WO2007094258A1

WO2007094258A1 - Method for producing isobutylene block copolymer

Info

Publication number: WO2007094258A1
Application number: PCT/JP2007/052374
Authority: WO
Inventors: Ryuji Fukuda
Original assignee: Kaneka Corporation
Priority date: 2006-02-13
Filing date: 2007-02-09
Publication date: 2007-08-23
Also published as: JPWO2007094258A1

Abstract

Disclosed is a method for producing an isobutylene block copolymer which is composed of a polymer block wherein the main monomer component is isobutylene and another polymer block wherein the main monomer component is not isobutylene. The isobutylene block copolymer stably exhibits excellent mechanical characteristics, while having stable fluidity when melted. In this method, a monomer component (a) mainly containing isobutylene and a monomer component (b) not mainly containing isobutylene are reacted by using, as a reaction solvent, at least one substance selected from primary and secondary monohalogenated hydrocarbons having 3-8 carbon atoms in the presence of a polymerization initiator having a specific structure, while maintaining the amount of primary and/or secondary alcohols having 3-8 carbon atoms present in the reaction solvent as impurities to 150 ppm or less.

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] An isobutylene-based block copolymer that also has a polymer block that has an isobutylene power and a polymer block that has an aromatic vinyl-based monomer power can be obtained by cationic polymerization of an aromatic butyl-based monomer such as isobutylene and styrene. It is known that it can be manufactured. 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 from isoprene and styrene in a mixed solvent having methylene chloride and hexane power.

[0003] Further, Patent Document 3 discloses that isoptiyl in a mixed solvent in which primary and Z or secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms and aliphatic and Z or aromatic hydrocarbons are combined. A method for producing a lenic block copolymer is disclosed. Further, as an effect of using such a solvent, it is disclosed that workability in the water washing step after polymerization is improved and that the solubility in water is low, so that waste water treatment after water washing can be performed relatively easily. And

[0004] However, a polymer block mainly composed of a polymer block having isoprene power and a polymer block power having aromatic bull monomer power by the methods described in these patent documents. When a triblock copolymer formed from a polymer block composed mainly of an isobutylene-based polymer block and an aromatic building block monomer is produced, the resulting triblock copolymer In some cases, the mechanical properties represented by the tensile strength of the coalescence were not constant and could deteriorate significantly.

Patent Document 1: US Patent No. 4946899 Specification Patent Document 2: Japanese Patent Publication No. 7-59601

Patent Document 3: Japanese Patent Laid-Open No. 11-349648

Disclosure of the invention

Problems to be solved by the invention

[0005] In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a polymer having isobutylene as a main component of a monomer, which stably exhibits excellent mechanical properties and has a stable fluidity at the time of melting. It is an object of the present invention to provide a method for stably producing an isobutylene block copolymer composed of a polymer block containing no block and isobutylene as a main monomer component. Means for solving the problem

[0006] As a result of extensive research, the present inventor has used at least one kind selected from primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms as a reaction solvent. The present inventors have found that the above-mentioned problems can be solved by conducting a polymerization reaction under the condition that the amount of primary and Z or secondary alcohol having 3 to 8 carbon atoms present as impurities is 150 ppm or less. .

[0007] That is, the present invention uses at least one kind selected from primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms as a reaction solvent, and has 3 to 3 carbon atoms present as impurities in the reaction solvent. In the presence of a polymerization initiator represented by the following general formula (1) in a state where the amount of primary and Z or secondary alcohol of 8 is 150 ppm or less, a monomer component (a) containing isobutylene as a main component in the presence of a polymerization initiator represented by the following general formula (1): A polymer block comprising isobutylene as the main monomer component and isobutylene as the main monomer component, characterized by reacting with the monomer component (b) without isobutylene as the main component! The present invention relates to a method for producing an isobutylene block copolymer having a polymer blocking power.

[0008] [Chemical 2]

(Wherein a plurality of R ^{1 s} represent the same or different hydrogen atoms or monovalent hydrocarbon groups having 1 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 1 to 6 carbon atoms, or a alkoxyl group having 1 to 6 carbon atoms, n is 1 to 6 (When multiple Xs are present, they may be the same or different.)

Further, the present invention provides the above production method under the same conditions as the polymerization initiator, the monomer component (a) containing isobutylene as a main component, and the monomer component (b) containing no isobutylene as a main component. The production lot of a polymer block having isobutylene as a main monomer component and an isobutylene block copolymer having a polymer block power not containing isobutylene as a main monomer component It relates to a method of stabilizing the quality of each.

[0010] Further, the present invention is the same as the above-described production method, in which the charging ratio of the monomer component (a) containing the polymerization initiator and isobutylene as the main component and the monomer component (b) containing no isobutylene as the main component is the same. An isobutylene block copolymer comprising a polymer block containing isobutylene as a monomer main component and a polymer block not containing isobutylene as a monomer main component, characterized in that it is carried out twice or more under conditions. The present invention relates to a method for stabilizing the weight average molecular weight of each production lot.

[0011] Further, the present invention is the same as the above-described production method in that the polymerization initiator, the monomer component (a) containing isobutylene as the main component, and the charge ratio of the monomer component (b) containing no isobutylene as the main component are the same. An isobutylene block copolymer comprising a polymer block containing isobutylene as a monomer main component and a polymer block not containing isobutylene as a monomer main component, characterized in that it is carried out twice or more under conditions. The present invention relates to a method for stabilizing mechanical characteristics for each production lot.

[0012] As a preferred embodiment, the present invention relates to the production method or the stabilization method, wherein the polymerization reaction is carried out in the presence of a Lewis acid.

[0013] As a more preferred embodiment, there is the above-described production method or stabilization method using tetrasalt / titanium as the Lewis acid.

In a preferred embodiment, the polymerization initiator represented by the general formula (1) is bis (1 chloro 1-methylethyl) benzene [C H (C (CH) C1)] or (1 chloro 1-methyl).

6 4 3 2 2

Ruthel) benzene [C H C (CH) C1] is at least one selected from the above

6 5 3 2

There are manufacturing methods or stabilizing methods. [0015] As a preferred embodiment, the above-described production method or stabilizing, wherein the monomer component (b) containing no isobutylene as a main component is a monomer component containing an aromatic vinyl monomer as a main component. There is a way.

[0016] In a more preferred embodiment, the manufacturing method or the stabilization described above, wherein the aromatic bur monomer is at least one selected from the group consisting of styrene, p-methyl styrene, α-methyl styrene, and indene force. There is a way.

[0017] Preferably, as an embodiment, an isobutylene-based block copolymer is a polymer block mainly composed of an aromatic vinyl-based monomer. A polymer block mainly composed of isobutylene is a main component composed of an aromatic butyl-based monomer. Polymer block force to be formed Triblock copolymer formed, polymer block mainly composed of isobutylene, polymer block mainly composed of aromatic butyl monomer From polymer block composed mainly of isobutylene The triblock copolymer to be formed, and the polymer block force mainly composed of an aromatic vinyl monomer, the polymer block force mainly composed of sobutylene, and the diblock copolymer force formed are selected from the group There are at least one of the above production methods or stabilization methods.

[0018] Preferred embodiments include primary monohalogen hydrocarbons having 3 to 8 carbon atoms and monohalogen hydrocarbons having secondary monohalogen hydrocarbon power having 3 to 8 carbon atoms. There is a production method or a stabilization method as described above, wherein polymerization is carried out in a mixed solvent of a system solvent and a non-halogen hydrocarbon solvent composed of an aliphatic hydrocarbon and a soot or aromatic hydrocarbon .

[0019] As a preferred embodiment, there is the production method or the stabilization method described above, which is at least one selected from the group consisting of monohalogenated hydrocarbon solvent power 1-chloropropane and 1 chlorobutane power.

[0020] Preferably, in an embodiment, the non-halogenated hydrocarbon solvent is at least one selected from the group consisting of hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane force. There is a method or a stabilization method.

Furthermore, the present invention uses at least one kind selected from primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms as a reaction solvent, and the number of carbons present as impurities in the reaction solvent. The above general formula (3-8) wherein the primary and cocoon or secondary alcohol amount is 150 ppm or less. In the presence of the polymerization initiator represented by 1), the monomer component (a) having isobutylene as the main component and the monomer component (b) not having isobutylene as the main component can be obtained by a method of reacting. The present invention relates to a polymer block having isobutylene as a main component of monomer and an isobutylene block copolymer having a polymer blocking force not having isobutylene as a main component of monomer. The invention's effect

[0022] According to the production method or the stabilization method of the present invention, a polymer block comprising isobutylene as a main monomer component, which stably exhibits excellent mechanical properties and has stable fluidity upon melting. An isobutylene block copolymer composed of a polymer block containing no isobutylene as a main monomer component can be stably obtained. For this reason, it is possible to obtain a molded product with less variation in properties such as processability and mechanical strength without greatly changing the properties of the polymer every polymerization.

BEST MODE FOR CARRYING OUT THE INVENTION

[0023] Hereinafter, the present invention will be described in detail.

In the method according to the present invention, at least one selected from primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms is used as a reaction solvent, and carbon existing as an impurity in the reaction solvent. A monomer component mainly composed of isobutylene in the presence of a polymerization initiator represented by the following general formula (1) under the condition that the amount of primary and Z or secondary alcohols of formula 3 to 8 is 150 ppm or less. (a) is reacted with a monomer component (b) which does not contain isobutylene as a main component.

[0025] [Chemical 3]

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

The monomer component (b) containing no isobutylene as a main component is preferably a monomer component having an isobutylene content of 30% by weight or less, more preferably 10% by weight or less. More preferably, it is 3% by weight or less. This is because when the isobutylene content is 30% or more, excellent mechanical strength is not exhibited.

[0027] The monomer other than isobutylene in the monomer component (b) that is not mainly composed of isobutylene of the present invention is not particularly limited as long as it is a cationically polymerizable monomer, but aliphatic olefins And monomers such as aromatic burs, gens, bur ethers, silanes, burcarbazole, 13-vinene, and acenaphthylene. These can be used alone or in combination of two or more.

[0028] 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.

[0029] The aromatic bur monomer is not particularly limited, and examples thereof include styrene, o-, m- or p-methylstyrene, α-methylstyrene, 13-methylolstyrene, 2,6 dimethylstyrene, 2, 4 Dimethylstyrene, α-methyl-ο-methylstyrene, α-methyl-m-methylstyrene, α-methyl-ρ-methylstyrene, j8-methyl-ο-methylstyrene, β-methyl-m-methylstyrene, 13-methyl-p-methyl Styrene, 2, 4, 6 Trimethylstyrene, α-Methyl-2,6 Dimethylstyrene, α-Methyl-2,4 Dimethylstyrene, 13-Methyl-2,6 Dimethylstyrene, 13-Methyl-2,4 Dimethylstyrene, o-, m- or ρ chlorostyrene, 2, 6 dichlorostyrene, 2, 4 dichlorostyrene, α chloro-o chlorostyrene, α chloro-m chloros Ren, alpha-chloro ρ chlorostyrene, - black hole. 1-chlorostyrene, 1-methylene chloride, β-chloro-ρ-chlorostyrene, 2, 4, 6 trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, j8-chloro-2 6 Dichloromethane Styrene, j8—Black Distiller 1,4 Dichlorostyrene, o—, m—or p—t—Butinorestire O-, m- or p-methoxystyrene, o-, m- or p-chloromethylenostyrene, o-

M- or p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, urnaphthalene and the like.

[0030] The gen-based monomer is not particularly limited, and examples thereof include butadiene, isoprene, cyclopentagen, cyclohexagen, dicyclopentagen, divininolebenzene, and ethylidene norbornene.

[0031] The butyl ether monomer is not particularly limited. For example, methyl beryl ether

, Ethyl vinyl ether, ( _n —, iso) propyl butyl ether, ( _n —, sec—, tert

-, Iso) butinorevinino reetenore, methinorepropenole ethenore, ethinolepropenole eleter and the like.

[0032] The silane compound is not particularly limited. Examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

[0033] The monomer component (b) that does not contain isobutylene of the present invention as a main component is a monomer component that contains an aromatic vinyl monomer as a main component from the viewpoint of physical properties and polymerization characteristics. I like it. The monomer component mainly composed of the aromatic bur monomer of the present invention preferably has an aromatic vinyl monomer content of 60% by weight or more, preferably 80% by weight or more. Is more preferable. Here, it is preferable to use at least one monomer selected from the group consisting of styrene, a-methylstyrene, P-methylstyrene, and indenka as the aromatic bur monomer. Particular preference is given to using styrene, a-methylstyrene, p-methylstyrene or mixtures thereof.

[0034] The monomer component (a) containing isobutylene as a main component may or may not contain a monomer other than isobutylene as a monomer component. % Or more, preferably 80% by weight or more. The monomer other than isobutylene is not particularly limited as long as it is a monomer capable of cationic polymerization. Monomers such as aliphatic olefins, aromatic burs, gens, bur ethers, silanes, bur carbazole, β-vinene, and acenaphthylene. These may be used alone or in combination of two or more.

[0035] The ratio of the polymer block mainly composed of isobutylene and the polymer block composed mainly of aromatic butyl but also having a component power is not particularly limited, but isobutylene is mainly used from the viewpoint of various physical properties. It is preferable that the polymer block as a component is 40 to 95% by weight, and the polymer block having a monomer component power mainly composed of aromatic vinyl is 5 to 60% by weight. It is particularly preferable that the polymer block is 50 to 85% by weight, and the polymer block having a monomer component power mainly composed of aromatic bur is 15 to 50% by weight.

[0036] The weight average molecular weight of the isobutylene-based block copolymer is not particularly limited, but the surface strength such as fluidity, property, property, etc. is 10,000 to 500,000. , Preference for power, which is between 30000 and 400000. When the weight average molecular weight of the isobutylene-based block copolymer is lower than the above range, the mechanical properties are not sufficiently expressed! On the other hand, when it exceeds the above range, the fluidity, It is disadvantageous in terms of workability. The above weight average molecular weight is determined by gel permeation chromatography (GPC) system manufactured by Waters (column: Shodex K-804, K 802.5 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: black mouth form). It is the value measured using.

[0037] Also preferred is an isobutylene block copolymer. As the block copolymer, from the viewpoint of physical properties, a polymer block-isobutylene containing an aromatic vinyl monomer as a main component is the main component. A polymer block consisting of an aromatic vinyl-based monomer as a main component and a block-blocking triblock copolymer, a polymer based on an aromatic vinyl-based monomer, and a block consisting mainly of isobutylene. Polymer block power diblock copolymer, polymer block mainly composed of aromatic bur monomer, and star block copolymer having 3 or more arms composed of polymer block power mainly composed of isobutylene. Examples thereof include polymers. These can be used alone or in combination of two or more in order to obtain the desired physical properties and molding power. Among these, from the viewpoint of processability and cost, in particular, it has a triblock structure, styrene, isobutylene, a styrene block copolymer, and a diblock structure. Styrene isobutylene block copolymers are preferred.

[0038] The compound represented by the general formula (1) serves as an initiator and serves as a starting point for cationic polymerization. Wherein a plurality of R ¹ may be the same or different and represents a monovalent hydrocarbon group having a hydrogen atom or 1 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 alkoxyl 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 there are a plurality of X, they may be the same or different.

[0039] Examples of the compound of the general formula (1) used in the present invention include the following compounds.

(1-Chloro- 1-methylethyl) benzene [C H C (CH) Cl], 1, 4 Bis (1-chloro

6 5 3 2

Ru- 1-methylethyl) benzene [1, 4-Cl (CH) CC H C (CH) Cl], 1, 3 Bi

3 2 6 4 3 2

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

3 2 6 4 3 2

1, 3, 5 Tris (1-chloro-1-methylethyl) benzene [1, 3, 5— (C1C (CH))

3 2

C H], 1, 3 Bis (1-chloro-1-methylethyl) -5- (tert-butyl) benzene

3 6 3

[1, 3— (C (CH) C1) 5— (C (CH)) C H]

3 2 2 3 3 6 3

Of these, (1 chloro 1-methylethyl) benzene [C H C

6 5

(CH) C1], bis (1 chloro 1-methylethyl) benzene [C H (C (CH) C1)],

3 2 6 4 3 2 2 Tris (1-chloro-1-methylethyl) benzene [(C1C (CH)) C H]. (

3 2 3 6 3

1-Chronole 1-Methylenoethinole) Benzene is ( _a -Black mouth isopropyl) benzene, (2-Chlo mouth one 2-Propyl) benzene, also called Tamil chloride, bis (1-Chlorone 1-Methyleno Ethino) ) Benzene is bis (α-chloro-isopropinole) benzene, bis (2-chloro 1-propyl) benzene! / Is also called dicmilk mouth-ride, and tris (1-chloro 1-methinore ethinore) benzene is It is also called tris (α-chloropropyl) benzene, tris (2-chloro-2-propyl) benzene or tritamilk chloride.

[0040] When an 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, V

4 4 3 3 3 2 4 5 5 6 5

Metal halides such as CI, FeCl, ZnBr, AlCl, AlBr; Et A1C1, EtAlCl, etc. Organometallic halides can be suitably used (Et represents an ethyl group). Among them, TiCl, BC1, and SnCl are used when considering the ability as a catalyst and industrial availability.

4 3 4 Preferred. The amount of Lewis 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 L00 molar equivalent can be used with respect to the compound represented by the general formula (1), preferably in the range of 1 to 50 molar equivalent.

[0041] When the isobutylene block copolymer is produced, an electron donor component can 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 narrow molecular weight distribution and a controlled structure. be able to. 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.

[0042] Examples of the electron donor component include 15 to 60 donors defined as one parameter representing the strength of various compounds as electron donors (electron donors). Specifically, 2,6 di-t-butylpyridine, 2 t-butylpyridine, 2,4,6 trimethylpyridine, 2,6 dimethylpyridine, 2-methylpyridine, pyridine, jetylamine, trimethylamine, triethylamine, tributylamine, N , N-dimethylaniline, N, N dimethylformamide, N, N dimethylacetamide, N, N dimethylacetamide, dimethyl sulfoxide, jetyl ether, methyl acetate, ethyl acetate, trimethyl phosphate, Xamethylphosphoric triamide, titanium (ΠΙ) methoxide, titanium

(IV) Titanium alkoxides such as methoxide, titanium (IV) isopropoxide, titanium (IV) butoxide; aluminum alkoxides such as aluminum triethoxide and aluminum tributoxide, etc. Di-Butylpyridine, 2,6 Dimethylpyridine, 2-Methylpyridine, Pyridine, Jetylamine, Trimethylamine, Triethylamine, N, N Dimethylformamide, N, N Dimethylacetamide, Dimethylsulfoxide, Titanium (IV) Iso Examples include propoxide and titanium (IV) butoxide. Regarding the number of donors for the various substances mentioned above, “Doners and Acceptors”, by Dardman, Daegu, It is shown in the translation by Okada, Academic Publishing Center (1983). Of these, 2-methylpyridine, N, N-dimethylacetamide, and titanium (IV) isopropoxide, which have a uniform reaction system, are particularly preferred.

[0043] The electron donor component is used in a molar amount of 0.01 to LO times with respect to the polymerization initiator. Of these, 0.2

It is preferable to use in the range of 6 times mole! /.

In the present invention, at the time of polymerization, at least one selected from primary and secondary monohalogenated hydrocarbon powers having 38 carbon atoms is used as a reaction solvent.

[0045] 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, and examples thereof include 1-chloropropane, 1-chloro-2-methinolevene. , 1 Chlorobutane, 1 Chromium 2-Methylolebutane, 1 Chromium 3-Methylbutane, 1-Cro-2, 2 Dimethylbutane, 1-Cro-3, 3 Dimethylbutane, 1 — Chromium 1, 2, 3 Dimethylbutane, 1 — Chrono Pentane, 1-black 1-methylpentane 1-black 3-methinorepentane, 1-black 4-methinorepentane, 1-black hexane, 1 chloro-2-methino hexane, 1 chloro 3-methino hexane, 1 Chloro-4-methino hexane, 1 chloro 5-methino hexane, 1 chlorooctane, 1 chlorooctane, 2 chloroprone, 2 chlorobutane, 2 chloropentane, 2 chlorohexane , It may be mentioned 2-black port heptane, 2-black port octane, a black hole benzene. These can be used alone or in combination of two or more. For example, a monohalogenated solvent having 3 carbon atoms, a monohalogen solvent having 4 carbon atoms, a combination of a monohalogen solvent having 3 carbon atoms and a monohalogen solvent having 4 carbon atoms, or a monohalogen having 48 carbon atoms. It may be a combination of at least one of the solvents. Of these, if importance is attached to the solubility of isobutylene block copolymer, ease of detoxification by decomposition, balance of cost, etc., it is particularly preferable to use 1-chloropropane and Z or 1-chlorobutane. Chlorobutane is preferred!

[0046] As the reaction solvent, in consideration of the balance of the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the polymer to be produced, primary grades with 3 to 8 carbon atoms and Z or secondary grades In addition to monohalogenated hydrocarbons, alkylbenzenes such as benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene; ethane, propane, butane, Linear aliphatic hydrocarbons such as pentane, neopentane, hexane, heptane, octane, nonane, decane; 2-methylpropane, 2-methylbutane, 2, 3, 3-trimethylpentane, 2, 2, 5 —Branched aliphatic hydrocarbons such as trimethylhexane; Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane; Paraffin oil obtained by hydrorefining petroleum fractions, etc. Also good. Two or more of these may be used. Among them, primary monohalogenated hydrocarbons having 3 to 8 carbon atoms and monohalogenated hydrocarbon solvents having Z or secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms and aliphatic hydrocarbons, and aliphatic hydrocarbons. And Z or aromatic hydrocarbons in a mixed solvent with a non-halogen hydrocarbon solvent, improving the workability in the washing process after polymerization and facilitating wastewater treatment after washing Sexual power is preferable. 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, ethyl cyclohexane, toluene and xylene power is preferred. Particularly preferred is at least one selected from the group consisting of xane, methylcyclohexane and ethylcyclohexane.

[0047] A monohalogenated hydrocarbon solvent composed of a primary monohalogenated hydrocarbon having 3 to 8 carbon atoms and Z or a secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms, and an aliphatic hydrocarbon Primary monohalogenated hydrocarbons having 3 to 8 carbon atoms and Z or carbon numbers 3 to 3 in a mixed solvent in combination with elemental and Z or non-halogenated hydrocarbon solvents that are aromatic hydrocarbon power The content of the secondary monohalogenated hydrocarbon solvent of No. 8 has a desired dielectric constant! /, May be set so that the solubility of the block copolymer can be obtained. % By weight, preferably 20 to 95% by weight.

[0048] The amount of the solvent used is a force determined in consideration of the viscosity of the resulting polymer solution and the ease of heat removal. Usually, the concentration of the polymer is 1 to 50% by weight, preferably 5 It should be ~ 35% by weight.

[0049] As a method for producing the isobutylene block copolymer of the present invention, a polymerization initiator is used to adjust the amount of primary and Z or secondary alcohols having 3 to 8 carbon atoms present as impurities in the reaction solvent. Other than the above, there is no particular limitation.For example, in the above solvent, the compound represented by the general formula (1) and a monomer component mainly composed of an aromatic vinyl monomer may be used. Adds a monomer component containing isobutylene as a main component and an electron donor component as necessary. Further, a Lewis acid is added as necessary to initiate polymerization, and the polymerization of the added monomer component is substantially At the end of the process, the other monomer component is added to the reaction solution and polymerized. If necessary, after the polymerization is substantially completed, another monomer component may be added to continue the polymerization.

[0050] A primary monohalogenated hydrocarbon having 3 to 8 carbon atoms and a secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms, which are used as a reaction solvent in the polymerization, are prepared and stored. Depending on the state, it may contain primary and Z or secondary alcohols with the same carbon number as impurities. This alcoholic impurity force affects the polymerization reaction.

In the present invention, the amounts of primary and secondary alcohols having 3 to 8 carbon atoms (hereinafter referred to as “impurity amount”) present as impurities in the reaction solvent measured by a calibration curve method using gas chromatography. The reaction is conducted at 150 ppm or less, preferably 10 ppm or less, more preferably 50 ppm or less. Here, the calibration curve method is to obtain a peak area corresponding to the alcohol in the gas chromatogram of a reaction solvent having several known alcohol concentrations, draw a calibration curve from the alcohol concentration and the peak area, and obtain the calibration curve. Originally, the concentration is quantified from the peak area corresponding to the alcohol in the chromatogram of the reaction solvent with an unknown alcohol concentration. When the amount of impurities is higher than 150 ppm, the polymer obtained tends to be significantly lower than the tensile strength of the polymer obtained under the same reaction conditions except that the amount of impurities is 150 ppm or less, and the amount of molecules tends to be lower. is there. The higher the impurity content is higher than 150 ppm, the lower the tensile strength and the lower the weight average molecular weight. For this reason, when a polymerization reaction is carried out with an impurity amount higher than 150 ppm, isobutylene block copolymers having different mechanical properties and molecular weights can be obtained, which makes it extremely difficult to use as a molded product.

[0052] A primary monohalogenated hydrocarbon having 3 to 8 carbon atoms and a monohalogenated hydrocarbon having 3 to 8 secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms. Examples of the primary alcohol and the secondary alcohol having 3 to 8 carbon atoms include 1 propanol, 2 methylpropanol, 1-butanol, 2-methylbutanol, 3-methylbutanol, 2,2 dimethylbutanol, 3,3 dimethyl Butanol, 2, 3 Dimethylbutanol , Pentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol mono-ole, hexanol, 2-methino hexanol, 3-methino hexanol, 1-chloro-4-methyl hexanol, 5-methyl hexanol, heptanol, There are octanol, 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol and phenol.

[0053] In carrying out the above polymerization, it is preferable to mix the above-described components under cooling, for example, at a temperature of 100 ° C or higher and lower than 0 ° C. Particularly preferred to balance the energy cost and the stability of the polymerization, the temperature range is from 80 ° C to 1-30 ° C.

[0054] Further, 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, and the like can be appropriately blended.

[0055] The antioxidant is not particularly limited, and examples thereof include hindered phenols and hindered amines.

[0056] The isobutylene-based block copolymer and the composition containing the same can be molded using a molding method and a molding apparatus generally employed for thermoplastic resin, such as extrusion molding, injection molding, press It can be melt molded by molding, blow molding or the like.

[0057] The isobutylene block copolymer and the composition containing the same produced by the method according to the present invention can be used for various applications similar to those of the conventional isobutylene block copolymer. For example, elastomer materials, modifiers such as resin, rubber, asphalt, adhesive base polymer, grease modifier, knocking materials, sealing materials, sealing materials such as gaskets, plugs, tubes, pipes, etc. Tubular molded products, dampers for weak electrical equipment such as CD dampers, dampers for construction, damping materials for automobiles, vehicles, home appliances, etc., cushioning materials, daily necessities, electrical parts, electronic parts, It can be suitably used as a sports member, grip or cushioning material, electric wire covering material, packaging material, various containers, and stationery parts. Example

[0058] 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 as long as the gist of the present invention is not changed. Changes can be made.

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

[0060] (Quantitative determination of impurities) The quantitative determination of the alcohol content of impurities was carried out by a calibration curve method using gas chromatography. For measurement, Supelco waxTM10 (manufactured by Supelco) is used as the column. The initial column temperature is 60 ° C for 3 minutes, then the temperature is raised to 200 ° C at 15 ° C / min and held at 200 ° C for 3 minutes. The temperature rising method was used to determine impurities from the peak area.

[0061] (Weight average molecular weight measurement) Water permeation gel permeation chromatography (GPC) system (column: Showa Denko Co., Ltd. Shodex K-804, K 802.5 (polystyrene gel), mobile phase: black mouth form , Detector: differential refraction detector).

[0062] (Tensile breaking strength)

In accordance with JIS K 6251, a 2 mm thick press sheet was punched into a No. 3 type with a dumbbell to prepare a test piece, which was used to measure the tensile strength at break. The tensile speed was 500 mmZ.

[0063] (Example 1)

After replacing the inside of the polymerization vessel of the 2 L separable flask with nitrogen, using a syringe, add n-hexane (dried with molecular sieves) 365 mL and butyl chloride (dried with molecular sieves) 525 mL, The concentration of butanol, which is an impurity in the mixed solvent, was measured by gas chromatography. Place the polymerization vessel in a dry ice Z methanol bath at 70 ° C and cool it. Then, 207 mL (2195 mmol) of isobutylene monomer is contained, and V is a Teflon (registered trademark) made in a pressure-resistant glass liquid tube with a three-way cock. The isoprene monomer was fed into the polymerization vessel by nitrogen pressure. p Dicumyl chloride 0.495 g (2.14 mmol) and N, N, -dimethylacetamide 0.932 g (10.7 mmol) were added. Next, 6.6 mL (59.9 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 sampled to confirm the reaction rate. Subsequently, 59.5 g (571.4 mmol) of styrene monomer was added into the polymerization vessel. 60 minutes after adding the mixed solution, the reaction was terminated by adding a large amount of water.

[0064] 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. The desired block copolymer was obtained by drying. The weight average molecular weight of the obtained block copolymer was measured by the above method.

[0065] The obtained block copolymer was melt kneaded at 180 ° C with a Laboplast mill (manufactured by Toyo Seiki Seisakusho), and the resulting kneaded product was 170 at a compression molding machine (manufactured by Shinto Metal Industry). 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.

[0066] Table 1 shows the measurement results of the amount of alcohol, which is an impurity in the reaction solvent, the weight average molecular weight, and the tensile strength, measured by the above method.

[0067] (Example 2)

Polymerization was carried out in the same manner as in Example 1 except that a polymerization solvent having a different amount of butanol was used. Table 1 shows the measurement results of the alcohol amount, weight average molecular weight, and tensile strength in the reaction solvent measured by the above method.

[Example 3]

Polymerization was carried out in the same manner as in Example 1 by adding butanol to the reaction solvent so that the amount of butanol described in Table 1 was obtained. Table 1 shows the results of measuring the alcohol content, weight average molecular weight, and tensile strength in the reaction solvent measured by the above method.

[0069] (Comparative Example 1)

[0070] (Comparative Example 2)

[0071] [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Impurity 8 4 7 1 4 0 2 1 5 3 2 9

Amount

(p p m)

Weight average 1 0 2 0 0 9 6 0 0 0 9 3 0 0 0 7 8 0 0 0 7 6 0 0 0

Molecular weight 0

Tensile strength 1 9 1 8 1 7 1 5 1 3

(MP a)

[Example 4]

After replacing the inside of the polymerization vessel of the 2 L separable flask with nitrogen, using a syringe, add 77 mL of n-hexane (dried with molecular sieves) and 694 mL of butyl chloride (dried with molecular sieves), The amount of butanol in the mixed solvent was measured. After the polymerization vessel is placed in a dry ice Z methanol bath at 70 ° C and cooled, a Teflon (registered trademark) feed is made into a pressure-resistant glass liquefaction sampling tube with a three-way cock containing isobutylene monomer 1671111 ^ (176911111101). A liquid tube was connected, and isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. P. Dicmilk mouthride 0.340 g (l. 47 mmol) and α picoline 0.36 g (3.9 mmol) were calorie free. Next, 2.26 mL (20.6 mmol) of tetrasalt-titanium was further added to initiate polymerization. After stirring for 80 minutes from the start of polymerization, about 1 mL of the polymerization solution was sampled to confirm the reaction rate. Subsequently, 47.95 g (406.2 mmol) of styrene monomer was added into the polymerization vessel. 105 minutes after adding the mixed solution, the reaction was terminated by adding a large amount of water.

[0073] After 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. The weight average molecular weight of the obtained block copolymer was measured by the above method.

[0074] 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 measurement results of the alcohol content, weight average molecular weight, and tensile strength in the reaction solvent measured by the above method.

[0075] (Comparative Example 3)

Polymerization was carried out in the same manner as in Example 4 by adding butanol to the reaction solvent so that the amount of alcohol described in Table 2 was obtained. Table 2 shows the measurement results of the alcohol content, weight average molecular weight, and tensile strength in the reaction solvent measured by the above method.

[0076] [Table 2] Example 4 Comparative Example 3

Impurities 暈 6 7 1 80

(p pm)

Weight average molecular weight 1 22000 1 0 5000

Tensile strength 1 8 1 5

(MPa) As shown from these examples, the isoprene-based block copolymer obtained by the production method of the present invention is composed of primary and Z or secondary carbon atoms of 38 and present as impurities in the reaction solvent. Compared to a block copolymer produced under the same conditions except that the amount of alcohol is 150 ppm or more, the tensile strength is stably high. In addition, the flowability at the time of melting shows a stable value with a high weight average molecular weight and a low low molecular weight component.

Claims

The scope of the claims

[1] A primary and secondary monohalogenated hydrocarbon power having 3 to 8 carbon atoms is also selected as the reaction solvent, and at least one kind of carbon atoms having 3 to 8 carbon atoms present as impurities in the reaction solvent is used. In the presence of a polymerization initiator represented by the following general formula (1) with a primary and Z or secondary X alcohol content of 150 ppm or less, a monomer component (a) comprising isobutylene as a main component and A polymer block containing isoprene as a main component of monomer and a polymer block containing isobutylene as a main component of monomer. A method for producing an isobutylene block copolymer.

(In the formula, a plurality of R ¹ represent the same or different hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms. R ² represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or X represents a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, n is an integer of 1 to 6 When multiple Xs are present, they may be the same or different.)

[2] The process according to claim 1, wherein the reaction is carried out in the presence of a Lewis acid.

[3] The production method according to claim 2, wherein a tetrasalt-titanium salt is used as the Lewis acid.

[4] The polymerization initiator represented by the general formula (1) is bis (1 chloro 1-methylethyl) benzene [C H (C (CH) C1)] or (1 chloro 1-methylethyl) benzene [C H C

6 4 3 2 2 6 5

(CH) C1] force The production according to any one of claims 1 to 3, which is at least one selected.

3 2

Method.

[5] The production method according to any one of claims 1 to 4, wherein the monomer component (b) containing isobutylene as a main component is a monomer component containing an aromatic vinyl monomer as a main component. .

6. The production method according to claim 5, wherein the aromatic bur monomer is at least one selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene, and indene power.

[7] A polymer block in which the isobutylene-based block copolymer is composed mainly of an aromatic vinyl monomer. A polymer block composed mainly of an isobutylene. A polymer block composed mainly of an aromatic vinyl-based monomer. Triblock copolymer formed from polymer block, polymer block mainly composed of isobutylene, polymer block composed mainly of aromatic vinyl monomer, polymer block force composed mainly of sobutylene A block copolymer, and a polymer block mainly composed of an aromatic butyl monomer, a polymer block force mainly composed of isobutylene, and a diblock copolymer force formed, at least selected from the group consisting of

The production method according to claim 5 or 6, which is one kind.

[8] A monohalogenated hydrocarbon solvent composed of a primary monohalogenated hydrocarbon having 3 to 8 carbon atoms and Ζ or a secondary monohalogenated hydrocarbon having 3 to 8 carbon atoms, and aliphatic carbonized The production method according to any one of claims 1 to 7, wherein the polymerization is carried out in a mixed solvent of hydrogen and a non-halogen soot hydrocarbon solvent having a soot or aromatic hydrocarbon power.

[9] The production method according to claim 8, wherein the monohalogenated hydrocarbon solvent is at least one selected from the group consisting of 1-chloropropane and 1-chlorobutane power.

[10] The process according to claim 8 or 9, wherein the non-halogenated hydrocarbon solvent is at least one selected from the group consisting of hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

[11] A primary and secondary monohalogenated hydrocarbon power having 3 to 8 carbon atoms is also selected as the reaction solvent, and at least one kind of 1 to 3 carbon atoms present as impurities in the reaction solvent is used. A monomer component (a) containing isobutylene as a main component in the presence of a polymerization initiator represented by the above general formula (1) in a state where the amount of grade and soot or secondary alcohol is 150 ppm or less, and isobutylene A polymer block containing isobutylene as the main monomer component and isobutylene as the main monomer component, obtained by reacting with the monomer component (b). An isobutylene block copolymer comprising a polymer block.

[12] The polymerization initiator, the monomer component (a) containing isobutylene as the main component and the main component of isobutylene! /, And the monomer component (b) are charged under the same charging ratio as defined in claim 1. Manufacturing method described The production of an isobutylene block copolymer comprising a polymer block containing isobutylene as the main monomer component and a polymer block not containing isobutylene as the main monomer component A method to stabilize the quality of each lot.

[13] The polymerization initiator, the monomer component (a) containing isobutylene as a main component and the main component of isobutylene! /, And the monomer component (b) are charged under the same charging ratio as defined in claim 1. An isobutylene block comprising a polymer block containing isobutylene as a main monomer component and a polymer block not containing isobutylene as a main monomer component, characterized in that the production method described above is carried out twice or more. A method of stabilizing the weight average molecular weight of each polymer production lot.

[14] The polymerization initiator, the monomer component (a) containing isobutylene as a main component and the main component of isobutylene! /, And the monomer component (b) are charged under the same charging ratio as claimed in claim 1. An isobutylene block comprising a polymer block containing isobutylene as a main monomer component and a polymer block not containing isobutylene as a main monomer component, characterized in that the production method described above is carried out twice or more. A method of stabilizing the mechanical properties of each production lot of polymer.