JPS6054977B2 - Halogen-containing polymer vulcanization composition - Google Patents

Description

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

Halogen-containing polymers such as polychloroprene, polyepichlorohydrin, epichlorohydrin-ethylene oxide copolymer, chlorine-containing acrylic rubber, chlorinated polyethylene, brominated butyl rubber, fluorine rubber, and polyvinyl chloride have heat resistance, oil resistance, It is known to be a material with excellent physical properties such as chemical resistance. However, since the carbon-halogen bond in the polymer is chemically stable, it has been difficult to vulcanize it effectively. The present applicant has already provided a composition for vulcanizing a halogen-containing polymer using a vulcanizing agent comprising 2,3-dimercaptopyrazine, 2,3-dimercaptoquinoxaline, or a derivative thereof and a metal compound serving as an acid acceptor. However, (Special Publication No. 144/1986 and Publication No. 1/1988)
No. 446) disclosed a specific group of compounds as activators particularly effective in 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 can be used in an extremely short period of time. Moreover, they succeeded in obtaining a vulcanizing composition that can be vulcanized even at low temperatures.

That is, the present invention provides each of the following components (a) to (d), (a
) Halogen-containing polymer 10 parts by mass (b) 2,3-dimercaptopyrazine or 2,3-dimercaptoquinoxaline or derivatives thereof 0.1 to 1 part by volume (c
) 1,8-diazabicyclo(5,4,0)undecene-7 or its salt 0.1 to W parts by weight (d) 0.1 to 5 parts by weight of a metal compound serving as an acid acceptor. This is a composition part for vulcanizing a halogen-containing polymer.

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, cross-sulfonated polyethylene, polyvinyl chloride, Chlorine acrylic rubber, chlorinated butyl rubber, polychloroprene, polyepichlorohydrin, epichlorohydrin-allyl glycidyl ether copolymer, epichlorohydrin-ethylene oxide copolymer, epic rehydrin-ethylene oxide-allyl glycidyl ether terpolymer, etc. Fluorine-based polymers consisting of copolymers of vinylidene fluoride and other copolymerizable fluorine-containing olefins, such as hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl Examples include copolymers with one or more of fluoride, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, etc. Specifically, vinylidene fluoride-hexafluoropropene copolymers, vinylidene fluoride-do Examples include tetrafluoroethylene-hexafluoropropene terpolymer.

Examples of brominated polymers include brominated butyl rubber.

These polymers may be used alone or as a blend of two or more of them. Other types of polymers, such as epoxide-containing polymers such as epoxide-containing acrylic rubber, can be blended with these halogen-containing polymers. 2,3-dimercaptopyrazine, 2,3-dimercaptoquinoxaline, or a derivative thereof, which is a vulcanizing agent in the composition of the present invention, is a compound represented by the following general formula (4).

However, in the above general formula (4), Rl and R2 may be the same or different, and each has a hydrogen atom or a carbon number of 1 to 8.
represents an alkyl group, or Rl, P2y type i-
7'',, IyCノ -Ki 礪1b↓May form a benzene ring which may have at least one selected substituent, R3 and R4 may be the same or different, and hydrogen Atom, alkali metal, -ma2-, L
7, or R3 and R4 may be bonded to each other to form a C=0 group.

In this case, R5 and R6 may be the same or different,
represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or R
5 and R6 may be bonded to each other to form a 6-membered hetero ring. Further, R7 represents a group having 1 to 18 carbon atoms selected from an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an aralkyl group, or represents 5R8, 湛-, and n=o or 1, When n=1, R
8 represents a group having 1 to 8 carbon atoms selected from alkylene groups and alkenylene groups, or a group having 6 to 12 carbon atoms selected from cycloalkylene groups and arylene groups. Also, the above (R
8, Σ- may form an ester bond within the same molecule or with a mercapto group of another 2,3-dimercaptopyrazine or 2,3-dimercaptoquinoxaline or a derivative thereof.

Specific examples of the compound represented by general formula (4) include 2,
3-dimercaptopyrazine, pyrazine-2,3-dithiocarbonate, 5-methyl-2,3-dimercaptopyrazine, 5-ethylpyrazine-2,3-dithiocarbonate, 5,6-dimethyl-2,3-dimercaptopyrazine ~ 5, 6-dimercaptopyrazine-2,3-dithiocarbonate, N-methyl-3(2-mercaptopyrazyl)sulfenamide, N,N-dicyclohexyl-3(5-
ethyl-2-mercaptopyrazyl) sulfenamide,
5-isopropyl-2-mercaptopyrazi-3-thiol benzoate, 5,6-dimethyl-2-mercaptopyrazi-3-thiol sebacate, 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-ethyl-2 , 3-dimercaptoquinoxaline ~ 6-methylquinoxaline-2,3-dithiocarbonate, 6,7-di(n-butyl)-2,3-dimercaptoquinoxaline, N,N-dicyclohexyl-3(2-mercaptoquinoxaline) Xalyl) sulfenamide, N-(n-butyl)-3(6-methyl-2-mercaptoquinoxalyl) sulfenamide, 6-isopropyl-2-mercaptoquinoxalyl-3-thiol acetate, 5,8-dimethyl-2-mercapto Quinoxalyl-3-thiol benzoate, 6-isobutyl-2-mercaptoquinoxalyl-3-thiol sebacate, 6-bromo-2,3-dimercaptoquinoxaline to 6-methoxyquinoxaline-2,3-dithiocarbonate, 6-nitro 2 , 3-dimercaptoquinoxaline to 6-carboxyquinoxaline-2,3-dithiocarbonate.

1,8-diazabicyclo(
5,4,0) Undecene-7 (DBU) is a compound represented by formula (1), and its salt is a compound represented by (2).

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

Examples of substances constituting these salts include carbonic acid, acetic acid, sorpic acid, salicyl residue, β-oxynaphthoic acid, phenol, cyanuric acid, mercaptobenzothiazole, and mercaptobenzimidazole. Metal compounds that can be used as acid acceptors of the present invention include those listed in the periodic table.
Oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites of group metals, oxides, basic carbonates, basic carboxylates of group a metals of the periodic table These include acid salts, basic phosphites, basic sulfites, and tribasic sulfates.

Specific examples include magnesium hydroxide,
Barium hydroxide, magnesium carbonate, barium carbonate, quicklime, slaked lime, calcium carbonate, silicic acid. Lucium,
Calcium stearate, zinc stearate, calcium phthalate, magnesium phosphite, calcium phosphite,
Zinc white, tin oxide, risarge, red lead, white lead, dibasic lead phthalate, dibasic carbonate, tin stearate, basic lead phosphite, basic tin phosphite, basic lead sulfite, Examples include tribasic lead sulfate. The proportion of each component in the vulcanizing composition of the present invention is 0.1 to 1 part, preferably 0.2 part, of the vulcanizing agent represented by general formula (4) to 10 parts of the halogen-containing polymer. ~5 parts by weight, represented by general formula (1) or (2).

1,8-diazabicyclo(5,4,0) undecene-7
Or 0.1 to 1 part of the salt, preferably 0.1 to 5 parts
parts by weight and 0.1 to 50 parts by weight of a metal compound serving as an acid acceptor;
Preferably, a range of 0.5 to 3 parts by weight is appropriate.

In the present invention, when a particularly rapid vulcanization rate is required, one or more of polyols, thiuram sulfides, dithiocarbamates, and glymes may be added to the composition of the present invention. It is valid.

Specific examples of such compounds include diethylene glycol, pentaerythritol, trimethylolpropane, trimethylolethane, sorbitol, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, dipentamethylene lenthiuram. Examples include tetrasulfide, tellurium diethyldithiocarbamate, nickel dibutyldithiocarbamate, pipecoline pipecolyldithiocarbamate, and polyethylene glycol. The compounding amount of these compounds is 0.1 to 10 parts by weight, particularly preferably 0.1 to 6 parts by weight, per 10 parts by weight of the halogen-containing polymer. In addition to the above, the composition of the present invention may optionally contain various compounding agents such as fillers, reinforcing agents, plasticizers, processing aids, anti-aging agents, pigments, flame retardants, etc. as commonly used in the art. It can be blended with. As a method for blending the composition of the present invention, any means conventionally used in the field of polymer processing can be used, such as mixing rolls, Panbury mixers, various kneaders, and the like.

The above-mentioned mixed composition is usually 100 to 20 (s) and 0
．． A vulcanizate can be obtained by heating the powder for 1 to 30 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. below,
The invention will be explained by way of examples.

Examples 1-10. Comparative Example 1 Each compound shown in Table 1 was kneaded with an open roll at 60 to 70°C, and the sheet was put into a mold, and the mixtures were mixed in Examples 1-
4 and Comparative Example 1 were press-molded at 155°C for 10 minutes, and Examples 5 to 10 were press-molded at 155°C for 3 powders.

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
Using an SR type culastometer, the amplitude angle 3 is set to the temperature 1.
The measurement was carried out at 55°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.

Claims (1)

[Scope of Claims] 1 (a) 100 parts by weight of halogen-containing polymer (b) 2
, 3-dimercaptopyrazine or 2,3-dimercaptoquinoxaline or derivatives thereof 0.1 to 10 parts by weight (c) 1,8-diazabicyclo(5,4,0)undecene-7 or a salt thereof 0.1 to 10 parts by weight 10 parts by weight (d) 0.1 to 50 parts by weight of a metal compound serving as an acid acceptor A composition for vulcanizing a halogen-containing polymer, comprising the above components (a) to (d).