CN1435416A - Dimercaptoacetate isooctyl ester dimethoxy-carbonylethyl-tin and preparing process thereof - Google Patents

Abstract

An isooctyl dimercaptoacetate-dimethoxycarbonyl ethyltin compound used as the optical and thermal stabilizer of haloethylene resin is disclosed. Its advantages are high effect on preventing high-temp color variation of haloethylene resin, and low cost.

Description

Dimercaptoacetic acid isooctyl ester dimethoxy-carbonyl ethyl tin compound and preparation method thereof

The technical field is as follows: the present invention relates to a vinyl halide resin, particularly to a PVC light and heat stabilizer.

Background art: currently, when vinyl halide resins and compositions containing vinyl halide resins are converted into products, the products are formed by thermoforming by heating to soften or melt the resin, i.e., converting a powdery resin composition into a molten mass, which is then extruded into a desired shape. In this process, heat is generated by friction occurring in the compound, and the amount of heat required to soften the vinyl halide resin composition varies depending on the composition, but is generally between 165 ℃ and 210 ℃. In order to solve the problems that vinyl halide resins degrade at temperatures higher than 100 ℃, which leads to discoloration and loss of physical properties of vinyl halides, and even blackening and embrittlement, which are not practical, various attempts have been made, such as U.S. Pat. No. 33919168 disclosing an organotin mercaptide, which is a highly efficient heat stabilizer for vinyl halide resins, such sulfur-containing organotin species having at least one organic group directly bonded to tin through a carbon atom and at least one sulfur atom bonded to tin alone, or a sulfur-containing group residue bonded to tin through a sulfur atom, and both sulfur units bonded to the organotin moiety and the sulfur-containing moiety residue can be bonded to the same organotin moiety. The heat stabilizer can ensure that the vinyl halide resin does not change color when meeting high temperature, but has the problems of high product cost and low raw material source, so the heat stabilizer is not suitable.

The invention comprises the following steps: overcomes the defects of the prior art and provides a vinyl halide resin, in particular a light and heat stabilizer of PVC, a dimercaptoacetic acid isooctyl ester dimethoxycarbonylethyltin compound and a preparation method thereof. The compound of dimercaptoacetic acid isooctyl ester dimethoxy carbonyl ethyl tin has the following structural formula:

the preparation process comprises the following steps: taking 3 parts of ethanol, 3 parts of concentrated hydrochloric acid, 2 parts of sodium chloride, 50 parts of C7-C8 fatty alcohol, 50 parts of metallic tin, 2 parts of hydrogen chloride, 3 parts of methyl acrylate, 3 parts of thioglycolic acid, 3 parts of benzene, 3 parts of chloroacetic acid-2-ethyl isooctanol, 2 parts of ionic resin, 2 parts of toluene, 2 parts of carbonate, 2 parts of sodium thiosulfate and a proper amount of water. a, preparation of dichlorodimethoxycarbonylethyltin compound: 1, adding metered methyl acrylate, water and a catalyst into a container with a stirrer, a reflux condenser and a gas conduit, keeping the reaction temperature between 10 and 60 ℃, gradually adding metallic tin powder under vigorous stirring, and simultaneously introducing dry hydrogen chloride through the gas conduit for reaction for about 3 to 30 hours. 2, after the metallic tin powder is completely reacted, evacuating and filtering the filtrate to obtain a white solid, wherein the white solid comprises the following components: dichloro (phenyl) methaneDimethoxycarbonylethyl tin and a small amount of trichloromonomethoxycarbonylethyl tin, then washing off the trichloromonomethoxycarbonylethyl tin compound by using benzene or toluene or other solvents, and then filtering and drying to obtain the dichlorodimethoxycarbonylethyl tin compound. b, preparing isooctyl thioglycolate, which comprises the following steps: catalyzing and esterifying chloroacetic acid-2-ethylhexanol by using chloroacetic acid-2-ethylhexanol to generate chloroacetic acid-2-ethanol ester, then reacting the chloroacetic acid-2-ethylhexanol with sodium thiosulfate in an ethanol-water solution to generate bunt salt, and acidifying, hydrolyzing and reducing the bunt salt to obtain mercaptoacetic acid-2-ethylhexanol by using the following reaction formula:

adding metered chloroacetic acid-2-ethylhexanol, a reaction solvent and a small amount of concentrated hydrochloric acid into a reaction kettle, heating and refluxing, continuously removing water generated in the reaction process through a water separator until water is not generated any more, distilling and recovering the solvent, neutralizing with a 2% sodium carbonate solution after cooling, washing with a saturated sodium chloride solution, drying with calcium chloride, distilling and collecting, and obtaining the chloroacetic acid-2-ethylhexyl ester at the temperature of 236-238 ℃. Adding the prepared chloroacetic acid-2-ethylhexyl ester into another reaction kettle, adding metered sodium thiosulfate, water and water-miscible C2-C7 fatty alcohol, heating and refluxing under stirring to react to form a homogeneous phase, continuing to react for 20 minutes, distilling and recovering the fatty alcohol, adding concentrated hydrochloric acid, heating to 90-95 ℃, stirring for 30 minutes, cooling to 25-30 ℃, adding excessive zinc powder under stirring in batches, maintaining the reaction temperature at 40-50 ℃, and reactingFiltering, standing for 1-5 hr, separating phases, washing organic phase with saturated sodium chloride solution, drying, vacuum distilling, collecting at 125-130 deg.C/1 and 6 × 10³Pa, and distilling to obtain the isooctyl thioglycolate. c, preparing dimethylene glycol dimethyl ether carbonyl ethyl tin dimercaptoacetate isooctyl ester, adding metered dichlorodimethoxycarbonyl ethyl tin, isooctyl ether thioglycolate, water, solvent and carbonate into a reaction kettle with a stirrer, a thermometer and a reflux condenser, controlling the reaction temperature to be 40-90 ℃, and then adding carbonate for reactionAnd (3) adjusting the pH value for 2-16 hours, and finishing the reaction. Cooling, filtering, standing for 30-60 min, separating out organic phase, washing with water, dewatering, and rectifying to obtain light yellow colorless liquid.

The inventive dimercaptoacetic acid isooctyl ester dimethoxy carbonyl ethyl tin compound can be used as heat stabilizer and light stabilizer of vinyl halide resin, which is effective for controlling the color change of vinyl halide resin at high temperature, without affecting the processing property, and keeping the original physical property, to make the product nontoxic and tasteless, and meet the requirement of environmental protection; meanwhile, the product has low cost, simple processing technology, wide material source and easy popularization and application.

Embodiment mode 1: taking ethanol 3KG, concentrated hydrochloric acid 3KG, sodium chloride 2KG, C7-C8 fatty alcohol 50KG, metal tin 50KG, hydrogen chloride 2KG, methyl acrylate 3KG, dimercaptoacetic acid 3KG, benzene 3KG, chloric acid isooctanol 3KG, ionic resin 2KG, toluene 2KG, carbonate 2KG, sodium thiosulfate 2KG, and a proper amount of water. Wherein, the ion resin can be 732 cation resin, and the carbonate can be sodium salt such as sodium carbonate, bicarbonate; it can also be potassium salt, magnesium salt, and calcium salt. a, preparation of dichlorodimethoxycarbonylethyltin compound: 1, adding metered methyl acrylate, water and a catalyst into a container with a stirrer, a reflux condenser and a gas conduit, keeping the reaction temperature between 10 and 60 ℃, gradually adding metallic tin powder under vigorous stirring, and simultaneously introducing dry hydrogen chloride through the gas conduit for reaction for about 3 to 30 hours. 2, after the metallic tin powder is completely reacted, evacuating and filtering the filtrate to obtain a white solid, wherein the white solid comprises the following components: dichlorodimethoxycarbonylethyl tin and a small amount of trichloromonomethoxycarbonylethyl tin, washing with benzene or toluene or other solvent to remove trichloromonomethoxycarbonylethyl tin compound, filtering, and drying to obtain dichlorodimethyltinAn oxycarbonylethyltin compound. b, preparing isooctyl thioglycolate, which comprises the following steps: esterifying chloroacetic acid-2-ethylhexanol with acid to obtain chloroacetic acid-2-ethanol ester, reacting with sodium thiosulfate in the aqueous solution of ethanol to obtain bunt salt, acidifying, hydrolyzing,Reducing to obtain thioglycolic acid-2-ethyl hexyl ester, wherein the reaction formula is as follows:

adding metered chloroacetic acid, 2-ethylhexanol, a reaction solvent and a small amount of concentrated hydrochloric acid into a reaction kettle, heating and refluxing, continuously removing water generated in the reaction process through a water separator until water is not generated any more, distilling and recovering the solvent, neutralizing with a 2% sodium carbonate solution after cooling, washing with a saturated sodium chloride solution, drying with calcium chloride, distilling and collecting, and obtaining the chloroacetic acid-2-ethylhexyl ester at the temperature of 236-238 ℃. Adding the prepared chloroacetic acid-2-ethylhexyl ester into another reaction kettle, adding metered sodium thiosulfate, water and water-miscible C2-C7 fatty alcohol, heating and refluxing to react under stirring to form a homogeneous phase, continuing to react for 20 minutes, distilling and recovering the fatty alcohol, adding concentrated hydrochloric acid, heating to 90-95 ℃, stirring for 30 minutes, coolingto 25-30 ℃, adding excessive zinc powder in batches under stirring, maintaining the reaction temperature at 40-50 ℃, reacting for 1 and 5 hours, filtering, statically separating phases, washing an organic phase with a saturated sodium chloride solution, drying, distilling under reduced pressure, collecting, distilling at 125-130 ℃/1 and 6 x 10℃, collecting³Pa, and distilling to obtain the isooctyl thioglycolate. c, preparing the dimercaptoacetic acid isooctyl ester dimethoxy carbonyl ethyl tin, adding metered dichlorodimethoxy carbonyl ethyl tin, mercaptoacetic acid isooctyl ester, water and a solvent into a reaction kettle with a stirrer, a thermometer and a reflux condenser, controlling the reaction temperature to be 40-90 ℃, then adding carbonate, reacting for 2-16 hours, adjusting the pH value, and finishing the reaction. Cooling, filtering, standing for 30-60 min, separating out organic phase, washing with water, dewatering, and rectifying to obtain light yellow colorless liquid.

Claims (2)

1. The compound of dimercaptoacetic acid isooctyl ester dimethoxycarbonyl ethyl tin is characterized in that: has the following structural formula:

2. the method for preparing the compound of dimercaptoacetic acid, isooctyl ester, dimethoxy-carbonylethyl-tin as claimed in claim 1, wherein: taking 3 parts of ethanol, 3 parts of concentrated hydrochloric acid, 2 parts of sodium chloride, 50 parts of C7-C8 fatty alcohol, 50 parts of metallic tin, 2 parts of hydrogen chloride, 3 parts of methyl acrylate, 3 parts of dimercaptoacetic acid, 3 parts of benzene, 3 parts of chloric acid isooctanol, 2 parts of ionic resin, 2 parts of toluene, 2 parts of carbonate, 2 parts of sodium thiosulfate and a proper amount of water. a, preparation of dichlorodimethoxycarbonylethyltin compound: 1, adding metered methyl acrylate, water and a catalyst into a container with a stirrer, a reflux condenser and a gas conduit, keeping the reaction temperature between 10 and 60 ℃, gradually adding metallic tin powder under vigorous stirring, and simultaneously introducing dry hydrogen chloride through the gas conduit for reaction for about 3 to 30 hours. 2, after the metallic tin powder is completely reacted, evacuating and filtering the filtrate to obtain a white solid, wherein the white solid comprises the following components: dichlorodimethoxycarbonylethyl tin and a small amount of trichloromonomethoxycarbonylethyl tin, then washing off the trichloromonomethoxycarbonylethyl tin compound by using benzene or toluene or other solvents, and then filtering and drying to obtain the dichlorodimethoxycarbonylethyl tin compound. b, preparing isooctyl thioglycolate, which comprises the following steps: catalyzing and esterifying chloroacetic acid and 2-ethylhexanol by acid to generate chloroacetic acid-2-ethanol ester, then reacting with sodium thiosulfate in an ethanol-water solution to generate bunt salt, acidifying, hydrolyzing and reducing the bunt salt to obtain thioglycolic acid-2-ethylhexanol, wherein the reaction formula is as follows:

adding metered chloroacetic acid-2-ethylhexanol, a reaction solvent and a small amount of concentrated hydrochloric acid into a reaction kettle, heating and refluxing, continuously removing water generated in the reaction process through a water separator until water is not generated any more, distilling and recovering the solvent, neutralizing with a 2% sodium carbonate solution after cooling, washing with a saturated sodium chloride solution, drying with calcium chloride, distilling and collecting, and obtaining the chloroacetic acid-2-ethylhexyl ester at the temperature of 236-238 ℃. Adding the prepared chloroacetic acid-2-ethylhexyl ester into another reaction kettle, adding metered sodium thiosulfate, water and water-miscible C2-C7 fatty alcohol, heating and refluxing under stirring to react to form a homogeneous phase, continuing to react for 20 minutes, distilling and recovering the fatty alcohol, adding concentrated hydrochloric acid, heating to 90-95 ℃, stirring for 30 minutes, cooling to 25-30 ℃, adding excessive zinc powder in batches under stirring, maintaining the reaction temperature at 40-50 ℃, reacting for 1 and 5 hours, filtering, standing for phase separation, washing an organic phase with a saturated sodium chloride solution, drying, distilling under reduced pressure, collecting, distilling at 125-130 ℃/1 and 6/10Pa, and distilling to obtain isooctyl thioglycolate. C, preparing the dimethylene dimethoxy carbonyl ethyl tin dimercaptoacetate isooctyl ester, adding metered dichlorodimethoxycarbonyl ethyl tin, isooctyl thioglycolate, water and a solvent into a reaction kettle with a stirrer, a thermometer and a reflux condenser, controlling the reaction temperature to be 40-90 ℃, then adding carbonate, reacting for 2-16 hours, adjusting the pH value, and finishing the reaction. Cooling, filtering, standing for 30-60 min, separating out organic phase, washing with water, dewatering, and rectifying to obtain light yellow colorless liquid.