WO2007043662A1 - Isobutylene polymer and method for producing same - Google Patents

Abstract

Disclosed is an isobutylene block copolymer which is hardly colored and has a stable color tone. Specifically disclosed is an isobutylene polymer obtained by polymerizing a monomer component containing isobutylene in the presence of a polymerization initiator and a Lewis acid catalyst. This isobutylene polymer is characterized in that the residual amount of metal derived from the Lewis acid catalyst in the isobutylene polymer is not more than 90 ppm. Also disclosed is a method for producing such an isobutylene polymer.

Description

 Specification

 Isobutylene polymer and method for producing the same

 Technical field

 The present invention relates to an isobutylene polymer and a method for producing the same.

 Background art

 [0002] An isobutylene polymer can be usually obtained by cationic polymerization of an isobutylene monomer together with other monomers as desired.

 Conventionally, cationic polymerization has been thought to be difficult to control the structure of a polymer due to the fact that chain transfer during the reaction is large and it is difficult to control the molecular weight and that it is difficult to introduce functional groups. However, it has recently been reported by Kennedy et al. That the number average molecular weight of the isobutylene polymer can be arbitrarily controlled by carrying out the reaction in the presence of a reaction solvent or a Lewis acid catalyst (Non-patent Document 1). According to this method, a polymer block mainly composed of isobutylene and a polymer block composed mainly of an aromatic vinyl monomer and having an isobutylene block copolymer which is composed mainly of an isobutylene homopolymer are also produced. (Patent Documents 1 and 2).

 [0004] Patent Document 1: US Patent No. 4946899 Specification

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

 Non-Patent Document 1: J. P. Kennedy and B. Ivan, Designed Polymers by Carbo reactive Molecular Engineering: Theory and Practice, Carl Hanser Verlag, Munich, 1992

 Disclosure of the invention

 Problems to be solved by the invention

[0005] When the isobutylene polymer was produced by the method described in Patent Documents 1 and 2, there was a problem that coloring of the coconut resin occurred depending on the production conditions.

An object of the present invention is to provide an isobutylene-based polymer that is less colored and has a stable color tone, and a method that can produce such an isobutylene-based polymer in view of the above-described problems of the prior art. It is what. Means for solving the problem

 [0007] As a result of extensive research, the present inventors have found that the isobutylene polymer is colored due to the influence of the metal residue derived from the Lewis acid catalyst, and have led to the present invention. It is.

 That is, the first present invention is an isobutylene polymer obtained by polymerizing a monomer component containing isoprene in the presence of a polymerization initiator and a Lewis acid catalyst,

 The isobutylene polymer is characterized in that the amount of metal residue derived from the Lewis acid catalyst in the isopylene polymer is 90 ppm or less.

[0009] A preferred embodiment relates to the isobutylene polymer in which the polymerization initiator has a structure represented by the following general formula (1).

(CR '^ X) R ³ (1)

(In the formula, X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group. R ¹ and R ² are the same or different, and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ³ represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic or alicyclic hydrocarbon group, n represents a natural number of 1 to 6.

[0010] In a more preferred embodiment, the polymerization initiator represented by the general formula (1) is represented by the formula C

 6

Bis (1 chloro 1-methylethyl) benzene represented by H (C (CH) C1) and the formula

4 3 2 2

 Is it a group consisting of (1 chloro 1-methylethyl) benzene represented by C H C (CH) C1?

6 5 3 2

 The above-mentioned isobutylene polymer is at least one selected from the group consisting of

[0011] As a preferred embodiment, the present invention relates to the above-mentioned isobutylene polymer in which the Lewis acid catalyst is tetrachloride-titanium.

 [0012] A preferred embodiment includes a polymer block (a) having the isobutylene-based polymer strength isobutylene monomer as a main component and a polymer block (b) having a monomer other than isopylene as a main component. It is related with the said isobutylene type polymer which is a block copolymer to do.

 [0013] A preferred embodiment relates to the isobutylene polymer which is a monomeric aromatic vinyl monomer other than the above isoprene.

[0014] In a more preferred embodiment, the aromatic vinyl monomer is styrene, p-methyl. The present invention relates to the above isobutylene polymer, which is at least one selected from the group consisting of rustyrene, monomethylstyrene, and indene force.

 As a preferred embodiment, the isobutylene polymer is

 • (Polymer block based on aromatic vinyl monomer) (Polymer block based on isobutylene monomer) (Polymer block based on aromatic vinyl monomer) ) Force formed triblock copolymer,

 • (Polymer block based on isobutylene monomer) (Polymer block based on aromatic vinyl monomer) (Polymer block based on isobutylene monomer) A triblock copolymer, and

 • Diblock copolymer formed from (polymer block based on aromatic vinyl monomer) (polymer block based on isobutylene monomer)

 The present invention relates to the above-mentioned isobutylene polymer, which is at least one block copolymer selected from the group consisting of:

 [0016] The second invention is a step (I) of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst;

 A step of deactivating the Lewis acid catalyst by bringing water into contact with the isobutylene polymer-containing solution obtained in the step (I) (ii);

 Further, after the step (ii), the obtained polymer-containing solution is washed with a basic aqueous solution having a pHIO or higher (III);

 It is related with the manufacturing method of the isobutylene type polymer characterized by including.

[0017] Preferably, as an embodiment, the polymer-containing solution obtained after the step (III) is further used.

In addition, the present invention relates to the above production method comprising the step (IV) of filtering with a filter capable of collecting 99% or more of particles having a diameter of 5 / zm or more when the differential pressure before and after the filter is 0.2 MPa.

[0018] Another aspect of the second aspect of the present invention is a step (I) of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst;

 A step of deactivating the Lewis acid catalyst by bringing water into contact with the isobutylene polymer-containing solution obtained in the step (I) (ii);

After the above step (II), the obtained polymer-containing solution was subjected to a pressure difference of 0.2 MPa before and after the filter. Filter with a filter capable of collecting 99% or more of particles with a diameter of 5 μm or more (IV);

 It is related with the manufacturing method of the isobutylene type polymer characterized by including.

[0019] As a preferred embodiment, the present invention relates to the above-mentioned production method, wherein the above-mentioned isobutylene polymer strength is mainly composed of isobutylene.

[0020] In a preferred embodiment, the isobutylene polymer is composed of a polymer block (a) containing an isobutylene monomer as a main component and a polymer block containing an aromatic butyl monomer as a main component ( b) It relates to the above production method which is a polymer which also has strength.

[0021] In a preferred embodiment, the polymerization reaction is carried out with at least one selected from the group consisting of primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms, aliphatic, alicyclic and aromatic. And at least one selected from the group consisting of group hydrocarbons.

 [0022] A preferred embodiment relates to the above production method, wherein the Lewis acid catalyst is a halogenated metal.

 [0023] A preferred embodiment relates to the above production method, wherein the halogenated metal is tetrasalt titanium.

 [0024] A preferred embodiment relates to the above production method, wherein the basic aqueous solution is a sodium hydroxide aqueous solution.

 Hereinafter, the present invention will be described in detail.

 [0026] <Monomer components constituting isoprene-based polymer>

The isobutylene polymer of the present invention is obtained by polymerizing a monomer component containing isobutylene in the presence of a polymerization initiator and a Lewis acid catalyst. The polymer is characterized in that the amount of metal residue derived from the Lewis acid catalyst is 90 ppm or less. The isobutylene-based polymer may be a homopolymer composed only of isoprene, or may be a copolymer obtained by polymerizing isopylene and other monomers. Especially, what has isobutylene as a main component is preferable. In the present specification, the “main component” means a monomer component that occupies 60% by weight or more of all monomers constituting the polymer (or polymer block). Of all monomers constituting the polymer, isobutylene More preferred is a polymer containing 80% by weight or more of ethylene.

[0027] The isobutylene-based polymer also includes a polymer block ( _a ) containing an isobutylene monomer as a main component and a polymer block (b) containing a monomer other than isobutylene as a main component. An isobutylene block copolymer is preferred.

 [0028] The monomer other than isobutylene as the main component in the block (b) is not particularly limited as long as it is a monomer capable of cationic polymerization, but an aliphatic or alicyclic olefin-based monomer. Monomers, aromatic vinyl monomers, gen monomers, butyl ether monomers, silane compounds, burcarbazole, 13 vinylene, and acenaphthylene. These can be used alone or in combination of two or more.

 [0029] The aliphatic or alicyclic olefin-based monomer is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 2-methyl 1-butene, 3-methyl 1-butene, and pentene. Hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexene, otaten, norbornene and the like.

[0030] The aromatic bulle monomer is not particularly limited. For example, styrene, o-, m- or p-methylstyrene, α-methylstyrene, 13-methylstyrene, 2, 6 dimethyl styrene, 2, 4 Dimethylstyrene, α-methyl-ο-methylstyrene, α-methyl-m-methylstyrene, ex-methyl-p-methylstyrene, j8-methyl-o-methylstyrene, 13-methyl-m-methylstyrene, 13-methyl-p-methylstyrene, 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-dichloro-styrene, 2, 4-dichloro styrene, shed one chloro o-chlorostyrene, shed one chloro _m - Rollostyrene, α-chloro ρ-chlorostyrene, j8-chloro-ο chlorostyrene, j8-chloro-m-chlorostyrene, / 3 chloro-p-chlorostyrene, 2, 4, 6 trichlorostyrene, α-chloro-2,6-dichlorostyrene , Α-Chloro-2,4-dichlorostyrene, j8-Chloro-2,6-dichlorostyrene, / 3-Chromatic 1,4 Dichlorostyrene, o-, m- or p-t-Butinorestylene, o-, m —Or p-methoxystyrene, o—, m—or p-chloromethylenostyrene, o 1, m- or p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, urnaphthalene and the like.

 [0031] The above-mentioned gen-based monomer is not particularly limited, and examples thereof include butadiene, isoprene, cyclopentane, cyclohexagen, dicyclopentagen, divininolebenzene, and ethylidene norbornene.

[0032] The butyl ether monomer is not particularly limited. For example, methyl butyl ether, ethyl butyl ether, ( _n— , iso) propyl butyl ether, ( _n— , sec-, t ert-, iso ) Butinorevininoreethenore, methinorepropenenoreethenore, ethinorepropenore ether and the like.

 [0033] The silanic compound is not particularly limited, and examples thereof include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, dibutydichlorosilane, dibutydimethoxysilane, Examples include dibutyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

 Of these, monomers other than the above-mentioned isobutylene, which is the main component of the polymer block (b), are preferably aromatic vinyl monomers from the balance of physical properties and polymerization characteristics. That is, a block copolymer in which the content of the aromatic vinyl monomer in the polymer block (b) is 60% by weight or more is preferred, and a block copolymer having 80% by weight or more is more preferred. Yes.

 [0035] It is preferable to use at least one monomer selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and indene as the aromatic bur monomer. From the viewpoint of cost, it is particularly preferable to use styrene, hymethylstyrene, ρ-methylstyrene or a mixture thereof.

 [0036] The polymer block (a) containing isobutylene as a main component may or may not contain a monomer other than isobutylene as a monomer component. However, among all the monomers constituting the polymer block (a), 60% by weight or more, preferably 80% by weight or more is isobutylene.

[0037] As a monomer other than isoprene included in the polymer block (a), cationic polymerization is possible. The monomer is not particularly limited as long as it is a simple monomer, such as aliphatic or cycloaliphatic olefins, aromatic burins, gens, butyl ethers, silanes, burcarbazole, β-vinene, and acenaphthylene. A monomer is mentioned. These may be used alone or in combination of two or more.

[0038] The ratio of the polymer block (a) mainly composed of isobutylene and the polymer block (b) mainly composed of an aromatic vinyl monomer in the entire isobutylene polymer is not particularly limited. However, from the viewpoint of various physical properties, the ratio of the polymer block ( _a ) based on the isobutylene monomer out of all the monomers in the isobutylene polymer S 40 to 95% by weight, aromatic vinyl type It is preferable that the ratio of the polymer block (b) based on the monomer is 5 to 60% by weight. The ratio of the polymer block (a) based on the isobutylene monomer is preferably from 50 to 50% by weight. It is particularly preferred that the proportion of the polymer block (b) containing 85% by weight of the aromatic bulbure monomer as a main component is 15 to 50% by weight.

 [0039] The number average molecular weight of the isobutylene-based polymer is not particularly limited, but the surface strength such as fluidity, processing 'property, physical properties', etc. is a power of 30000-500000 S, preferably 50000-400000 It is especially preferred. If the number average molecular weight of the isobutylene polymer is lower than 30000, the mechanical properties tend not to be fully expressed, whereas if it exceeds 500,000, it is disadvantageous in terms of fluidity and workability. . The above number average molecular weight is measured using a gel permeation chromatography (GPC) system manufactured by Waters (columns: Shodex K 804, K 802.5 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: black mouth form). This is the measured value.

[0040] Among the isobutylene block copolymers, the block copolymer is particularly preferred as a block copolymer (polymer block mainly composed of an aromatic vinyl monomer) from the viewpoint of balance of physical properties. Polymer block mainly composed of a monomer) (Polymer block composed mainly of an aromatic vinyl monomer) Triblock copolymer (a polymer block composed mainly of an isobutylene monomer) (Polymer block containing aromatic vinyl monomer as the main component) (Polymer block containing isobutylene monomer as the main component) Powerful triblock copolymer (Mainly aromatic vinyl monomer) Polymer block as component) (Polymer block mainly composed of isobutylene monomer) Powerful diblock copolymer, and (Aromatic bulle system) A polymer block having a monomer as a main component) and a polymer block having an isobutylene monomer as a main component) and a star block copolymer having three or more powerful arms. These can be used alone or in combination of two or more in order to obtain the desired physical properties and moldability. Among these, in view of processability and cost, (tristyrene)-(isobutylene)-(styrene) block copolymer, diblock structure (styrene)-(isobutylene) block co Polymers are preferred.

[0041] <About polymerization initiator>

 The isobutylene polymer of the present invention is obtained by superposing predetermined monomer components in the presence of a polymerization initiator. The polymerization initiator is not particularly limited, but the general formula (1)

(CR '^ X) R ³ (1)

(In the formula, X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group. R ¹ and R ² are the same or different, and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ³ represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic or alicyclic hydrocarbon group, and n represents a natural number of 1 to 6. It is preferable to use the compound as an initiator. Polymerization initiator is the starting point for cationic polymerization

[0042] 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

 [0043] Among these, (1 chloro 1-methylethyl) benzene [C H C (

 6 5

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

3 2 6 4 3 2 2 Lith (1-chloro-1-methylethyl) benzene [(C1C (CH)) CH]. (1 —Chronole 1-methinoreethinole) benzene is also called (one-clonal isopropyl) benzene, (2-chloro 2-propyl) benzene or tamilolide, and bis (1 chloro 1-methinoreethinore) benzene is bis (chloro). Mouth isopropinole) benzene, bis (2-chloro-2-2-propyl) benzene! / Is also called Dicumulium mouthride, Tris (1-Chlorone 1-methinoreethinore) benzene is Tris (cyclomouth isopropyl) Also called benzene, tris (2-chloro-2-benzene) benzene or tritamilk chloride.

<About Lewis Acid Catalyst>

 The isobutylene polymer of the present invention is obtained by polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst. The Lewis acid is not particularly limited as long as it can be used for cation polymerization. For example, TiCl, TiBr, BCl

 4 4

, BF, BF -OEt, SnCl, SbCl, SbF, WC1, TaCl, VC1, FeCl, ZnBr,

3 3 3 2 4 5 5 6 5 5 3 2

Metal halides such as A1C1 and AlBr; Organometallic halides such as Et A1C1 and EtAlCl

3 3 2 2

 A halogenated metal such as a compound can be preferably used (Et represents an ethyl group). Of these, TiCl, BCl, SnCl,

 4 3 4

TiCl (titanium tetrachloride) is particularly preferred, with A1C1 and Et A1C1 being preferred. Use of Lewis acid

3 2 4

 The amount is not particularly limited, but can be set in consideration 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 polymerization initiator, and preferably in the range of 1 to 50 molar equivalent.

 [0045] <Other components>

 When the isobutylene polymer is polymerized, an electron donor component can be further present if necessary. This electron donor component is considered to have an effect of stabilizing the growing carbon cation during cationic polymerization, and a polymer having a structure with a narrow molecular weight distribution controlled by the addition of the electron donor. Can be generated. 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.

[0046] As the electron donor component, the number of donors defined as one parameter representing the strength as an electron donor (electron donor) of various compounds is 15-60, t-butylpyridine, 2-t-butylpyridine, 2, 4, 6 trimethylpyridine, 2,6 dimethylpyridine, 2-methylpyridine, pyridine, jetylamine, trimethylamine, triethylamine, tributylamine, N, N-dimethyla -Phosphorus, N, N-dimethylformamide, N, N dimethylacetamide, N, N jetylacetamide, dimethylsulfoxide, diethyl ether, methyl acetate, ethyl acetate, trimethyl phosphate, hexamethyl phosphate triamide, titanium (III) Titanium alkoxides such as methoxide, titanium (IV) methoxide, titanium (IV) isopropoxide, titan (IV) butoxide; power capable of using aluminum alkoxide such as aluminum triethoxide and aluminum triboxide, etc. 2,6 g t-butylpyridine, 2 , 6 Dimethyl pyridine, 2 Methyl pyridine, Pyridine, Diethylamine, Trimethylamine, Triethylamine, N, N Dimethylformamide, N, N-Dimethylacetamide, Dimethyl sulfoxide, Titanium (IV) isopropoxide, Titanium ( IV) Butoxide and the like. The number of donors for the various substances mentioned above is shown in “Donor and Acceptor”, by Dardman, Otsuki, Okada, and 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.

 [0047] The electron donor component is used in a molar amount of 0.01 to LO times with respect to the polymerization initiator. Of these, it is preferably used in the range of 0.2 to 4 moles.

 [0048] The polymerization of the isobutylene polymer can be carried out in a solvent, if necessary. 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-butyl chloride, chloride can be used. Halogenated hydrocarbons such as benzene; alkylbenzenes such as benzene, toluene, xylene, ethylbenzene, propylbenzene, and butylbenzene; linear chains such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, and decane Aliphatic hydrocarbons; branched aliphatic hydrocarbons such as 2-methylpropane, 2-methylbutane, 2, 3, 3 trimethylpentane, 2, 2, 5 trimethylhexane; cyclohexane, methylcyclohexane, Alicyclic hydrocarbons such as ethylcyclohexane; paraffin oil obtained by hydrorefining petroleum fractions, etc. It can be mentioned.

[0049] These solvents are used for the polymerization characteristics and formation of the monomers constituting the isobutylene polymer. Considering the balance of the solubility of the polymer, it can be used alone or in combination of two or more. Among them, at least one selected from the group consisting of primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms, and group power consisting of aliphatic, alicyclic and aromatic hydrocarbons are selected. Polymerization in a mixed solvent containing at least one kind is preferable from the viewpoint of improving workability in the water washing step after polymerization and ease of waste water treatment after water washing.

 [0050] The primary monohalogenated hydrocarbons having 3 to 8 carbon atoms and the secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms are not particularly limited, and examples thereof include 1-chloropropane, 1-chloro-2- Methylpropane, 1-chlorobutane, 1-black mouth 2-methylbutane, 1-black mouth one 3-methyl butane, 1-black mouth 2,2 dimethylbutane, 1-black mouth 3,3 dimethylbutane, 1 — 1,3 Dimethylbutane, 1-Black mouthpentane, 1-Black mouthpiece 2-Methylpentane, 1-Black mouthpiece 3-Methinorepentane, 1-Black mouthpiece 4-Methinorepentane, 1-Black mouth hexane 1 chloro-2-methino hexane, 1 chloro 3-methino hexane, 1 chloro 4-methino hexane, 1 chloro 5-methino hexane, 1-heptane, 1 chlorooctane, 2-chloro-prone, 2- Chloro Tan, 2 black port pentane, hexane 2 black port, 2-black port heptane, 2-black port octane, can be exemplified black port benzene. 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, or a monohalogen having 4 to 8 carbon atoms. It may be a combination of at least one of the solvating solvents. Of these, if importance is attached to the solubility of isobutylene polymer, ease of detoxification by decomposition, balance of cost, etc., it is preferable to use 1-chloropropane and Z or 1-chlorobutane, especially 1-chlorobutane. preferable.

[0051] The aliphatic or alicyclic hydrocarbon and the aromatic hydrocarbon as the non-halogen solvent are not particularly limited. For example, butane, pentane, neopentane, hexane, heptane, octane, cyclohexane, Examples include methylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, ethylbenzene and the like. These can be used alone or in combination of two or more. Solubility of isobutylene polymer From the balance of cost, dielectric constant, etc., at least one selected from the group consisting of hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and xylene is preferred hexane, methylcyclohexane and ethylcyclo Particularly preferred is at least one selected from the group having hexane power.

 [0052] The content of the monohalogen 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 isobutylene polymer. However, it is generally 10 to 98% by weight, preferably 20 to 95% by weight. This is because when the content of the monohalogen hydrocarbon solvent is less than 10%, the reaction rate may become extremely slow, or the polymer may precipitate during the polymerization, and a preferred isobutylene polymer can be obtained. This is because there is not. On the other hand, if it exceeds 98% by weight, it may be difficult to control the reaction with a high polymerization rate.

 [0053] The amount of the solvent used is determined in consideration of the viscosity of the resulting polymer solution and the ease of heat removal. It is preferable that the concentration of the polymer be 1 to 50% by weight. More preferably, the content is 5 to 35% by weight.

 [0054] The isobutylene polymer in the present invention is characterized in that the amount of metal residue derived from the Lewis acid catalyst is 90 ppm or less. Among them, the above metal residue is preferably 80 ppm or less, more preferably 60 ppm or less, and even more preferably 40 ppm or less. When the amount of metal residue exceeds 90 ppm, the coloring of the polymer, particularly yellowing, becomes remarkable. For example, when an isobutylene polymer is molded into a sheet having a thickness of 2 mm, the yellowness (Y. I.) is a value exceeding 25. When the yellowness is 25 or more, it can be seen visually that the color is yellow, and the coloration feels remarkable. The amount of metal residue is a value measured by a calibration curve method using an ICP emission spectrophotometer (Seiko Instruments Inc., SPS-1700R type).

 [0055] <About manufacturing method>

The method for producing the isobutylene polymer of the present invention is not particularly limited except that the polymerization of the monomer component containing isobutylene in the presence of a polymerization initiator and a Lewis acid catalyst is performed. For example, the above-mentioned solvent, the compound represented by the general formula (1), and, if necessary, an electron donor component are charged into a reaction vessel, and then isobutylene is the main component. And a method of polymerizing by adding a Lewis acid and further adding a Lewis acid. When obtaining a block copolymer, after the polymerization of the monomer component added to the reaction vessel is substantially completed, the block copolymer may be added by adding another monomer component. it can . Furthermore, if necessary, after the polymerization is substantially completed, another monomer component may be added to continue the polymerization.

 [0056] After completion of the polymerization, although not particularly limited, for example, as described in JP-A-11-349648, after completion of the polymerization, the reaction solution is added to a large amount of water to deactivate the Lewis acid catalyst. After removal, the resulting mixture is also subjected to a post-treatment such as removing water, followed by a washing operation. There is no particular limitation on the method for reducing the amount of metal residue derived from the Lewis acid catalyst of the isobutylene polymer. For example, as described in JP-A-11 349648, there is a method of increasing the number of water washing operations. Also, use a basic aqueous solution with a high pH value when washed with water.

 As another method, the Lewis acid catalyst may be easily removed by lowering the solution concentration during purification. Specifically, the solution concentration at the time of polymerization may be lowered, or a diluting solvent may be added to lower the polymer concentration of the polymerization solution after the polymerization is completed. In addition, a method of reducing the amount of metal residue by adding an additive such as a surfactant or an antifoaming agent may be employed. Furthermore, a method of adding a metal alkoxide to a polymerization solution, filtering the precipitated polymerization catalyst residue and fractionating, as described in JP-A-2001-131222, can be mentioned. These methods may be performed alone, or a plurality of methods may be combined.

 [0058] In carrying out the 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. In order to balance energy cost and polymerization stability, a particularly preferred temperature range is from -80 ° C to 1-30 ° C.

 [0059] It should be noted that the isobutylene polymer of the present invention has a reinforcing agent, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a pigment and the like within a range not impairing the physical properties according to the required characteristics according to each application. , Surfactants, reaction retarders, flame retardants, fillers, reinforcing agents and the like may be appropriately blended. The antioxidant is not particularly limited, and examples thereof include hindered phenols and hindered amines.

[0060] The isobutylene-based polymer obtained by the above method is generally adopted for thermoplastic resin. For example, it can be melt-molded by extrusion molding, injection molding, press molding, blow molding or the like.

 [0061] Regarding the production method according to the second invention>

 The second aspect of the present invention relates to a method for producing an isobutylene polymer. Specifically, a step (I) of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst; water is brought into contact with the isobutylene polymer-containing solution obtained in the step (I); The step of deactivating the Lewis acid catalyst (Π);

 Further, after the step (ii), the obtained polymer-containing solution is washed with a basic aqueous solution having a pHIO or higher (III);

 (Hereinafter, this method will be referred to as Production Method [A]).

[0062] As another aspect,

 A step of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst (I); a solution containing the isobutylene polymer obtained in the step (I) is contacted with water to lose the Lewis acid catalyst. Process to make it live (Π);

 After the above step (II), the obtained polymer-containing solution is filtered with a filter that can collect 99% or more of particles having a diameter of 5 μm or more when the differential pressure before and after the filter is 0.2 MPa. Degree (IV);

 The present invention relates to a process for producing an isobutylene polymer characterized by containing (hereinafter, this process is referred to as Process [B]).

 [0063] <About manufacturing method [A]>

 The production method [A] is a production method including the above steps (iii) to (III). Details will be described below.

 [0064] · About process (I)

Step (I) is a step of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst. The polymerization method is not particularly limited as long as it is carried out in the presence of a Lewis acid catalyst. For example, the above-mentioned solvent, the compound represented by the following general formula (1), and, if necessary, an electron donor component are charged into a reaction vessel, and then a monomer component mainly composed of isobutylene is added. And a method in which a Lewis acid is added to perform polymerization. When obtaining block copolymers For example, after the polymerization of the monomer component added to the reaction vessel is substantially completed, block copolymerization can be performed by adding another monomer component. Furthermore, if necessary, after the polymerization is substantially completed, another monomer component may be added to continue the polymerization.

 [0065] The monomer component is not particularly limited as long as it contains isobutylene, but those having isobutylene as a main component are preferred.

 [0066] The monomer other than isoprene included in the monomer component is not particularly limited as long as it is a monomer that can be cationically polymerized. For example, aliphatic or alicyclic olefins, aromatic bulls. And monomers such as gens, butyl ethers, silanes, burcarbazole, β-vinene, and acenaphthylene. These may be used alone or in combination of two or more.

 [0067] Further, the isobutylene polymer obtained in the present invention contains a polymer block (a) containing isobutylene as a main component and a polymer block (b) containing a monomer other than isobutylene as a main component. An isobutylene block copolymer is included.

 [0068] The monomer other than isobutylene which is the main component of the block (b) is not particularly limited as long as it is a monomer capable of cationic polymerization, but aliphatic or alicyclic olefin-based monomers, Examples thereof include monomers such as aromatic vinyl monomers, gen monomers, butyl ether monomers, silane compounds, burcarbazole, 13 vinylene, and acenaphthylene. These can be used alone or in combination of two or more.

 [0069] In particular, the monomer other than the above isobutylene, which is the main component of the polymer block (b), is preferably an aromatic vinyl monomer from the balance of physical properties and polymerization characteristics.

 [0070] The Lewis acid catalyst used in the present invention is not particularly limited as long as it can be used for cationic polymerization, and examples thereof include metal halides such as TiCl, BC1, BF, A1C1, and SnCl.

 4 3 3 3 4

 be able to. Among them, tetrasalt 匕 titanium (TiCl) is the reactivity of isobutylene polymer, its

 Four

 From the viewpoint of ease of catalyst recovery and safety of recovered catalyst, it is preferable.

[0071] The polymerization solvent used in the step (I) is not particularly limited, and a solvent having a halogenated hydrocarbon power, a non-halogen solvent, or a mixture thereof can be used. Of these, the group power of primary and secondary monohalogenated hydrocarbons with 3 to 8 carbon atoms is also selected. Mixed solvent power containing at least one kind and group power consisting of aliphatic, cycloaliphatic and aromatic hydrocarbon powers s Also preferred is the surface area of solubility of isobutylene polymers .

 [0072] The primary and Z or secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms are not particularly limited, and examples thereof include 1-chlorobutane and black benzene. Among these, 1 chlorobutane is preferred because of the solubility of the isobutylene block copolymer, the ease of detoxification by decomposition, and the balance force such as cost.

 [0073] The aliphatic and Z or aromatic hydrocarbons are not particularly limited. For example, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and the like. Is mentioned. One or more selected from the group consisting of methylcyclohexane, ethylcyclohexane and toluene power are particularly preferred.

[0074] In step (I), although it is not essential, it is preferable to carry out the polymerization in the presence of a polymerization initiator. The polymerization initiator is not particularly limited, but a compound represented by the general formula (1) is preferable.

(CR '^ X) R ³ (1)

(In the formula, X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group. R ¹ and R ² are the same or different, and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ³ represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic or alicyclic hydrocarbon group, n represents a natural number of 1 to 6.

[0075] Specific examples of the compound of the general formula (1) include (1 chloro 1-methylethyl) benzen [CHC (CH) Cl], 1, 4 bis (1-chloro-1-methylethyl) benzene [1, Four-

 6 5 3 2

 C1 (CH) CC H C (CH) CI], 1, 3 Bis (1-chloro-1-methylethyl) benze

3 2 6 4 3 2

 [1, 3-Cl (CH) CC H C (CH) Cl], 1, 3, 5 Tris (1-chloro- 1-methyl

 3 2 6 4 3 2

 Ethyl) benzene [1, 3, 5- (ClC (CH)) C H], 1, 3 bis (1 chloro 1-me

 3 2 3 6 3

 Tinoleetinole) 5 (tert Butinole) benzene [1, 3— (C (CH) C1) — 5— (C (CH

 3 2 2 3

)) C H] and the like.

 3 6 3

 [0076] Among these, bis (1 chloro 1-methylethyl) benzene [C H

 6

(C (CH) C1)], tris (1-chloro-1-methyl ヱ til) benzene [(C1C (CH)) C H]. [In addition, bis (1-chloro-1 1-methylethyl) benzene is bis (α

6 3

 Isopropyl) benzene, bis (2-chloro-2-propynole) benzene! / ヽ is also called dicumino chloride, and tris (1-chloro-1-1-methylethyl) benzene is tris (cyclochloroisopropyl) benzene, tris ( 2—Black 1 2-Propyl) Benzene! / ト リ is also known as Tricuminolecide Ride].

 [0077] In the polymerization in the step (I), an electron donor component can be further present if necessary. Examples of such compounds include pyridines, amines, amides, sulfoxides, esters, or metal compounds having an oxygen atom bonded to a metal atom.

 [0078] In carrying out the actual polymerization, the respective components are mixed under cooling, for example, at a temperature of 100 ° C or higher and lower than 0 ° C. A particularly preferred temperature range is -80 ° C to -30 ° C to balance energy costs and polymerization stability.

 [0079] Further, the number average molecular weight of the resulting isobutylene block copolymer is not particularly limited! /, Force From the viewpoint of fluidity, processability, physical properties, etc., the power is preferably 30,000 to 500,000 S, preferably 500 00 Especially preferred power to be ~ 400000!

 [0080] Next, step (ii) will be described in detail.

 In the step (II), the isobutylene polymer-containing solution (also referred to as “polymer solution” or “polymer-containing solution” in this specification) is mainly composed of isobutylene using a Lewis acid catalyst. This is a solution obtained after polymerization of monomer components. In the step (ii), the Lewis acid catalyst is deactivated by bringing water into contact with such a polymer-containing solution.

 [0081] In the step (ii), a container equipped with a stirrer is preferably used as the apparatus used for deactivation of the Lewis acid catalyst. Arbitrary blades such as screw blades, propeller blades, anchor blades, blade blades, pitched paddle blades, turbine blades, large-size blades, and the like, are not particularly limited in the shape of the stirring blades of the stirrer.

[0082] In addition, the vessel used for deactivation should be a reaction vessel equipped with a generally used stirrer and jacket, which is not particularly limited in shape and shape as long as it has a function of controlling the internal temperature. Can do. In addition, a baffle or similar effect can be used to increase the efficiency of stirring. There is no problem even if the thermometer with protective tube is in the container.

 [0083] In the step (ii), the temperature at which the catalyst is deactivated is not particularly limited, but a range of 4 to 100 ° C is preferable from the viewpoint of production cost and safety which is preferable in operation. ° C is particularly preferred.

 Next, step (III) will be described.

 In step (III), after the above step (II), the obtained polymer-containing solution is washed by adding a basic aqueous solution of pHIO or more, thereby sufficiently inactivating the Lewis acid and further removing it. Do. Usually, after the Lewis acid catalyst is deactivated, the polymer solution is sufficiently washed with water, and then a basic aqueous solution is added to the polymer solution.

 [0085] In the step (ii), the temperature at the time of washing is not particularly limited, but the range of 4 to 100 ° C is preferably 20 to 80 ° C from the viewpoint of manufacturing cost and safety which is preferable in operation. Particularly preferred.

 [0086] The amount of the aqueous solution used for cleaning is not particularly limited, but the ratio of (aqueous solution: polymer solution) is in the range of 1Z5 to LOZl (volZvol) from the viewpoint of production cost. It is particularly preferable that the production power of the manufacturing cost is in the range of 1Z5 to 5Z1 (volZvol). In addition, the pH value of the basic aqueous solution used should be 10 or more in order to remove the catalyst sufficiently. In terms of productivity and safety, the pH value is particularly preferably 10 to 13. Furthermore, the basic aqueous solution to be used is not particularly limited, but it is preferable to use sodium hydroxide (caustic soda) in terms of cost and ease of handling.

 [0087] In order to reduce the liquid viscosity of the polymer-containing solution and improve the separation of the catalyst residue, if necessary, the primary and secondary carbons having 3 to 8 carbon atoms similar to the polymerization solvent may be used. Mixed solvent or halogenation containing at least one selected from the group consisting of monohalogenated hydrocarbons and at least one selected from the group consisting of aliphatic, alicyclic and aromatic hydrocarbons A single solvent of hydrocarbon, aliphatic hydrocarbon or aromatic hydrocarbon can also be added to the polymer-containing solution after completion of polymerization. The amount of the solvent to be added is not particularly limited, but it is preferable that the ratio of (water: polymer solution) is in the range of 1Z10 to 10Z1 (volZvol) from the viewpoint of production cost. A range of ˜2Z1 (volZvol) is particularly preferred.

[0088] As described above, in steps (II) and (III), the catalyst is deactivated with water, and then the polymer solution is dissolved. By adding a basic aqueous solution of pHIO or higher to the solution, the catalyst residue can be enlarged, and the catalyst residue can be sufficiently removed by filtration or the like. As a result, the polymer can be prevented from being clouded or colored, and a highly transparent polymer can be provided. The step (IV) described below may be further performed after the step (III). This can further enhance the effect of removing the catalyst residue.

 [0089] About the manufacturing method [B]>

 Next, production method [B] will be described. Production method [B] is a production method comprising the steps (1), (ii) and (IV). Of these, steps (I) and (ii) are as already described in the section of production method [A].

 [0090] · About process (IV)

 In step (IV), water is brought into contact with the polymer solution in step (II) to deactivate the Lewis acid catalyst, and the resulting polymer solution is subjected to a pressure difference of 0.2 before and after the filter. Filter with a filter capable of collecting 99% or more of particles with a diameter of 5 μm or more when the pressure is set to MPa. Preferably, a filter capable of collecting 99% or more of particles having a diameter of 1 m or more is used. By performing filtration in this manner, the catalyst can be sufficiently removed, and coloring of the resulting polymer can be reduced. The shape of the filter eyes is not particularly questioned. Further, in order to sufficiently remove the polymer force of the metal derived from the Lewis acid catalyst during filtration, it is preferable to separate the water from the polymer solution force before the filtration through the filter after the catalyst is deactivated. .

 [0091] The material of the filter is not particularly limited as long as it is a material that does not dissolve in the polymer-containing solution under normal use, such as polypropylene, nylon, and cotton.

 The filter 1 may be used in multiple stages in order to sufficiently remove the catalyst even with one stage.

[0093] In addition, in order to reduce the liquid viscosity and improve the separability, the group of primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms, which is the same as the polymerization solvent, if necessary. Mixed solvent containing at least one selected from the group consisting of aliphatic, alicyclic and aromatic hydrocarbons, or halogenated hydrocarbon, aliphatic hydrocarbon or A single aromatic hydrocarbon solvent may be added to the polymer solution. The amount of the solvent to be added is not particularly limited, but the ratio of (water: polymer solution) is not limited. The range of 1Z10 to 2Zl (vol / vol) is particularly preferable from the viewpoint of production cost, which is preferably in the range of the force SlZlO to 10Zl (volZvol).

 The invention's effect

 [0094] The isobutylene-based polymer with few metal residues derived from the catalyst of the present invention has little coloration and a stable color tone. Therefore, it can be suitably used for applications requiring transparency and hygiene, and molded products colored with dyes and pigments, particularly molded products colored with light colors. Further, according to the production method of the present invention, an isobutylene polymer with little coloring can be produced.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0095] 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 changed without departing from the scope of the present invention.

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

[0097] (Molecular weight)

 The molecular weight of the isobutylene polymer shown in this example was measured by the following method. Waters GPC system (column: Shodex K-804 (polystyrene gel), Showa Denko KK, mobile phase: black mouth form). The number average molecular weight is expressed in terms of polystyrene.

[0098] (Colorability)

 The test piece was a 2 mm thick press sheet, and the yellowness (Y. L) of this test piece was measured using a spectroscopic color difference meter (Spectroo Color Meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd.). It was.

[0099] (Appearance)

 The appearance of the isobutylene polymer was visually observed to determine whether yellowness was observed. A colorless one was marked with ◯, a slightly yellow colored one was marked with Δ, and a yellow colored one was marked with X.

[0100] (Example 1)

To a 500 mL reaction vessel with a stirrer, add 15 mL of n-hexane (dried with molecular sieves) and 128 mL of butyl chloride (dried with molecular sieves). After cooling the reaction vessel in a dry ice Z methanol bath at 70 ° C, 41.3 mL of isobutylene is contained, and a Teflon (registered trademark) feeding tube is placed in a pressure-resistant glass liquid collecting tube with a three-way cock. Was connected, and isoprene monomer was fed into the polymerization vessel by nitrogen pressure. 0.088 g of p-dic milk mouthride and 0.08 g of dimethylacetamide were added. Next, 0.55 mL of titanium tetrachloride was further added to initiate polymerization, and the mixture was stirred at −70 ° C. for 1.5 hours. Next, 13.5 g of styrene was added to the reaction solution, and further reacted for 1 hour to obtain a polymer solution. Next, 125 g of pure water and 0.038 g of Newcol-561H (manufactured by Nippon Emulsifier Co., Ltd.) were added to another 2 L reaction vessel equipped with a stirrer. The obtained polymer solution was put into the reaction vessel, heated to 55 ° C., and stirred for 1 hour. After stirring, the mixture was allowed to stand for 30 minutes to remove the aqueous phase. Further, 75 g of pure water was added to the obtained polymer solution and stirred for 30 minutes. Stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the aqueous phase was removed. The above washing operation using pure water was further repeated twice. The obtained polymer solution was a highly transparent solution. The solvent was distilled off from the obtained polymer solution, and further dried for 24 hours in a vacuum dryer at 80 ° C. to obtain an isobutylene block copolymer solid. As a result of measuring the molecular weight of the obtained isobutylene block copolymer, the number average molecular weight was 78,000 and the molecular weight distribution was 1.43.

 [0101] The obtained isobutylene block copolymer was melt-kneaded at 180 ° C by a Laboplast mill (manufactured by Toyo Seiki Seisakusho). The obtained kneaded material was press-molded at 170 ° C. using a compression molding machine (manufactured by Shinfuji Metal Industry Co., Ltd.) to obtain a 2 mm thick sheet. Using the obtained sheet, appearance observation and yellowness measurement were performed. In addition, the amount of residual Ti was measured by a calibration curve method using an ICP emission spectroscopic analyzer (manufactured by Seiko Instruments Inc., SPS-1700R type). The results are shown in Table 1.

 [0102] (Comparative Example 1)

 Polymerization was carried out in the same manner as in Example 1 except that Newcol-561H (manufactured by Nippon Emulsifier Co., Ltd.) was not used! /. The results are shown in Table 1.

[0103] (Example 2)

After the inside of the polymerization vessel (2 L separable flask) was purged with nitrogen, 68 mL of n-hexane (dried with molecular sieves) and 613 mL of butyl chloride (dried with molecular sieves) were collected using a syringe. . Polymerization vessel—70 ° C dry ice Z-Metal Cooled in a Nord bath. After that, connect a Teflon (registered trademark) liquid feeding tube to a pressure-resistant glass liquid tube with a three-way cock containing 139.7 mL of isobutylene monomer, and place the isoprene monomer with nitrogen pressure in the polymerization vessel. Liquid was sent. 0.35 g of p-dic milk mouthlid and 0.35 g of α-picoline were added to the polymerization vessel. Next, 2.20 mL of titanium tetrachloride was added to initiate the polymerization. After stirring for 90 minutes from the start of polymerization, about 1 mL of the polymerization solution was sampled. Subsequently, 46.7 g of styrene monomer was charged into the polymerization vessel. The polymer concentration in the reaction solution was about 20% by weight. Ninety minutes after adding the mixed solution, the polymerization vessel was poured into a large amount of water to terminate the reaction. Purification and drying were carried out in the same manner as in Example 1 to obtain an isobutylene block copolymer solid. As a result of measuring the molecular weight of the resulting isobutylene-based block copolymer, the number average molecular weight was 72,000 and the molecular weight distribution was 1.38. The obtained polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0104] (Comparative Example 2)

 Isobutylene type block copolymer was obtained in the same manner as in Example 2 except that 2.46 mL of tetrachloride-titanium was used. As a result of measuring the molecular weight of the obtained isobutylene block copolymer, the number average molecular weight was 74,000 and the molecular weight distribution was 1.45. The obtained polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0105] (Comparative Example 3)

After replacing the inside of the polymerization vessel of the 2 L separable flask with nitrogen, using a syringe, add 68 mL of n-hexane (dried with molecular sieves) and 613 mL of butyl chloride (dried with molecular sieves), Place the polymerization vessel in a dry ice Z methanol bath at 70 ° C, cool it, and then supply Teflon (registered trademark) into a pressure-resistant glass liquid collecting tube with a three-way cock containing 185.9 mL of isobutylene monomer. A tube was connected, and isoprene monomer was fed into the polymerization vessel by nitrogen pressure. 0.46 g of p-dic milk mouthride and 0.41 g of α-picoline were added. Next, 2.84 mL of titanium tetrachloride was further added to initiate polymerization. After stirring the polymerization initiation force for 75 minutes, about 1 mL of the polymerization solution was withdrawn for the polymerization solution force for sampling. Subsequently, 62.2 g of styrene monomer was added into the polymerization vessel. The polymer concentration in the reaction solution was about 22% by weight. Add mixed solution Ninety minutes after that, the reaction was terminated by adding a large amount of water. Purification and drying were carried out in the same manner as in Example 1 to obtain an isobutylene block copolymer solid. As a result of measuring the molecular weight of the resulting isobutylene block copolymer, the number average molecular weight was 71,000 and the molecular weight distribution was 1.40. The obtained polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]

 After replacing the inside of the polymerization vessel of the 2 L separable flask with nitrogen, using a syringe, add 68 mL of n-hexane (dried with molecular sieves) and 613 mL of butyl chloride (dried with molecular sieves), Place the polymerization vessel in a dry ice Z methanol bath at 70 ° C and cool it. Then, transfer the liquid made of Teflon (registered trademark) into the pressure-resistant glass liquid collecting tube with a three-way cock containing 185.9 mL of isobutylene monomer. A tube was connected, and isoprene monomer was fed into the polymerization vessel by nitrogen pressure. 0.46 g of p-dic milk mouthride and 0.36 g of dimethylacetamide were added. Next, 2.84 mL of titanium tetrachloride was further added to initiate polymerization. After stirring for 75 minutes from the start of polymerization, about 1 mL of the polymerization solution was withdrawn from the polymerization solution for sampling. Subsequently, 62.2 g of styrene monomer was added into the polymerization vessel. Ninety minutes after the addition of this mixed solution, the contents of the polymerization vessel were poured into a large amount of water to complete the reaction. After adding 22 ml of n-hexane and 202 ml of butyl chloride, the solution was washed with water. The obtained polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0107] (Comparative Example 4)

After the inside of the polymerization vessel (2 L separable flask) was purged with nitrogen, 68 mL of n-hexane (dried with molecular sieves) and 613 mL of butyl chloride (dried with molecular sieves) were collected using a syringe. . The polymerization vessel was cooled in a dry ice Z methanol bath at 70 ° C. Then, connect a Teflon (registered trademark) liquid feeding tube to a pressure-resistant glass liquid tube with a three-way cock containing 185.9 mL of isobutylene monomer, and put the isoprene monomer in the polymerization vessel under nitrogen pressure. Liquid was sent. p-Dicmilk mouthlid 0.46 g and dimethylacetamide 0.36 g were added to the polymerization vessel. Next, 2.84 mL of titanium tetrachloride was added to initiate the polymerization. After stirring for 75 minutes from the start of polymerization, About 1 mL of the liquid was sampled. Subsequently, 62.2 g of styrene monomer was added to the polymerization vessel. Ninety minutes after adding the mixed solution, the polymerization vessel was poured into a large amount of water to terminate the reaction. Purification and drying were carried out in the same manner as in Example 1 to obtain an isobutylene block copolymer solid. The obtained polymer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0108] [Table 1]

 [0109] By comparing Example 1 and Comparative Example 1, it is possible to reduce the amount of metal residue by mixing and stirring the polymer solution after completion of polymerization with pure water supplemented with an emulsifier. As a result, it can be seen that coloring can be reduced. In addition, it can be seen that the amount of metal residue can be reduced by performing polymerization at a low concentration of the resin or by diluting the resin with a solvent after polymerization (Examples 3 and 4). Comparison of Comparative Examples 2-4).

 [0110] As can be seen from these examples, the isobutylene block copolymer having a metal residue derived from the Lewis acid catalyst of the present invention of 90 ppm or less is stable in color, particularly in color with low yellowness. is doing.

 [0111] From the above, by setting the amount of metal residue to 90 ppm or less, it is possible to suppress the coloration of the polymer, and it is possible to color with applications that require transparency and hygiene, and with dyes and pigments. It can be seen that it can be suitably used for molded products to be performed, particularly molded products to be colored in light colors.

 [0112] Although an example using a TiCl catalyst has been described above, other metal catalysts were used.

 Four

 Needless to say, even when used, it is possible to suppress coloring similarly by setting the amount of metal residue to 90 ppm or less.

[0113] (Production Example 1)

In a 3L reaction vessel equipped with a stirrer, water was removed with 1-chlorobutane (molecular sieves). Things) 1196g, 105g hexane, p Dicc milk mouth ride 1. 44g. After cooling the reaction vessel to 70 ° C, 1.04 g of N, N dimethylacetamide and 240 g of isobutylene were added. Further, 7.6 g of tetrachloride-titanium was added to initiate polymerization, and the reaction was carried out for 2 hours while stirring the solution at 70 ° C. Next, 102 g of styrene was added to the reaction solution, and the reaction was continued for another 30 minutes. The obtained polymer solution was poured into a large amount of water and the reaction was stopped by deactivating the Lewis acid catalyst. Thereafter, the polymer solution phase and the aqueous phase were separated by a separating funnel to obtain a polymer solution.

[0114] (Production Example 2)

 After stopping the reaction in the same manner as in Production Example 1, the polymer solution phase was washed twice with water. After confirming that the aqueous phase became neutral! /, The polymer solution phase was vacuum dried at 60 ° C. for 24 hours to obtain an isobutylene block copolymer.

[0115] A GPC analysis of this isobutylene block copolymer revealed that the number average molecular weight was 6

The molecular weight distribution was 5,000 and the molecular weight distribution was 1.24.

[0116] (Example 4)

 1 L of distilled water was charged into a 3 L separable flask equipped with a stirring blade, a condenser and a baffle, and the pH was adjusted to 10 by adding NaOH and heated to 60 ° C. Thereafter, 1 L of the polymer solution after the catalyst deactivation obtained by the method of Production Example 1 was added and maintained at 60 ° C. with stirring (first washing with water). After 1 hour from the start of stirring, stirring was stopped and the polymer solution phase and the aqueous phase were separated. After discharging the aqueous phase, the same operation was further performed with distilled water (second washing with water) to obtain a polymer solution. Further, the obtained polymer solution was vacuum dried at 60 ° C. for 24 hours to obtain a polymer.

 [0117] The obtained polymer was heated to 180 ° C for 10 minutes with a press machine to form a sheet having a thickness of 2 mm, and the YI value was measured with a color difference meter. The YI value was 15.1. (Table 2).

 [0118] (Example 5)

 A polymer was obtained in the same manner as in Example 4 except that the aqueous NaOH solution used for the first washing was replaced with one having a pH of 12. When the Y.I. value of the obtained polymer was measured, the Y.I. value was 14.6 (Table 2).

[0119] (Example 6)

After the first washing, distilled water was used without adjusting the pH (without adding NaOH). The procedure was the same as in Example 4, followed by washing with water to obtain a polymer. The YI value of the obtained polymer was measured and found to be 21.7 (Table 2).

[0120] (Example 7)

 The polymer solution after catalyst deactivation obtained in Production Example 1 was formed into a sheet without being washed with water. When the Y.I. value of the obtained polymer was measured, the Y.I. value was 21.7 (Table 2).

[0121] [Table 2]

 [0122] As described above, the polymers obtained in Examples 4 and 5 are coagulants having excellent transparency with very little coloration. According to the method of the present invention, the coloration of the coagulants is improved. I found that it was possible.

 [0123] (Production Example 3)

 To a 3L reaction vessel equipped with a stirrer was added 1196 g of 1-chlorobutane (water removed by molecular sieves), 105 g of hexane, and 1.44 g of p-dic milk mouthride. 70 to the reaction vessel. After cooling to C, 1.04 g of Hiichipicoline and 240 g of isobutylene were added. Further, 7.6 g of titanium tetrachloride was added to initiate polymerization, and the reaction was allowed to proceed for 2 hours while stirring the solution at -70 ° C. Next, 102 g of styrene was added to the reaction solution, and the reaction was continued for another 30 minutes. The obtained polymer solution was poured into a large amount of water to deactivate the catalyst, thereby stopping the reaction. Thereafter, the polymer solution phase and the aqueous phase were separated with a separatory funnel to obtain a polymer solution after deactivation of the catalyst.

[0124] A 3 L separable flask equipped with a stirring blade, a condenser and a baffle was charged with 1 L of distilled water and heated to 60 ° C. Then, 1 L of the polymer solution after deactivation of the catalyst was added, and the mixture was not stirred. Force S was maintained at 60 ° C (first washing with water). Stirring was stopped 1 hour after the start of stirring, and the polymer solution phase and the aqueous phase were separated. After draining the aqueous phase, the remaining polymer solution phase is placed in distilled water. Further, the same water washing operation was carried out (2nd water washing) to obtain a water washing polymer solution.

[0125] The GPC analysis of the isobutylene block copolymer contained in the obtained water-washed polymer solution revealed that the number average molecular weight was 65,000 and the molecular weight distribution was 1.24.

[0126] (Example 8)

 The total amount of the washing polymer solution obtained in Production Example 1 was DC- セ ン ト ラ ル -001-500 manufactured by Central Filter Industry Co., Ltd. (99% or more of particles having a diameter larger than that when the differential pressure before and after the filter was 0.2 MPa) It filtered using the filter which can be collected. When the amount of Ti in the polymer solution after filtration (the amount of metal residue derived from the Lewis acid catalyst) was analyzed, it was 38 ppm based on the solid content of the polymer.

[0127] Further, the obtained water-washed polymer solution was vacuum-dried at 60 ° C for 24 hours to obtain a polymer.

[0128] A sheet having a thickness of 2 mm was produced from the obtained polymer with a press. The sheet was produced as follows. The polymer of about 10g placed Fellow plate, 7 minutes preheating at ^{180 ° C, 10kg / cm 2} - 1 minute at G, yet 50KgZcm ² - after pressurizing 2 minutes at G, 50kgZcm ² - 3 minutes cooling at G did. When the obtained sheet was measured with a color difference meter, the YI value was 14.0 as shown in Table 3.

[Example 9]

 Other than using NXA0.5-5-20 (a filter that can collect 99% or more of particles with a diameter of 0.5 μm or more when the differential pressure before and after the filter is 0.2 MPa) as a filter. Was filtered in the same manner as in Example 8. When the amount of Ti in the polymer solution after filtration (the amount of metal residue derived from the Lewis acid catalyst) was analyzed, it was 19 ppm with respect to the solid content of the polymer.

 [0130] The Y. I. value of the obtained polymer was measured in the same manner as in Example 8. As a result, the value was 10.4 (Table 3).

[0131] (Example 10)

Filtration was carried out in the same manner as in Example 8 except that a filter capable of collecting 99% or more of particles having a diameter of 5 μm or more when the differential pressure before and after the filter was 0.2 MPa. When the amount of Ti in the polymer solution after filtration (the amount of metal residue derived from the Lewis acid catalyst) was analyzed, it was 80 ppm based on the solid content of the polymer. [0132] The YI value of the obtained polymer was measured in the same manner as in Example 8. The value was 21.9 (Table 3).

[0133] (Comparative Example 5)

 For the polymer solution obtained in Production Example 1 (without filtration)! The amount of Ti contained (the amount of metal residue derived from the Lewis acid catalyst) was analyzed and found to be 240 ppm based on the solid content of the polymer.

 [0134] The Y. I. value of the obtained polymer was measured in the same manner as in Example 8. As a result, it was 52.8 (Table 3).

 [0135] (Comparative Example 6)

 Filtration was carried out in the same manner as in Example 8 except that a filter capable of collecting 99% or more of particles having a diameter of 10 μm or more when the differential pressure before and after the filter was 0.2 MPa. When the amount of Ti in the polymer solution after filtration (the amount of metal residue derived from the Lewis acid catalyst) was analyzed, it was 120 ppm based on the solid content of the polymer.

 [0136] The Y. I. value of the obtained polymer was measured in the same manner as in Example 8. As a result, the value was 29.5 (Table 3).

 [0137] [Table 3]

 [0138] As described above, the polymers obtained in Examples 8 to 10 became a resin having good transparency with very little coloring, and according to the method of the present invention, the coloring of resin can be improved. It was found that this is possible.

 Industrial applicability

[0139] The isobutylene-based polymer obtained by the above method is generally employed for thermoplastic resin. For example, it can be melt-molded by extrusion molding, injection molding, press molding, blow molding or the like.

The isobutylene polymer of the present invention can be used in various applications similar to conventional isobutylene polymers. For example, elastomer materials, modifiers such as resin, rubber, asphalt, adhesive base polymer, resin modifiers, knocking materials, sealing materials, sealing materials such as gaskets and plugs, CD dampers, etc. Dampers for weak electrical appliances, dampers for construction, automobiles, vehicles, household appliances, etc. It can be suitably used for wire covering materials, packaging materials, various containers, and stationery parts.

Claims

The scope of the claims

 [1] An isobutylene polymer obtained by polymerizing a monomer component containing isobutylene in the presence of a polymerization initiator and a Lewis acid catalyst,

 An isobutylene polymer, wherein the amount of metal residue derived from the Lewis acid catalyst in the isopylene polymer is 90 ppm or less.

[2] The isobutylene polymer according to [1], wherein the polymerization initiator has a structure represented by the following general formula (1).

(CR '^ X) R ³ (1)

(In the formula, X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group. R ¹ and R ² are the same or different, and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ³ represents a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic or alicyclic hydrocarbon group, n represents a natural number of 1 to 6.

[3] The polymerization initiator represented by the general formula (1) is a bis represented by the formula C H (C (CH) C1).

 6 4 3 2 2

 (1 Chlor 1-methylethyl) benzene and the formula C H C (CH) C1 (1

 6 5 3 2

 The isobutylene-based polymer according to claim 2, which is at least one selected from a group force of (chloro 1-methylethyl) benzene force.

[4] The isobutylene polymer according to any one of [1] to [3], wherein the Lewis acid catalyst is tetrachloride-titanium.

 [5] The isobutylene-based polymer force is a block copolymer containing a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of a monomer other than isobutylene. Item 2. The isobutylene polymer according to Item 1.

6. The isobutylene polymer according to any one of claims 1 to 5, which is an aromatic vinyl monomer other than the isobutylene monomer.

7. The isoprene-based polymer according to claim 6, wherein the aromatic bur monomer is at least one selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene, and indene force.

[8] The isobutylene polymer is

• (Polymer block composed mainly of aromatic vinyl monomers) (Isobutylene monomer) Polymer block with main component) (Polymer block with aromatic vinyl monomer as main component) Force formed triblock copolymer,

 • (Polymer block based on isobutylene monomer) (Polymer block based on aromatic vinyl monomer) (Polymer block based on isobutylene monomer) A triblock copolymer, and

 • Diblock copolymer formed from (polymer block based on aromatic vinyl monomer) (polymer block based on isobutylene monomer)

 The isobutylene polymer according to claim 6 or 7, which is at least one block copolymer selected from the group consisting of

[9] A step of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst (I); water is brought into contact with the isobutylene polymer-containing solution obtained in the step (I); Step of deactivating the catalyst (Π);

 Further, after the step (ii), the obtained polymer-containing solution is washed with a basic aqueous solution of pHIO or higher (III);

 A process for producing an isobutylene polymer, comprising:

[10] A step of polymerizing a monomer component containing isobutylene in the presence of a Lewis acid catalyst (I); water is brought into contact with the isobutylene polymer-containing solution obtained in the step (I); Step of deactivating the catalyst (Π);

 After the step (II), the obtained polymer-containing solution is filtered with a filter capable of collecting 99% or more of particles having a diameter of 5 μm or more when the differential pressure before and after the filter is 0.2 MPa. Degree (IV);

 A process for producing an isobutylene polymer, comprising:

[11] Further, after the step (III), the obtained polymer-containing solution is subjected to a pressure difference between before and after the filter.

10. The production method according to claim 9, comprising a step (IV) of filtering with a filter capable of collecting 99% or more of particles having a diameter of 5 μm or more at 2 MPa.

[12] The isobutylene-based polymer strength, which is mainly composed of an isobutylene monomer.

The production method according to any one of 9 to 11.

[13] An isobutylene-based polymer has a polymer block (a) containing an isobutylene monomer as a main component. A polymer block mainly comprising an aromatic vinyl monomer (b)

9 to 11 is a manufacturing method.

[14] The polymerization in the step (I) is carried out at least one selected from the group consisting of primary and secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms, aliphatic, alicyclic and 14. The production method according to claim 9, wherein the production is carried out in a mixed solvent containing at least one selected from the group consisting of aromatic hydrocarbons.

15. The production method according to any one of claims 9 to 14, wherein the Lewis acid catalytic power is a halogenated metal.

 16. The method according to claim 15, wherein the halogenated metal is tetrasalt titanium.

17. The production method according to claim 9, wherein the basic aqueous solution is a sodium hydroxide aqueous solution.