the polymerization initiator. Of these, it is preferably used in the range of 0.2 to 4 moles.

[0042] The polymerization can be carried out in a solvent, if necessary. As the solvent, any conventionally known solvent can be used as long as it does not essentially inhibit cationic polymerization. Specifically, methyl chloride, dichloromethane, n-propyl chloride, n-butinorechloride can be used. Halogenated hydrocarbons such as benzene, toluene, xylene, ethylbenzene, alkylbenzenes such as propylbenzene, butylbenzene; ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, etc. Linear aliphatic hydrocarbons; branched aliphatic hydrocarbons such as 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, 2,2,5-trimethylhexane; cyclohexane, Cycloaliphatic hydrocarbons such as methylcyclohexane and ethylcyclohexane; paraforms obtained by hydrogenation of petroleum fractions Mention may be made of the fin oil, and the like. These homogeneous IJs are used alone or in combination of two or more in consideration of the balance of the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer. . Among them, monohalogenated hydrocarbon solvents composed of primary monohalogenated hydrocarbons having 3 to 8 carbon atoms and / or secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms, aliphatic hydrocarbons and / or Alternatively, polymerization in a mixed solvent with a non-halogen hydrocarbon solvent composed of an aromatic hydrocarbon improves workability in the water washing step after polymerization, and facilitates wastewater treatment after water washing. Preferred from.

[0043] The primary monohalogenated hydrocarbon having 3 to 8 carbon atoms and the secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms are not particularly limited. For example, 1_chloropronone, 1_black port _ 2_ methyl propane, 1 _ chlorobutane, 1 _ black mouth 1 _ methyl butane, 1 _ black mouth _ 3-metheno levane, 1 _ chloro _ 2, 2- dimethyl butane, 1 _ chloro _ 3, 3-dimethyl butane, 1 —Black mouth _ 2, 3—Dimethylbutane, 1 _Black mouth pentane, 1 _Black mouth _ 2—Methyl pentane 1 Chloro-3-methinorepentane, 1 Chloro-4-methenorepentane, 1-Hexane Hexane, 1-Chlorochi-one 2-Methinorehexane, 1-Chloro-one 3-Metinorehexane, 1-Chloro-One 4 —Methinorehexane, 1—Black mouth 5—Methinorehexane, 1—Black mouth heptane, 1—Chlorooctane, 2 — Black mouth prono ヽ. , 2-chlorobutane, 2-chloropentane, 2-hexane hexane, 2-chloroheptane, 2-chlorooctane, chlorobenzene, and the like. These can be used alone or in combination of two or more.

For example, a monohalogenated solvent having 3 carbon atoms, a monohalogenated solvent having 4 carbon atoms, a combination of a monohalogenated solvent having 3 carbon atoms and a monohalogenated solvent having 4 carbon atoms, monohalogenated with 4 to 8 carbon atoms It may be a combination of at least one of the solvents. Of these, if importance is attached to the balance of the solubility of the isobutylene block copolymer, the ease of detoxification by decomposition, the balance of costs, etc., it is particularly preferable to use 1_black propane and Z or 1_chlorobutane. _Chlorobutane is preferred.

[0044] The aliphatic hydrocarbon and the aromatic hydrocarbon as the non-halogen solvent are not particularly limited. For example, butane, pentane, neopentane, hexane, heptane, octane, cyclohexane, methylcyclohexane , Ethylcyclohexane, benzene, toluene, xylene, ethylbenzene and the like. These can be used alone or in combination of two or more. From the balance of solubility, cost, dielectric constant, etc. of the block copolymer, at least one selected from the group consisting of hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and xylene is preferred. Particularly preferred is at least i selected from the group consisting of methylcyclohexane and ethylcyclohexane.

[0045] The polymerization solvent in the present invention is a monohalogenated hydrocarbon comprising the primary monohalogenated hydrocarbon having 3 to 8 carbon atoms and / or the secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms. And a non-halogenated hydrocarbon solvent composed of an aliphatic hydrocarbon and / or an aromatic hydrocarbon. The content of the monohalogenated hydrocarbon solvent in the mixed solvent is not particularly limited, and may be set so as to obtain a desired dielectric constant or solubility of the block copolymer. 98% by weight, preferably 20 to 95% by weight. [0046] The amount of the solvent used is determined in consideration of the viscosity of the resulting polymer solution and the ease of heat removal. Usually, the concentration of the polymer is adjusted to 1 to 50 wt%, preferably 5 Set to ~ 35wt%.

[0047] The method for producing the isobutylene block copolymer of the present invention is not particularly limited except that the amount of water during the reaction is adjusted using a polymerization initiator. For example, the above general formula is used in the above solvent. Add the compound represented by (1) and, if necessary, an electron donor component, a monomer component mainly composed of an aromatic butyl monomer or a monomer component mainly composed of isobutylene, and further add Lewis Polymerization is started by adding an acid, and after the polymerization of the added monomer component is substantially completed, another monomer component may be added and polymerized. Furthermore, if necessary, another monomer component may be added after the polymerization is substantially completed, and the polymerization may be continued.

[0048] In the present application, the water content is a value measured by a Karl Fischer moisture meter.

This value is liquid at normal temperature and normal pressure among the water content of the reaction solvent used for polymerization and the monomer components added to the polymerization system before the start of polymerization (before the addition of Lewis acid catalyst). The amount of water present in the reaction system can be calculated from the total amount of water of the monomer components, the reaction solvent weight, and the monomer weight. In the measurement of the amount of water, the monomer component is a component that is added to the polymerization system before the start of polymerization, including the initiator and electron donor component, which are composed of only the monomer component constituting the polymer. Shall be included.

[0049] In the present invention, the reaction is carried out in a state where the water content relative to the total weight of the reaction solvent and the monomer component is kept at 75 ppm or less. The water content is preferably 50 ppm or less, more preferably 2 Oppm or less. When the moisture content is higher than 75 _PP m, the tensile strength of the polymer obtained under the same reaction conditions except for the moisture content is 75 ppm or less. The flow characteristics of the The higher the water content, the lower the tensile strength and the higher the melt flow rate. For this reason, when a polymerization reaction is carried out with a water content higher than 75 ppm, an isobutylene block copolymer having different mechanical properties and flow properties during heating and melting depending on the water content during polymerization can be obtained. When used as a processed product, it becomes extremely difficult to use. [0050] In carrying out the above polymerization, it is preferable to mix the above-mentioned components under cooling, for example, at a temperature of 100 ° C or higher and lower than 0 ° C. Especially preferred to balance energy cost and polymerization stability, the temperature range is 80 ° C 30 ° C.

[0051] In addition, the isobutylene block copolymer of the present invention has a reinforcing agent, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, and the like within a range that does not impair the physical properties according to the required characteristics according to each application. , Pigments, surfactants, reaction retarders, flame retardants, fillers, reinforcing agents, etc. can be added as appropriate.

[0052] Examples of the antioxidant include, but are not limited to, hindered phenols and hindered amines.

[0053] The isobutylene block copolymer and the composition containing the same can be molded using a molding method and a molding apparatus generally employed for thermoplastic resins, such as extrusion molding, injection molding, and press molding. It can be melt molded by blow molding or the like.

[0054] The isobutylene block copolymer produced by the method according to the present invention and the composition containing the same can be used for various applications similar to those of the conventional isobutylene block copolymer.

For example, elastomer materials, resin, rubber, asphalt modifiers, adhesive base polymers, resin modifiers, packing materials, sealing materials, gaskets, sealing materials such as plugs, and CD dampers Dampers, dampers for buildings, damping materials for automobiles, vehicles, household appliances, etc., anti-vibration materials, automotive interior materials, cushioning materials, daily necessities, electrical components, electronic components, sports materials, grips or cushioning materials, wire coating materials It can be suitably used as packaging materials, various containers, and stationery parts.

Example

[0055] The present invention will be described more specifically with reference to the following examples. It should be noted that the present invention is not limited in any way by these examples, and can be appropriately modified without departing from the scope of the present invention.

Prior to the examples, various measurement methods, evaluation methods, and examples will be described.

[0057] (Tensile breaking strength)

In accordance with JIS K 6251, a 2mm thick press sheet is punched into No. 3 with a dumbbell and tested. A piece was prepared and used to measure the tensile strength at break. The tensile speed was 500 mm / min.

[0058] (Melt flow rate)

As a test sample, a 2 mm thick press sheet was cut into about 3 mm square and used. In accordance with JIS K7201 A method, measurement was performed at 230 ° C and 2.16 kg load with Menoleto Indexer F—F01 (manufactured by Toyo Seiki Seisakusho).

[Example 1]

After replacing the inside of the polymerization vessel of the 2 L separable flask with nitrogen, use a syringe to add 387 mL of n-xane (dried with molecular sieves) and 547 mL of butyl chloride (dried with molecular sieves) in a mixed solvent. The water content of was measured with a Karl Fischer water meter. Place the polymerization vessel in a _70 ° C dry ice / methanol bath and cool it, and then add 150 mL (1600 mmol) of isobutylene monomer to the pressure-resistant glass liquefied collection tube with a three-way cock made of Teflon (registered trademark) The liquid feeding tube was connected, and isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. 0.456 g (l. 97 mmol) of p-dic milk mouthride and 0 · 345 g (3.96 mmol) of N N′-dimethylacetamide were added. Then, 6. lmL (55.2 mmol) of tetrasalt-titanium was further added to initiate polymerization. After stirring for 120 minutes from the start of polymerization, about ImL of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, 38.5 g (369. 7 mmol) of styrene monomer was added into the polymerization vessel. 75 minutes after adding the mixed solution, the reaction was terminated by adding a large amount of water. Thereafter, the reaction solution was washed twice with water, the solvent was evaporated, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain the desired block copolymer.

[0060] The obtained block copolymer was melt kneaded at 180 ° C with a Laboplast mill (manufactured by Toyo Seiki Seisakusho), and the obtained kneaded product was 170 at a compression molding machine (manufactured by Shinto Metal Industries). A 2 mm thick sheet was obtained by press molding at ° C. Using the obtained sheet, a test piece was prepared according to the above method, and the tensile strength was measured. Table 1 shows the amount of moisture in the reaction system measured by the above method and the measurement results of tensile strength.

[Example 2]

In the same manner as in Example 1, polymerization was carried out using polymerization solvents having different water contents. Above Table 1 shows the water content in the reaction system measured by the method and the measurement results of tensile strength.

[Example 3]

Polymerization was carried out in the same manner as in Example 1 by adding water to the solvent so that the moisture described in Table 1 was obtained. Table 1 shows the moisture content in the reaction system measured by the above method and the measurement results of tensile strength.

[0063] (Comparative Example 1)

Superposition | polymerization was implemented like Example 1 except having used the separable flask without nitrogen substitution. Table 1 shows the moisture content in the reaction system measured by the above method and the measurement results of tensile strength.

[0064] (Comparative Example 2)

Polymerization was carried out in the same manner as in Example 1 except that a solvent that was not dried with a molecular sieve was used. Table 1 shows the moisture content in the reaction system measured by the above method and the measurement results of tensile strength.

[0065] (Comparative Example 3)

[0066] [Table 1]

(Example 4)

After replacing the inside of the polymerization vessel of the 2 L separable flask with nitrogen, add 290 mL of n-hexane (dried with molecular sieves) and 418 mL of butyl chloride (dried with molecular sieves) using a syringe. The water content was measured with a Karl Fischer water meter. After the polymerization vessel is cooled by placing it in a dry ice / methanol bath at 70 ° C, a Teflon (registered trademark) feed is sent to a pressure-resistant glass liquefied collection tube with a three-way cock containing 142 mL (1504 mmol) of isobutylene monomer. Connect the liquid tube to the polymerization vessel The isoprene monomer was fed into the inside by nitrogen pressure. 0.289 g (1.25 mmol) of p-dic milk mouthride and 0.222 g (2.5 mmol) of N, N′-dimethylacetamide were added. Next, 5.92 mL (54 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring for 90 minutes from the start of polymerization, about 1 mL of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, 40.81 g (391.9 mmol) of styrene monomer was added into the polymerization vessel. Sixty minutes after adding the mixed solution, the reaction was terminated by adding a large amount of water. Thereafter, the reaction solution was washed twice with water, the solvent was evaporated, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain the target block copolymer.

[0068] A press sheet was produced from the obtained block copolymer in the same manner as in Example 1, and the tensile strength was measured. Table 2 shows the moisture content in the reaction system measured by the above method and the measurement results of tensile strength.

[0069] (Example 5)

Polymerization was carried out in the same manner as in Example 4 by adding water to the solvent so that the moisture described in Table 2 was obtained. Table 2 shows the moisture content in the reaction system measured by the above method and the measurement results of tensile strength.

[0070] (Comparative Example 4)

[0071] [Table 2]

(Example 6)

After substituting the inside of the polymerization vessel of the 2 L separable flask with nitrogen, add 68 mL of n-hexane (dried with molecular sieves) and 613 mL of butyl chloride (dried with molecular sieves) using a syringe. The water content was measured with a Karl Fischer water meter. After cooling the polymerization vessel in a dry ice / methanol bath at 70 ° C, with a three-way cock containing isobutylene monomer (178, 4 mL, 1889 mmol) A Teflon (registered trademark) feeding tube was connected to a pressure-resistant glass liquefaction collection tube, and isoprene monomer was fed into the polymerization vessel by nitrogen pressure. 0.636 g (2.75 mmol) of p-dic milk mouthride and 0.46 g (4.95 mmol) of α-picoline were added. Next, 1.96 mL (17. 88 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring for 75 minutes from the start of polymerization, about ImL of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, 45.36 g (535.6 mmol) of styrene monomer was added into the polymerization vessel. Sixty minutes after adding the mixed solution, the reaction was terminated by adding a large amount of water. Thereafter, the reaction solution was washed twice with water, the solvent was evaporated, and the resulting polymer was vacuum-dried at 60 ° C. for 24 hours to obtain the desired block copolymer.

[0073] A press sheet was produced from the obtained block copolymer in the same manner as in Example 1, and the tensile strength was measured. Table 3 shows the measurement results of water content, tensile strength, and melt flow rate in the reaction system measured by the above method.

[Example 7]

Polymerization was carried out in the same manner as in Example 6 by adding water to the solvent so that the moisture described in Table 3 was obtained. Table 3 shows the measurement results of water content, tensile strength, and melt flow rate in the reaction system measured by the above method.

[0075] (Comparative Example 5)

[0076] [Table 3]

(Example 8)

After substituting the inside of the polymerization vessel of the 2L separable flask with nitrogen, use a syringe to add 23 mL of n-xan (dried with molecular sieves) and 209 mL of butyl chloride (dried with molecular sieves). Karl Fischer water in the water Measured with a minute meter. After placing the polymerization vessel in a dry ice / methanol bath at 70 ° C and cooling, a Teflon (registered trademark) made in a pressure-resistant glass liquefied collection tube with a three-way cock containing 55.5 mL (534 mmol) of isobutylene monomer The liquid feeding tube was connected, and isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. 0.13 g (0.44 mmol) of p_dicumulose mouthride and 0.1 l lg (l. 18 mmol) of hi-picoline were added. Next, 0.68 mL (6.22 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring for 60 minutes from the start of polymerization, about 1 mL of the polymerization solution was extracted from the polymerization solution for sampling.

Subsequently, 14.48 g (139 mmol) of styrene monomer was charged into the polymerization vessel. 135 minutes after adding the mixed solution, the reaction was terminated by adding a large amount of water. Thereafter, the reaction solution was washed twice with water, the solvent was evaporated, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain the target block copolymer.

[0078] A press sheet was produced from the obtained block copolymer in the same manner as in Example 1, and the tensile strength was measured. Table 4 shows the moisture content in the reaction system measured by the above method and the measurement results of tensile strength.

[0079] (Example 9)

Polymerization was carried out in the same manner as in Example 8 by adding water to the solvent so that the moisture described in Table 4 was obtained. Table 4 shows the moisture content in the reaction system measured by the above method and the measurement results of tensile strength.

[0080] (Comparative Example 6)

[0081] [Table 4]

As shown in these examples, the isobutylene block copolymer produced by the production method of the present invention has a tensile strength higher than that of a block copolymer produced under the same polymerization conditions and a water content of 75 ppm or more. Shows a stable high value and low fluidity during melting. It was found to show a fixed value.

Claims

The scope of the claims

A single amount mainly composed of isobutylene in the presence of a polymerization initiator represented by the following general formula (1) in a state where the water content relative to the total weight of the reaction solvent and the monomer component is maintained at 75 _P pm or less. A polymer block containing isobutylene as a main component of monomer and an isobutylene as a main monomer, characterized by reacting a body component (a) with a monomer component (b) containing no isobutylene as a main component. A process for producing an isobutylene block copolymer comprising a polymer block which is not used as a component.

(In the formula, a plurality of R ^{1 s} are the same or different and each represents a hydrogen atom or a monovalent hydrocarbon group having from 6 to 6 carbon atoms. R ² represents a monovalent or polyvalent aromatic hydrocarbon group or Represents a monovalent or polyvalent aliphatic hydrocarbon group, X represents a halogen atom, an alkoxyl group having from 6 to 6 carbon atoms, or an alkoxyl group having from 1 to 6 carbon atoms, and n is from 1 to Represents an integer of 6. When there are multiple Xs, they may be the same or different.

[2] The process for producing an isobutylene block copolymer according to [1], wherein the water content relative to the total weight of the reaction solvent and the monomer component is maintained at 50 ppm or less.

[3] The process for producing an isobutylene block copolymer according to [1], wherein the water content relative to the total weight of the reaction solvent and the monomer component is maintained at 20 ppm or less.

[4] The production method according to any one of claims 1 to 3, wherein the reaction is carried out in the presence of a Lewis acid.

[5] The production method according to claim 4, wherein titanium tetrachloride is used as the norelic acid.

[6] The polymerization initiator represented by the general formula (1) is bis (1 chloro 1-methylethyl) benzene. Zen [CH (C (CH) CI)] or (1-chloro- 1-methylethyl) benzene [CHC (

6 4 3 2 2 6 5

The production method according to claim 1, which is at least one selected from CH 3) CI].

3 2

Law.

7. The production method according to any one of claims 1 to 6, wherein the monomer component (b) not containing isobutylene as a main component is a monomer component containing an aromatic vinyl monomer as a main component.

[8] The production method according to claim 7, wherein the aromatic bur monomer is at least one selected from the group consisting of styrene, ρ-methylstyrene, monomethylstyrene, and indene.

[9] The isobutylene-based block copolymer is a polymer mainly composed of an aromatic vinyl monomer, and a block polymer composed mainly of an aromatic vinyl monomer. A triblock copolymer formed from a combined block, a polymer block composed mainly of isobutylene, a polymer block composed mainly of an aromatic vinyl monomer, and a polymer block composed mainly of an aromatic vinyl monomer. At least selected from the group consisting of a diblock copolymer formed from a polymer block composed mainly of an isobutylene polymer block

The production method according to claim 7 or 8, which is one kind.

[10] A monohalogenated hydrocarbon solvent composed of a primary monohalogenated hydrocarbon having 3 to 8 carbon atoms and / or a secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms, and an aliphatic hydrocarbon 10. The production method according to claim 1, wherein the polymerization is carried out in a mixed solvent with a non-halogenated hydrocarbon solvent comprising elemental and / or aromatic hydrocarbon.

11. The production method according to claim 10, wherein the monohalogenated hydrocarbon solvent is at least one selected from the group consisting of 1-chloropropane and 1-chlorobutane.

12. The production method according to claim 10 or 11, wherein the non-halogenated hydrocarbon solvent is at least one selected from the group consisting of hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane.