Thiadiazoles derivative for halopolymer vulcanization crosslinking and synthetic method for the same

Abstract

A thiobiazole derivative containing halogen polymer for vulcanized cross-linking and its synthesis are disclosed. The process is carried out by taking DMTD, metal strong alkaline and acyl halide as raw materials, taking ethanol solution as composite solvent, taking concentrated inorganic acid as acidifying reagent, and synthesizing selectively to obtain final product. It costs low and is simple, convenient, and controllable. It has less consumption, short flow path and no use for oxidant.

Description

Technical field [0001] The present invention relates to a thiadiazole derivative and a synthesis method thereof, in particular to a thiadiazole derivative of structural formula (1) or (2) that can be used for vulcanization and crosslinking of halogen-containing polymers, especially halogen-containing rubber, and a synthesis method thereof . [0002] [0003] Among them: the R group in the above structural formula is: aromatic or C 1-17 alkyl. Background technique [0004] Halogen-containing polymers include halogen-containing rubber, halogen-containing plastics, rubber-plastic blending materials, etc. Among them, halogen-containing rubber is an important part of special rubber. The main varieties are: chlorinated polyethylene rubber (CPE, CM), neoprene (CR), chloroether rubber (CO), epichlorohydrin rubber (ECO), chlorosulfonated polyethylene rubber (CSM), polyvinyl chloride (PVC), chloroprene rubber, CPE / PVC, IIR (brominated Butyl rubber), polyacrylate rubber, etc. Because halo...

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Problems solved by technology

Foreign countries have also started research on the vulcanization of halogen-containing rubber very early. Hercules Corporation of the United States has developed mercaptothiadiazole compounds, and Nakamura and others in Japan have developed trimercaptotriazine derivatives for the crosslinking of halogen-containing rubber. Both vulcanizing agents have disadvantages: although the vulcanization speed of mercaptothiadiazole compound is fast, the anti-scorch performance is not good, and the vulcanization speed of trimercaptotriazine compound is too slow

However, the use of oxidizing agents (hydrogen peroxide) in the production of this type of vulcanizing agent increases the danger in the production process, and due to the use of oxidizing agents, the mercapto groups of 2,5-dimercapto-1,3,4-thiadiazole (DMTD) It is easy to be oxidized to dimer or polymer compound. The viscosity of the product is very high during post-treatment, which is not conducive to the separation and purification of the product. The yield of the product is very low or even the target product cannot be obtained. The conditions for the reaction are strict. A slight difference in the process will generate a large amount of resinous by-products, making the post-processing of the product very difficult, which is not conducive to the realization of industrialization

[0011] 2. In U.S. Patent No. 5,849,925, it is introduced that a compound of structural formula (4) can also be used for vulcanization and crosslinking of halogen-containing rubber, but this type of compound also needs to use an oxidant during production, and the control of reaction conditions is also required Relatively strict, not conducive to the realization of industrialization

[0013] 3. In Chinese patent 200610004725.3, a novel compound of structural formula (5) is introduced: bis-DMTD, which is a derivative of DMTD, can be used in lubricating oil as an extreme pressure and anti-wear additive, but has not yet been seen There are reports that bis-DMTD can be used as a vulcanizing agent in halogenated rubber

[0015] 4. In Japanese Patent Laid-Open No. 61-238,838 (1986), a compound of structural formula (6) was reported: poly 2,5-dimercapto-1,3,4-thiadiazole, which can be used to vulcanize halogen-containing rubber , such as chlorinated polyethylene rubber (CPE, CM), chloroprene rubber (CR), epichloroether rubber (EGO) used as a vulcanizing agent works well, but in this patent it is introduced to produce poly 2,5-di For mercapto-1,3,4-thiadiazole, an oxidizing agent (hydrogen peroxide) should be selected. If the speed is too fast during the addition of hydrogen peroxide, the reaction will be intense and exothermic. The reaction temperature is not easy to control, and it is easy to generate a large amount of yellow floc matter, which affects the yield of the product, so this method is also unfavorable for realizing industrialization

[0017] 5. In Japanese Patent Laid-Open No. 54-58,750 (1979), it was mentioned that 2,5-dimercapto-1,3,4-thiadiazole can be used for vulcanization and crosslinking of chlorinated polyethylene (CPE) rubber, but rubber The overall performance of the product is poor

[0018] 6. Eurpat Appl.Ep78,155 (1983) reported that polymercapto compounds-thiadiazoles can be used for vulcanization and crosslinking of chlorinated polyethylene rubber (CPE), but did not introduce the production of mercapto-thiadiazoles method

[0023] In a word, there are no reports or studies on the industrial production of thiadiazole derivatives used for vulcanization and crosslinking of halogen-containing polymers in China so far.

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