JPS59227947A - Vulcanizable halogen-containing polymer composition - Google Patents

Abstract

PURPOSE:To provide a compsn. which can be vulcanized even at a low temp. in a short time, containing a halogen-contg. polymer, a specified vulcanizing agent, 1,8-diazabicyclo (5,4,0)undecene-7 or its salt and a metallic compd. CONSTITUTION:A vulcanizable compsn. contains 100ptw.wt. halogen-contg. polymer, 0.1-10pts.wt. 2,3-dimercaptopyrazine, 2,3-dimercaptoquinoxaline or derivative thereof, 0.1-10pts.wt. 1,8-di-azabicyclo(5,4,0)undecene-7 or its salt and 0.1- 50pts.wt. metallic compd. serving as an acid acceptor. Examples of said derivatives are 5-methyl-2,3-dimercaptopyrazine, 6-methylquinoxaline-2,3-dithiocarbonate, etc. When it is necessary to accelerate the vulcanization of the composn. one or more members selected from polyols, thiuram sulfides, dithiocarbamates and glimes can be added.

Description

[Detailed description of the invention] The present invention relates to compositions for vulcanizing halogen-containing polymers.

Polychloroprene, polyepichlorohydrin.

Halogen-containing polymers such as shrimp chlorohydrin-ethylene oxide copolymer, chlorine-containing acrylic rubber, chlorinated polyethylene, brominated butyl rubber, fluororubber, and polyvinyl chloride are heat resistant, oil dent resistant, and polyvinyl chloride resistant when vulcanized. It is known to be a material with excellent physical properties such as chemical properties. However, since the halogen-halogen bond in the polymer is chemically stable, it has been difficult to effectively vulcanize it.

The present applicant has already developed a method for vulcanizing halogen-containing polymers using 2,3-dimercapto-pyrazine or 2,3-dimercaptoquinoxaline or a vulcanizing agent consisting of these M conductors and a metal compound serving as an acid acceptor. (Japanese Patent Publication No. 58-14468 and Japanese Patent Publication No. 58-1446)
No. 9) disclosed a specific group of compounds as activators that are particularly effective when vulcanizing low-reactivity halogen-containing polymers. However, from the viewpoint of energy saving and improvement of productivity, which are becoming increasingly popular these days, it has been desired to develop a composition having an even faster vulcanization rate.

As a result of repeated research in order to meet the above-mentioned needs, the present inventors have discovered an activator that is dramatically superior to the compound group disclosed in the specification of the earlier application, and has been found in an extremely short story. Moreover, they succeeded in obtaining a vulcanizing composition that can be vulcanized even at low temperatures.

That is, the present invention comprises the following components (a) to (d): (a) 100 parts by weight of a halogen-containing polymer (b)
2,3-dimercaptopyrazine or 2,3-dimercaptoquinolinoline or Ic is a derivative thereof
0.1 to 10 parts by weight (c) 1.8-diazabicyclo(5,4,0) undecene-7 or its salt 0.1 to 10 parts by weight (d'') Metal compound to serve as an acid acceptor 0.1 50 parts by weight of a halogen-containing polymer vulcanization composition.

Examples of halogen-containing polymers that are the object of the present invention include chlorinated polyethylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-propylene-nonconjugated diene terpolymer, chlorosulfonated polyethylene, polyvinyl chloride, Chlorinated acrylic rubber, chlorinated butyl rubber.

Polychloroprene, polyepichlorohydrin.

Chlorine-based polymers such as epichlorohydrin-allyl glycidyl ether copolymer, epichlorohydrin-ethylene oxenoid copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether ternary copolymer,
A fluoropolymer consisting of a copolymer of vinylidene fluoride and its copolymerizable fluorine-containing olefin;
For example, hexafluoropropene, pentafluoropropene,
pen, 1-lifluoroethylene, trifluorochloroethylene.

Examples include copolymers with one or more of tetrafluoroethylene, vinylfluor A-ride, perfluoromediyl vinyl ether, perfluoropropyl vinyl ether, etc. Specifically, copolymers with one or more of tetrafluoroethylene, vinylfluor A-lide, perfluoromediyl vinyl ether, perfluoropropyl vinyl ether, etc. Polymers such as vinylidene fluor A light-topped draflu A roethylene-hekylyfluoropropene terpolymer and the like.

Examples of brominated polymers include brominated butyl rubber. These polymers may be used alone or as a blend of two or more of them. These halogen-containing polymers can be blended with other polymers, such as epoxide-containing acrylic rubbers.

The vulcanizing agent of the composition of the present invention, 2,3-dimercaptopyrazine or 2,3-dimercap-1 hequinoxaline, or a derivative thereof, is a compound represented by the following general formula (A>).

However, in the above general formula (A), R1 and R' may be the same or different, and each has a hydrogen atom or a carbon number of 1 to 8.
A benzene ring having at least one substituent selected from a halogen, a 21-ro group, a carboxyl group, a lower alkyl group, and a lower alkoxy group, with an alkyl group or R1 and R2 bonded together. may be formed. R3 and R4 may be the same or different, or a hydrogen atom, an alkali metal, or R3 and R4 may be bonded to each other to form a ":;c=o group. In this case, R5 and Re are the same However, they may be different, such as a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group.

Aryl group, aralkyl group, or R5, R
6 may be bonded to each other to form a 6-membered hetero ring. In addition, R7 is a group having 1 to 18 carbon atoms selected from an alkyl group, a cycloalkylene group, an alkenyl group, an aryl group, and an aralkyl group, and when n=1, Re is a group selected from a fluorkylene group and an alkenylene group. Selected carbon number 1~
8 group, or a group having 6 to 12 carbon atoms selected from a cycloalkylene group and an arylene group, or an ester with a mercapto group of another 2,3-dimercaptopyrazine or 2,3-dimercaptoquinoxaline or a derivative thereof May be combined.

Specific examples of the compound represented by general formula (A) include 2.
3-dimercap 1-pyrazine, pyrazine-2,3-dithiocarbon-1-, 5-medyl-2,3-dimercap 1
-pyrazine, 5-ethylpyrazine-2,3-dithiocarbonate, 5.6-dimethyzyl-2,3-dimercab-1-pyrazine, 5.6-dimethylpyrazine-2,3-dithiocarbonate, N~methyl- 3(2-mercaptoviradyl sulzenamide, N.N-dicyclohexyl-3(5-I-thyl-2-mercaptovirazyl)sulfenamide, 5-isopropyl-2-mercaptovirazyl-3-
Thiol benzoate, 5,6-dimethyl-2-mercapl-hebiradil-3-
Diolrebacate, 2,3-dimercaptoquinoxaline, 4-→Norin-2,3-dithiocarbonate, 6-
Ethyl-2,3-dimerkab 1-junotozarin, 6-medylquinoxaline-2. 3-Jig-bonate, 6,7-di(11-butyl)-2,3-dinolkab 1-
Kinogi→No'rin, N. N-disycyl■hexyl-3(2-mercapt.
Quino 4: lylyl) sulzenamide, N-(n-butyl l-3(G-methyl-2-mercabutoquinocyrillyl) sulfurinamide, 6-inpropyl-2-mercap 1-
Quino 4-4noryl-3-thiol acetate-1-, 5,8-dimethyl-2-mercaptoquinoxalyl-3-
Thiol benzoate, 6-diol sebacate, 6-bromo-2,3-dimercab 1 to kinoki 4-naline, 6-medoxyquinokilyline-2,3-didi A carbonate, 6 -nitro-2,3-dimercaptoquinoxyline, 6-carpoxyquinoxaline-2,3-didiocarbone-, and the like.

1,8-diazabiscif [1] used in the composition of the invention
(5,4.0) Undesen-7 (DBLJ) is (1
It is a compound represented by the following formula, and its salt is a compound represented by the formula (2).

(1) (2) Suitable salts for (2) include carbonates, carboxylates, salts with phenolic substances, salts with enolic substances, salts with thiols, and the like.

An example of the substances that make up these salts is carbonic acid.

Examples include acetic acid, sorbic acid, lyridylic acid, β-oxynaphthoic acid, 71nol, cyanuric acid, mercaptobenzodeazole 4-mercap1-benzimidazole, and the like.

Examples of the metal compounds of the acid acceptor of the present invention include oxides, hydroxides, carbonates, and carboxylates of Group I metals of the periodic table;
Kuishin JM, How Ill! hmm.

Phosphite 1 An oxide of a Group IV metal of the periodic table.

Basic carbonates, basic carboxylates, 9-resistant phosphites,
There are basic sulfites, tribasic sulfates, etc. Specific examples include magnesia, magnesium hydroxide, and barium hydroxide.

Magnesium carbonate, barium carbonate, quicklime.

Slaked lime, calcium carbonate, calcium silicate.

Calcium stearate, zinc stearate.

Calcium phthalate, magnesium phosphite.

Calcium phosphite, zinc white, tin oxide, resin, red lead,
Examples include white lead, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic tin phosphite, basic lead sulfite, and tribasic lead sulfate.

The compounding ratio of each component in the vulcanizing composition of the present invention is 0.1 to 10 mff 1 part, preferably 0.2 to 10 mff, of the vulcanizing agent represented by the general formula (A) per 100 parts by weight of the halogen-containing polymer.
5 parts by weight, 1,8- represented by general formula (1) or (2)
Diazabicyclo(5,4,0) Cunderene-7 or a salt thereof 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight
Heavy M part and 0.1 to 50 parts by weight of a metal compound serving as an acid acceptor,
Preferably, a range of 0.5 to 30 suspended parts is appropriate.

In the present invention, when a particularly rapid vulcanization rate is required, it is effective to further add one or more of polyols, thiuram sulfides, dithiocarbamates, and glymes to the composition of the present invention. be. Specific examples of such compounds include diethylene glycol, pentaerythritol, trimedylolpropane, trimethylolethane, sorbyl, tetramethylthiuram monosulfide, te(-ramedyldiuram disulfide, te-i- Laedil diuram disulfide, dipentamylene dithiocarbamate 1~rasulfide, diethyldithiocarbamate, lulu, dibderdithiocarbamate nickel, bipecolyl didiocarbamate, poly]
Examples include nitrogen glycol. The compounding amount of these compounds is 0.1 to 10 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the halogen-containing polymer.
This is the hexagonal stone section.

In addition to the above, the composition of the present invention may contain various additives commonly used in the art, such as fillers, reinforcing agents, plasticizers, processing aids, anti-aging agents, pigments, and flame retardants. It can be mixed arbitrarily.

As a method for blending the composition of the present invention, any means conventionally used in the field of polymer processing, such as mixing rolls, Banbury mixer 1 various kneaders, etc., can be used.

The above mixed composition is usually heated to 100°C and 0°C at 200°C.
．． A vulcanizate can be obtained by heating for 1 to 300 minutes. As the vulcanization molding method, methods such as pressure molding using a mold, injection molding, steam can, heating using an air bath, infrared rays, microwave, etc. can be used.

The present invention will be explained below with reference to Examples.

Examples 1 to 10, Comparative Example 1 Each of the formulations shown in Table 1 was kneaded with an A-punn roll at 60 to 10°C, and the sheet was put into a mold.
4 and Comparative Example 1 were pressure molded at 155°C for 10 minutes, and Examples 5 to 10 were pressure molded at 155°C for 30 minutes.

Physical property tests were conducted on each of the obtained vulcanizates, and the results are shown in Table 2. In addition, the vulcanization curves of the formulations of Example 1 and Comparative Example 1 were measured using a JSR type Curastometer.
Measurements were made at an oscillation angle of 3° and a temperature of 155°C, and the results are shown in FIG.

In addition, Comparative Example 1 is a composition containing the accelerator disclosed in the specification of the earlier application.

[Brief explanation of drawings]

FIG. 1 shows the vulcanization curves of Example 1 and Comparative Example 1. Applicant: Osaka Soda Co., Ltd. Agent: Patent Attorney Toru Dojo

Claims (1)

[Claims] (a) 100 parts by weight of halogen-containing polymer (b) 2
．． 3-dimercaptopyrazine or 2,3-dimercaptoquino 4: lilin or derivatives thereof
o, i ~ 10 parts by weight (C) 1.13-Sifsat::
Schiff 0 (5,,4,0) Undecene-1 or its salt o, i to 10 heavy parts (d) Metal compound serving as an acid acceptor 0.1 to 50 heavy suspended parts (a) to (d' ) A composition for vulcanizing a halogen-containing polymer, characterized by containing each component.