JPS6215096B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to compositions for vulcanizing chlorine-containing polymers. More specifically, the present invention provides (a) a chlorine-containing polymer, (b) sulfur and/or thiuram sulfides represented by the following general formula () or (), and a morpholine polysulfide represented by the following general formula (). Sulfur-donating compounds selected from (However, in general formulas () and (),
R ¹ , R ² , R ³ and R ⁴ are hydrocarbon residues having 1 to 4 carbon atoms. Moreover, a ₁ and a ₂ are integers of 1 to 6. In the general formula (), a ₃ is an integer of 1 to 6. ) (c) A quaternary salt selected from quaternary ammonium salts or quaternary phosphonium salts represented by the following general formula () and quaternary pyridinium salts represented by the following general formula () (However, in the general formula (), Z is N or P
and R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and are groups selected from alkyl groups having 1 to 17 carbon atoms, cyclohexyl groups, phenyl groups, and benzyl groups. In the general formula (), R ⁹ is selected from the same group as R ⁸ in the general formula (). Also, in the general formulas () and (),
X is a group selected from halogen and saturated or unsaturated monocarboxylic acids having 1 to 18 carbon atoms. ) (d) Polyhydric hydroxy compound selected from polyhydric alcohols and polyhydric phenols (e) Calcium hydroxide 0.1 to 10 parts of component (b) per 100 parts by weight of component (a) above.
Component (c) 0.1 to 10 parts by weight, component (d) 0.1 to 15 parts by weight, and component (e) 0.5 to 20 parts by weight. . When chlorine-containing polymers such as chlorinated polyethylene, polyvinyl chloride, polychloroprene, and polyepichlorohydrin are vulcanized, they become materials with excellent physical properties such as heat resistance, oil resistance, and chemical resistance, and these are used in various industries. It is used as a useful material in the field. However, since the carbon-halogen bonds in these chlorine-containing polymers are chemically stable, it has been difficult to effectively vulcanize them. It is well known that sulfur or sulfur-donating compounds can be excellent vulcanizing agents for natural rubber, SBR, etc. On the other hand, it is also well known that it is very difficult to vulcanize chlorine-containing polymers with this vulcanizing agent. The present inventors added a vulcanization accelerator such as a quaternary ammonium salt, a quaternary phosphonium salt, or a quaternary pyridinium salt, a polyvalent hydroxy compound, and calcium hydroxide to the vulcanizing agent consisting of sulfur or a sulfur-donating compound. The present invention was achieved based on the discovery that when used in combination, chlorine-containing polymers, which were conventionally difficult to vulcanize, can be rapidly and effectively vulcanized and the physical properties of the polymers can be improved. Examples of the chlorine-containing polymer (a) to be used in the present invention include polyepichlorohydrin, epichlorohydrin-allyl glycidyl ether copolymer, epichlorohydrin-ethylene oxide copolymer, and epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. Examples include epichlorohydrin-based polymers such as polyvinyl chloride, vinyl chloride-based polymers such as vinyl chloride-ethylene copolymer, chlorinated polyethylene, and polychloroprene. Among the sulfur-donating compounds of component (b) used as the vulcanizing agent in the present invention, typical examples of thiuram sulfides represented by the general formula () or () include tetramethylthiuram monosulfide. , tetramethylthiuram disulfide,
Examples include tetraethylthiuram disulfide, tetrabutylthiuram hexasulfide, N,N'-dimethyl-N,N'-diphenylthiuram disulfide, and dipentamethylenethiuram tetrasulfide. The above general formula () which is also a sulfur-donating compound
Typical examples include morpholine disulfide and morpholine tetrasulfide. (c) used as a vulcanization accelerator in the present invention
R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ of quaternary ammonium salts, quaternary phosphonium salts and quaternary pyridinium salts represented by the above general formulas () and () of the components
Examples of an alkyl group include a methyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, and the like. When X is a halogen, examples include chlorine, bromine, and iodine, and examples of saturated or unsaturated monocarboxylic acids having 1 to 18 carbon atoms include acetic acid, caproic acid, lauric acid, stearic acid, and oleic acid. Examples include acids. These quaternary salts may be used alone or in combination. To give specific examples of these quaternary salts, compounds of general formula () include tetrapropylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium iodide, tetrabutylphosphonium bromide, triethylhexadecylphosphonium Bromide, ethyltrioctylphosphonium chloride, tetrabutylphosphonium laurate, triethylhexylammonium oleate, etc., and examples of the compound of general formula () include dodecylpyridinium bromide. (d) used as a vulcanization accelerator in the present invention
The component polyhydric hydroxy compound is selected from polyhydric alcohols or polyhydric phenols, and these may be used alone or in combination. Examples of polyhydric hydroxy compounds include diethylene glycol, pentaerythritol, trimethylolpropane, trimethylolethane, sorbitol, catechol, resorcinol, pyrogallol, gallic acid, bisphenol A, and the like. The composition of the present invention includes (b) 0.1 to 10 parts by weight of sulfur and/or a sulfur-donating compound, based on 100 parts by weight of the chlorine-containing polymer;
Preferably 0.2 to 6 parts by weight, (c) quaternary salt 0.1 to 10 parts by weight, preferably 0.2 to 6 parts by weight, (d) polyhydric hydroxy compound 0.1 to 15 parts by weight, preferably 0.5 to 8 parts by weight, ( e) It is appropriate to contain 0.5 to 20 parts by weight of calcium hydroxide, preferably 1 to 10 parts by weight. If the amount of the vulcanizing agent (component (b)) is less than 0.1 part by weight, effective vulcanization will not be possible, and if it exceeds 10 parts by weight, the vulcanizate will become too rigid. When an elastomer is used, it cannot exhibit the performance as a rubber material. If even one component of the vulcanization accelerators (c) to (e) is missing, vulcanization will not take place, and if the amount of each component is less than the above, rapid vulcanization cannot be expected. On the other hand, if the blending amount of each component exceeds the above-mentioned amount, the storage stability and processing stability of the composition will be lost, which is not preferable. The composition of the present invention may contain various fillers, reinforcing agents, plasticizers, processing aids, etc., as commonly practiced in the art.
An acid acceptor, anti-aging agent, pigment, flame retardant, etc. can be optionally added. Particularly, from the viewpoint of thermal stability of the composition of the present invention, it is preferable to add a metal compound or an epoxy compound to serve as an acid acceptor. Such metal compounds include oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites of metals from group a of the periodic table, and oxidations of metals from group a of the periodic table. basic carbonates, basic carboxylates,
These include basic phosphites, basic sulfites, and tribasic sulfates. Specific examples include magnesia, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, quicklime, 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,
Examples include basic lead phosphite and basic lead sulfite. Examples of the epoxy compound include epoxidized soybean oil, a reaction product of bisphenol A and epichlorohydrin, and the like.
The amount of these acid acceptors added is 100% of the chlorine-containing polymer.
It is preferably 20 parts by weight or less. Known vulcanizing agents and vulcanization accelerators may also be added to the composition of the present invention. Examples include selenium, tellurium, thiazoles, dithiocarbamates, amines, etc. Specifically, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, -Zinc salt of mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, piperidine pentamethylene dithiocarbamate, zinc dimethyldithiocarbamate, tellurium dimethyldithiocarbamate, diphenylguanidine, reaction product of n-butyraldehyde and aniline, etc. Can be mentioned. 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 mixers, various kneaders, etc., can be used. The composition of the present invention usually has a temperature of 0.5 to
It can be made into a vulcanizate by heating for 120 minutes. Further, as a method of vulcanization molding, any method such as pressure molding using a mold, injection molding, steam can, air bath, or heating using infrared rays, microwaves, etc. can be used. Hereinafter, the present invention will be specifically explained with reference to Examples. Examples 1 to 5, Comparative Examples 1 and 2 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.
Pressure molding was carried out at 155°C and 80Kg/cm ³ for 30 minutes. Physical property tests were conducted on each of the obtained vulcanizates, and the results are shown in Table 2. Further, the vulcanization curves of the formulations of Example 5 and Comparative Examples 1 and 2 were measured using a JSR type cuelastrometer at an amplitude angle of 3° and 155°C, and the results are shown in FIG.

【table】

【table】

[Table] Example 6 Polyvinyl chloride* 100 parts by weight Calcium carbonate 100 parts by weight Dioctyl phthalate 70 parts by weight Dibutyltin malate 1 part by weight * "Zeon 103EP" manufactured by Nippon Zeon Co., Ltd. A mixture with the above ratio was heated in an open air at 150°C. 100 parts by weight of the mixture kneaded with a roll, 0.2 parts by weight of sulfur, 1 part by weight of tetramethylthiuram disulfide, 0.5 parts by weight of tetrabutylphosphonium bromide,
2 parts by weight of pentaerythritol and 3 parts by weight of calcium hydroxide were added and kneaded using open rolls at 100°C. The vulcanization curve of this compound was measured using a JSR model cuelastrometer at an amplitude angle of 3° and 170°C, and the results are shown in Figure 2.

[Brief explanation of the drawing]

FIG. 1 shows the vulcanization curves of Example 5 and Comparative Examples 1 and 2, and FIG. 2 shows the vulcanization curves of Example 6.

Claims (1)

[Scope of Claims] 1 (a) Chlorine-containing polymer (b) Sulfur and/or thiuram sulfides represented by the following general formula () or () and morpholine polysulfides represented by the following general formula () A sulfur-donating compound selected from (However, in general formulas () and (),
R ¹ , R ² , R ³ and R ⁴ are hydrocarbon residues having 1 to 4 carbon atoms. Moreover, a ₁ and a ₂ are integers of 1 to 6. In the general formula (), a ₃ is an integer from 1 to 6). (c) A quaternary salt selected from quaternary ammonium salts or quaternary phosphonium salts represented by the following general formula () and quaternary pyridinium salts represented by the following general formula () (However, in the general formula (), Z is N or P
and R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and are groups selected from alkyl groups having 1 to 17 carbon atoms, cyclohexyl groups, phenyl groups, and benzyl groups. In the general formula (), R ⁹ is selected from the same group as R ⁸ in the general formula (). Also, in the general formulas () and (),
X is a group selected from halogen and saturated or unsaturated monocarboxylic acids having 1 to 18 carbon atoms. ) (d) Polyhydric hydroxy compound selected from polyhydric alcohols and polyhydric phenols (e) Calcium hydroxide 0.1 to 10 parts of component (b) per 100 parts by weight of component (a) above.
1. A composition for vulcanizing a chlorine-containing polymer, characterized in that it contains 0.1 to 10 parts by weight of component (c), 0.1 to 15 parts by weight of component (d), and 0.5 to 20 parts by weight of component (e).