JPS6338070B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD OF THE INVENTION The present invention relates to compositions for vulcanizing halogen-containing polymers. (Prior art) Halogen-containing polymers such as polyvinyl chloride, polychloroprene, chlorinated polyethylene, and polyepichlorohydrin have heat resistance and
It is a material with excellent physical properties such as oil resistance and chemical resistance, and is used as a useful material in various industrial fields. However, since the carbon-halogen bonds in these halogen-containing polymers are chemically stable, it has hitherto been difficult to effectively vulcanize them. It is well known that sulfur or sulfur-donating compounds are excellent vulcanizing agents for natural rubber, SBR, etc., but it is extremely difficult to vulcanize halogen-containing polymers with these vulcanizing agents. It is also known that there are (Purpose of the Invention) As a result of intensive studies aimed at obtaining an effective vulcanization method for the above-mentioned halogen-containing polymer, the present inventors have discovered that sulfur or a sulfur-donating compound can be used in the coexistence of a metal compound serving as an acid acceptor. , found that 1,8-diazabicyclo(5,4,0)undecene-7 or its salt significantly accelerates the vulcanization reaction, and that this vulcanization significantly improves the physical properties of halogen-containing polymers. This invention has been achieved. (Structure of the Invention) The present invention provides each component consisting of the following (a) to (d): (a) a halogen-containing polymer (b) a sulfur and/or sulfur-donating compound (c) 1,8-diazabicyclo(5 , 4,0) Undecene-7 or its salt (d) A halogen-containing polymer vulcanizing composition characterized by containing a metal compound serving as an acid acceptor. Examples of the halogen-containing polymer (a) of the present invention include chlorinated polyethylene, chlorinated ethylene-propylene copolymer, chlorinated ethylene-propylene-conjugated diene terpolymer, chlorosulfonated polyethylene, polyvinyl chloride, and chlorinated polyethylene. Acrylic rubber, chlorinated butyl rubber, brominated butyl rubber, fluoro rubber,
Examples include polychloroprene, polyepichlorohydrin, epichlorohydrin-allyl glycidyl ether copolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, and the like. The sulfur-donating compound as component (b) of the present invention is selected from thiuram sulfides represented by the following general formula () or () or morpholine polysulfides represented by the general formula (). In the above general formulas () and (), R ¹ ,
R ² , R ³ and R ⁴ are hydrocarbon residues having 1 to 4 carbon atoms, and x and y are integers of 1 to 6. Representative examples of general formulas () and () include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram hexasulfide,
Examples include N,N'-dimethyl-N,N'-diphenylthiuram disulfide and dipentamethylenethiuram tetrasulfide. Moreover, in the general formula (), z is an integer of 1 to 6. Representative examples of general formula () include morpholine disulfide, morpholine tetrasulfide, and the like. (c) 1,8-diazabicyclo(5,4,
0) Undecene-7 (hereinafter referred to as DBU) is a compound represented by the following formula (), and its salt is a compound represented by the following formula ().

【formula】

[Formula] Examples of the DBU salt of the above formula () 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, sorbic acid, salicylic acid, β-oxynaphthoate, phenol, cyanuric acid, mercaptobenzothiazole, mercaptobenzimidazole, and the like. (d) The metal compound serving as the acid acceptor of the present invention includes:
Oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites of metals in group A of the periodic table, oxides and basic carbonates of metals in group a of the periodic table, There are basic carboxylates, basic phosphites, basic sulfites, tribasic sulfates, etc. Specific examples include magnesia, magnesium hydroxide,
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, litharge, red lead , white lead, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic tin phosphite, basic lead sulfite, tribasic lead sulfate, and the like. The composition of the present invention comprises (a) halogen-containing polymer 100
Based on the weight part, (b) 0.1 to 10 parts by weight, preferably 0.2 to 6 parts by weight of sulfur and/or sulfur-donating compound,
(c) 0.1 to 10 parts by weight of DBU or DBU salt, preferably 0.2 to 6 parts by weight, (d) 0.1 part of a metal compound to serve as an acid acceptor.
It is suitable to contain up to 50 parts by weight, preferably 0.5 to 30 parts by weight. The composition of the present invention includes various compounding agents commonly used in the technical field, such as fillers, reinforcing agents, plasticizers, processing aids, anti-aging agents, pigments, flame retardants, and ingredients other than the above component (d). An acid acceptor, etc. can be optionally blended. The composition of the present invention can be mixed using any means conventionally used in the field of polymer processing, such as mixing rolls, Banbury mixers, and various kneaders.
Furthermore, the composition of the present invention is usually vulcanized at 100 to 200°C.
It can be made into a vulcanizate by heating for 0.5 to 300 minutes. As the vulcanization molding method, any method such as pressure molding using a mold, injection molding, steam can, air bath, or heat molding using infrared rays, microwaves, etc. can be adopted. (Effects of the Invention) The composition of the present invention replaces sulfur or sulfur-donating compounds, which are inexpensive and common vulcanizing agents in natural rubber and diene-based synthetic rubbers, with halogen-containing polymers, which are considered unsuitable as vulcanizing agents. It is a composition applied as a component of a vulcanization system, and can be vulcanized using conventional vulcanization equipment, has a rapid vulcanization rate, and has excellent vulcanization properties. Therefore, it is useful as a polymeric material that can effectively utilize the excellent physical properties of the vulcanized halogen-containing polymer. (Examples) Examples 1 to 5 Comparative Example 1 Each compound shown in Table 1 was kneaded with an open roll at 60 to 70°C to form a sheet, and this was put into a mold.
Pressure molding was carried out at 155°C and 80 kg/cm ² for 30 minutes. The physical properties of each of the obtained vulcanizates were measured 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 at the amplitude angle using a JSR type culastometer.
3° and a temperature of 155°C, and the results are shown in Figure 1.

【table】

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 shows the vulcanization curves of Example 1 and Comparative Example 1.

Claims (1)

[Scope of Claims] 1 (a) halogen-containing polymer (b) sulfur and/or sulfur donating compound (c) 1,8-diazabicyclo(5,4,0) undecene-7 or its salt (d) acid acceptor A composition for vulcanizing a halogen-containing polymer, characterized by containing each of the components (a) to (d) above.