JP2006193682A - Method for modifying polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To introduce an organic functional group derived from a disulfide compound into a polymer chain. <P>SOLUTION: A method for modifying the polymer is carried out as follows. The polymer (A) is modified with a radical initiator (B) and a compound (C) represented by formula (I) or formula (II). Thereby, the organic group X derived from formula (I) or (II) is introduced into the polymer (A). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for modifying a polymer, and more specifically, a disulfide compound is used together with a radical initiator to react with a polymer to generate a radical in a polymer chain, and an organic group derived from the disulfide compound is introduced into the polymer chain to form a polymer. It relates to a method of denaturation.

  Various attempts have been made to impart functional groups on polymer chains in order to enhance the function of the polymer. In particular, many techniques for introducing a functional group into a polymer chain by a graft reaction using a radical initiator are known. For example, Non-Patent Document 1 discloses a technique for introducing a functional group into polypropylene using maleic anhydride, and Patent Document 1 discloses a technique for introducing a functional group using acrylic acid. Non-Patent Document 2 describes grafting of glycidyl acrylate onto polyethylene or polypropylene. Patent Document 2 describes a method of introducing a functional group into polyisoprene or polypropylene using a radical initiator and a stable free radical derivative. On the other hand, Patent Document 3 discloses a method of modifying a diene rubber by using a peptizer accelerator having a functional group. This method modifies the diene rubber by utilizing the property that the thiyl radical of the peptizer accelerates the rubber radical generated during the mastication of the diene rubber (see Non-Patent Document 3, for example).

JP 51-70254 A JP 2004-182926 A JP 2002-201312 A Polymer chemistry, 25, 107 (1968) J. Polym. Sci., A, Polm. Chem., 31, 3405 (1993) Journal of Japan Rubber Association, 63, 639 (1990)

  However, attempts to introduce functional groups into the polymer chain by actively generating a polymer radical on the polymer molecular chain using a radical initiator and capturing it with a compound that generates a thiyl radical, such as a peptizer. Never before.

  Accordingly, an object of the present invention is to introduce an organic group derived from a disulfide compound onto a polymer chain by reacting a disulfide compound having an organic group with a polymer using a radical initiator.

  According to the invention, the polymer (A) is converted into a radical initiator (B) and a formula (I) or (II):

A modification method of the polymer comprising introducing the organic group X derived from the formula (I) or (II) into the polymer (A) is provided by modifying the compound (C) represented by formula (I).

  According to the present invention, the radical initiator (B) and the disulfide compound (C) represented by the formula (I) or (II) are added to the polymer (A) to thereby add the formula (I) to the polymer (A). Alternatively, an organic group X derived from (II) can be introduced to introduce a desired organic group into the polymer (A).

  The inventors of the present invention added a disulfide compound having an organic substituent X to the polymer together with the radical initiator (B), and reacted. As illustrated in the following reaction formula, the organic group derived from the disulfide compound It was found to be introduced onto the chain of the polymer (A).

  Preferred examples of the organic substituent X of the formulas (I) and (II) include alkyl groups having 1 to 30 carbon atoms, phenyl group, allyl group, amino group, isocyanate group, hydroxyl group, thiol group, vinyl group, Examples include organic groups including epoxy groups, thiirane groups, carboxyl groups, acid anhydride groups, amide groups, ester groups, imide groups, nitrile groups, alkoxysilyl groups, silyl groups, and thiocyan groups.

  Examples of the polymer (A) that can be modified by the method of the present invention include any polymer capable of generating a polymer radical by the radical initiator (B), specifically, a styrene-butadiene-styrene block. Copolymer, styrene-isoprene-styrene copolymer, styrene-ethylene-butene-styrene block copolymer, styrene-ethylene-propylene-styrene copolymer, polyethylene, polypropylene, polystyrene, polyaromatic vinyl, polyolefin, natural Rubber, polyisoprene, various styrene-butadiene copolymers, various polybutadienes, acrylonitrile-butadiene copolymers, polyisobutylene, polybutene, butyl rubber, halogenated butyl rubber, brominated isobutylene-paramethylstyrene copolymer Styrene-isoprene-butadiene copolymer, chloroprene rubber, ethylene-propylene-diene terpolymer rubber, ethylene-propylene copolymer, ethylene-propylene-butene terpolymer, acrylic rubber, silicone rubber, Fluorine rubber, epichlorohydrin rubber, various polymethacrylates, various polyethers, various polysulfides, various polyvinyl ethers, various polyesters, various polyamides, cellulose, starch, various polyurethanes, various polyureas, various polyamines and the like can be mentioned.

  Examples of the radical initiator (B) that can be used in the method of the present invention include benzoyl peroxide (BPO), t-butyl peroxybenzoate (Z), dicumyl peroxide (DCP), and t-butyl cumylper. Oxide (C), di-t-butyl peroxide (D), 2,5-dimethyl-2,5-di-t-butylperoxyhexane (2,5B), 2,5-dimethyl-2,5- Di-t-butylperoxy-3-hexyne (Hexyne-3), 2,4-dichloro-benzoyl peroxide (DC-BPO), di-t-butylperoxy-di-isopropylbenzene (P), 1, 1-bis (t-butylperoxy) -3,3,5-trimethyl-cyclohexane (3M), n-butyl-4,4-bis (t-butylperoxy) ) Valerate, organic peroxides such as 2,2-bis (t-butylperoxy) butane and azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), 2,2′-azobis- (2 -Amidinopropane) dihydrochloride, dimethyl 2,2'-azobis (isobutyrate), azobis-cyanvaleric acid (ACVA), 1,1'-azobis- (cyclohexane-1-carbonitrile) (ACHN), 2,2 Radicals such as' -azobis- (2,4-dimethylvaleronitrile) (ADVN), azobismethylbutyronitrile (AMBN), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Examples include generators.

  Examples of the disulfide compound that can be used in the method of the present invention include the polysulfide compounds of the above formula (I) and / or (II). In the formula (I) or (II), the group X is, for example, C1-C30 alkyl group, phenyl group, allyl group, amino group, isocyanate group, hydroxyl group, thiol group, vinyl group, epoxy group, thiirane group, carboxyl group, carbonyl group-containing group (for example, succinic anhydride, anhydrous Examples thereof include cyclic acid anhydrides such as maleic acid, glutaric anhydride, and phthalic anhydride), amide groups, ester groups, imide groups, nitrile groups, thiocyan groups, silyl groups, alkoxysilyl groups, and the like.

  In the modification method of the present invention, the ratio of the polymer (A), the radical initiator (B) and the compound (C) represented by the formula (I) or (II) is not particularly limited, but preferably the polymer (A) It is preferable to use 0.01 to 10 mol of the initiator (B) and 0.01 to 20 mol of the compound (C) of the formula (I) or (II) per 1 mol of the structural unit.

  Modified polymers modified by the method of the present invention include, for example, diene rubbers, polyolefin rubbers, thermoplastic TPE, polyolefins, thermoplastic resins, thermosetting resins and other polymers, reinforcing fillers such as carbon black and silica, Vulcanizing or cross-linking agents, vulcanizing or cross-linking accelerators, various oils, anti-aging agents, plasticizers and other commonly added additives can be blended. The composition can be kneaded and vulcanized to be used for vulcanization or crosslinking. As long as the amount of these additives is not contrary to the object of the present invention, the conventional general amounts can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.

Example 1 and Comparative Example 1
The raw materials used are as follows.
Butyl rubber: Bayer's BUTYL301
O, O'-Dibenzamide diphenyl disulfide: Nouchiizer SS manufactured by Ouchi Shinsei Chemical Co., Ltd.
Di-t-butyl peroxide: Perbutyl D manufactured by NOF Corporation

Example 1
350.0 g (butyl unit 6.22 mol) of butyl rubber, 45.6 g (0.187 mol) of di-t-butyl peroxide and 85.5 g (0.187 mol) of O, O′-dibenzamide diphenyl disulfide at a temperature of 60 ° C. The mixture was placed in a closed banbury set to 1, and mixed for 15 minutes. The resulting mixture was kneaded in a closed banbury set at 100 ° C., and the temperature after nitrogen substitution for 5 minutes was raised to 175 ° C. while kneading, and further kneaded for 15 minutes. A part of the obtained polymer was dissolved in toluene, and the polymer was isolated and purified by reprecipitation operation. By performing ¹ H-NMR analysis and elemental analysis using the purified product, the phenyl group introduction rate was calculated, and the number average molecular weight was measured by gel permeation chromatography (GPC). The results are shown in Table I.

Comparative Example 1
30.0 g of butyl rubber (6.22 mol of butyl unit) and 85.5 g (0.187 mol) of O, O′-dibenzamide diphenyl disulfide were placed in a closed Banbury set at a temperature of 60 ° C. and mixed for 15 minutes. The resulting mixture was purged with nitrogen for 5 minutes while kneading in a closed banbury set at 100 ° C. While kneading, the temperature was raised to 175 ° C. and kneading was continued for 15 minutes. A part of the obtained polymer was dissolved in toluene, and the polymer was isolated and purified by reprecipitation operation. By performing ¹ H-NMR analysis and elemental analysis using the purified product, the phenyl group introduction rate was calculated, and the number average molecular weight was measured by gel permeation chromatography (GPC). The results are shown in Table I.

  According to the present invention, as described above, since a desired organic group can be introduced by generating a radical in the polymer (A), adhesion to an inorganic material or metal, impact resistance and mechanical strength of a polymer alloy are achieved. It is useful for improving

Claims (4)

Polymer (A) is converted to radical initiator (B) and formula (I) or (II):

A method for modifying a polymer, wherein the organic group X derived from the formula (I) or (II) is introduced into the polymer (A) by modification using the compound (C) represented by formula (I).   The modification | denaturation method of Claim 1 using the compound of the formula (I) and (II) whose bond position in the benzene ring of the organic group X and a sulfur atom is ortho position.   In the formulas (I) and (II), X is an alkyl group having 1 to 30 carbon atoms, phenyl group, allyl group, amino group, isocyanate group, hydroxyl group, thiol group, vinyl group, epoxy group, thiirane group, carboxyl group, The organic anhydride group, at least one organic group selected from the group consisting of organic groups including an amide group, an ester group, an imide group, a nitrile group, an alkoxysilyl group, a silyl group, and a thiocyan group. The modification method.   The modified polymer obtained by the modification | denaturation method of any one of Claims 1-3.