阅读说明：本技术 一种高含锡月桂酸硫醇逆酯甲基锡热稳定剂及其制备方法 (High-tin-content lauric acid reverse ester methyl tin mercaptan heat stabilizer and preparation method thereof ) 是由 陈树 易强顺 楚斌 徐万立 胡洋 李祥彦 刘莉 张权议 胡艳华 雷志豪 唐菲 于 2019-09-04 设计创作，主要内容包括：一种高含锡月桂酸硫醇逆酯甲基锡热稳定剂及其制备方法,所述稳定剂是由CH<Sub>3</Sub>Sn(SCH<Sub>2</Sub>CH<Sub>2</Sub>OOCC<Sub>11</Sub>H<Sub>23</Sub>)<Sub>3</Sub>、CH<Sub>3</Sub>SnS(SCH<Sub>2</Sub>CH<Sub>2</Sub>OOCC<Sub>11</Sub>H<Sub>23</Sub>)、(CH<Sub>3</Sub>SnS)<Sub>2</Sub>S、(CH<Sub>3</Sub>)<Sub>2</Sub>SnS、(CH<Sub>3</Sub>)<Sub>2</Sub>Sn(SCH<Sub>2</Sub>CH<Sub>2</Sub>OOCC<Sub>11</Sub>H<Sub>23</Sub>)SSn(CH<Sub>3</Sub>)<Sub>2</Sub>(SCH<Sub>2</Sub>CH<Sub>2</Sub>OOCC<Sub>11</Sub>H<Sub>23</Sub>)和(CH<Sub>3</Sub>)<Sub>2</Sub>Sn(SCH<Sub>2</Sub>CH<Sub>2</Sub>OOCC<Sub>11</Sub>H<Sub>23</Sub>)<Sub>2</Sub>组成的混合物。由月桂酸巯基逆酯、甲基氯化锡水溶液、硫化盐水溶液为主要原料反应制得。稳定剂无毒安全,润滑性较好,热稳定性能较优良。制备方法简单,反应条件温和,工艺易受控制,适于工业规模化批量生产。(a high-tin-content methyl tin methyl laurate thiolate stabilizer is a mixture of CH 3 Sn (SCH 2 CH 2 OOCC 11 H 23 ) 3 , CH 3 SnS (SCH 2 CH 2 OOCC 11 H 23 ), (CH 3 SnS) 2 S, (CH 3 ) 2 SnS, (CH 3 ) 2 Sn (SCH 2 CH 2 OOCC 11 H 23 ) SSn (CH 3 ) 2 (SCH 2 CH 2 OOCC 11 H 23 ) and (CH 3 ) 2 Sn (SCH 2 CH 2 OOCC 11 H 23 ) 2 .)

1. the high-tin-content lauric acid reverse ester methyl tin mercaptide heat stabilizer is characterized by comprising the following six substances:

CH₃Sn(SCH₂CH₂OOCC₁₁H₂₃)₃、(CH₃)₂Sn(SCH₂CH₂OOCC₁₁H₂₃)₂、(CH₃)₂Sn＝S、

2. The preparation method of the high-tin-content lauric acid reverse ester methyl tin mercaptide heat stabilizer as claimed in claim 1, which is characterized by comprising the following steps:

(1) Firstly, adding mercaptoethyl laurate and methyl tin chloride aqueous solution into a reactor, and starting stirring; the mass ratio of the mercaptoethyl laurate to the chloride ions in the methyl tin chloride aqueous solution is (0.4-0.7): 1;

(2) Slowly dripping a sulfide aqueous solution into the reactor for reaction to form Sn-S-Sn and Sn-S; wherein the matching coefficient of the mercaptoethyl laurate to the sulfide salt is (0.4-0.7): (0.7-0.4);

(3) Dropwise adding an alkali liquor into the reactor while dropwise adding a sulfide aqueous solution, neutralizing HCl released in the step (2) by reaction, controlling the reaction temperature within 35 ℃, and avoiding saponification until the pH value reaches 7-9;

(4) heating the materials in the reactor to 50-60 ℃ to promote the reaction to be complete, then stopping stirring, and standing for phase splitting;

(5) Taking the lower organic phase, adding pure water, washing with water under a stirring state, and then standing for phase splitting;

(6) and taking the lower organic phase for filtering, distilling under reduced pressure to remove water, and filtering again to finally obtain the high-tin-content lauric acid thiol reverse ester methyl tin heat stabilizer.

3. the method for preparing the high-tin-content lauric acid reverse mercaptan methyl tin heat stabilizer as claimed in claim 2, wherein the methyl tin chloride aqueous solution is a mixed aqueous solution consisting of methyl tin trichloride and dimethyl tin dichloride.

4. The method for preparing the high-tin-content lauric acid reverse ester methyl tin mercaptide heat stabilizer as claimed in claim 2, wherein the sulfide salt is Na₂S or K₂S。

5. The method for preparing the high-tin-content lauric acid reverse ester methyl tin thermal stabilizer according to claim 2, wherein the alkali liquor is ammonia water, NaOH aqueous solution or Na₂CO₃one in aqueous solution.

Technical Field

the invention belongs to the technical field of synthesis of organic tin heat stabilizers, and particularly relates to a high-tin-content lauric acid thiol reverse ester methyl tin heat stabilizer and a preparation method thereof.

Background

Methyl tin mercaptide is also called reverse ester type methyl tin mercaptide, and is a novel organic tin heat stabilizer developed in the last decade and used in the plastic processing process. The structure of the compound is different from that of the traditional methyl tin mercaptide, the sulfhydryl ester raw material-SH of the traditional methyl tin is connected with acid, and the sulfhydryl ester raw material-SH of the methyl tin mercaptide is connected with alcohol in the opposite positions. Due to the structural difference, the methyl tin mercaptide reverse ester not only has high-efficiency thermal stability, but also shows better lubricity, overcomes the defect of poor self-lubricity of the traditional methyl tin, and greatly expands the application field of the methyl tin, such as the fields of pipe materials, pipe fittings, sectional materials, CPVC (chlorinated polyvinyl chloride) processing and the like.

Currently, tin methyl mercaptide is receiving increasing attention from industry workers. The synthesis of tin mercaptide is researched by Li Jianfeng, Longgequai and the like, and a paper 'synthetic research on tin mercaptide as a PVC stabilizer' introduces a method for preparing tin mercaptide by taking methyl tin chloride, mercaptoethanol and oleic acid as raw materials, mainly researches on synthesis process conditions and esterification rate, and finally, the prepared product is the reverse ester type mercaptoethyl oleate methyl tin, has low tin content, smells smelly and pungent, has certain limitation on the thermal stability of the product, and causes application limitation. The patent CN201110393519.7 discloses a preparation method of reverse ester methyl tin mercaptide containing a sulfur bridge, the method comprises the steps of firstly preparing mercaptoethyl oleate by using oleic acid and mercaptoethanol, and then preparing reverse ester type mercaptoethyl oleate methyl tin containing the sulfur bridge by using the mercaptoethyl oleate, methyl tin chloride aqueous solution and sodium sulfide aqueous solution, wherein the content of tin in the obtained product is below 22%, the smell is sharp, and the method is not suitable for the fields of certain high-end PVC processing and CPVC processing. Patent CN201210297834.4 discloses a fatty acid mercaptoethanol ester methyl tin type heat stabilizer and a preparation method thereof, the reverse ester type methyl tin mercaptide prepared by the invention has wide raw material selectivity and wide application field, but is not applicable to the fields of high-end PVC processing and CPVC processing which require high tin content and good lubricity for some heat stabilizers.

disclosure of Invention

The invention aims to solve the defects of the prior art and provides the high-tin-content lauric acid thiol reverse ester methyl tin heat stabilizer which is non-toxic, safe, good in lubricating property, excellent in thermal stability, suitable for some high-end PVC processing and CPVC processing fields, simple in preparation method, mild in reaction condition, easy to control in process, easy in raw material obtaining and suitable for industrial large-scale batch production, and the preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

A high-tin-content lauric acid reverse ester methyl tin mercaptide heat stabilizer comprises the following six substances:

CH₃Sn(SCH₂CH₂OOCC₁₁H₂₃)₃、(CH₃)₂Sn(SCH₂CH₂OOCC₁₁H₂₃)₂、(CH₃)₂Sn＝S、And

The preparation method of the high-tin-content lauric acid reverse ester methyl tin mercaptide heat stabilizer comprises the following steps:

(1) Firstly, adding mercaptoethyl laurate and methyl tin chloride aqueous solution into a reactor, and starting stirring; the mass ratio of the mercaptoethyl laurate to the chloride ions in the methyl tin chloride aqueous solution is (0.4-0.7): 1;

The amount of a substance is mass/molar mass, and the ratio of the amounts of substances can express the relationship between the two substances more concisely;

(2) Slowly dripping a sulfide aqueous solution into the reactor for reaction to form Sn-S-Sn and Sn-S; wherein the matching coefficient of the mercaptoethyl laurate to the sulfide salt is (0.4-0.7): (0.7-0.4);

according to the invention, mercaptoethyl laurate and sulfide salt respectively react with methyltin chloride, the mass ratio of the mercaptoethyl laurate to the sulfide salt is the ratio, and the tin content of the final product can be adjusted by adjusting the ratio coefficient. For example, a mercaptoethyl laurate coefficient of 0.4 corresponds to a sulfide salt coefficient of 0.7;

(3) dropwise adding an alkali liquor into the reactor while dropwise adding a sulfide aqueous solution, neutralizing HCl released in the step (2) by reaction, controlling the reaction temperature within 35 ℃, and avoiding saponification until the pH value reaches 7-9;

(4) Heating the materials in the reactor to 50-60 ℃ to promote the reaction to be complete, then stopping stirring, and standing for phase splitting;

(5) Taking the lower organic phase, adding pure water, washing with water under a stirring state, and then standing for phase splitting;

(6) And taking the lower organic phase for filtering, distilling under reduced pressure to remove water, and filtering again to finally obtain the high-tin-content lauric acid thiol reverse ester methyl tin heat stabilizer.

the methyl tin chloride of the inventionThe aqueous solution is a mixed aqueous solution composed of monomethyltin trichloride and dimethyltin dichloride, and the types of the aqueous solution of the monomethyltin chloride can be 10/90, 20/80, 30/70, 40/60, 50/50, 60/40, 70/30, 80/20 and 90/10. The sulfide salt is Na₂s or K₂And S. The alkali liquor is ammonia water, NaOH aqueous solution and Na₂CO₃One in aqueous solution.

The reaction equation of the preparation method of the invention is as follows:

CH₃SnCl₃+3RSH→CH₃Sn(SR)₃+3HCl (1)；

(CH₃)₂SnCl₂+2RSH→(CH₃)₂Sn(SR)₂+2HCl (2)；

2CH₃SnCl₃+3Na₂S→(CH₃SnS)₂S+6NaCl (5)

(CH₃)₂SnCl₂+Na₂S→(CH₃)₂SnS+2NaCl (6)

HCl + lye → chloride + H₂O (7)

In the above formulae (1) to (6): r is C₁₁H₂₃COOCH₂CH₂-。

The invention provides a high-tin-content lauric acid reverse ester methyl mercaptan tin heat stabilizer which is prepared from CH₃Sn(SCH₂CH₂OOCC₁₁H₂₃)₃、CH₃SnS(SCH₂CH₂OOCC₁₁H₂₃)、(CH₃SnS)₂S、(CH₃)₂SnS、(CH₃)₂Sn(SCH₂CH₂OOCC₁₁H₂₃)SSn(CH₃)₂(SCH₂CH₂OOCC₁₁H₂₃) And (CH)₃)₂Sn(SCH₂CH₂OOCC₁₁H₂₃)₂The product structure of the formed mixture is different from that of the methyl tin mercaptide stabilizer with the traditional structure, and the mixture is of a reverse ester mercaptide type, and has good self-lubricating property and excellent thermal stability. The tin content can be adjusted according to requirements by controlling the type of the methyl tin chloride aqueous solution and the proportion of the mercaptoethyl laurate to the sulfide salt, and can reach 20-30 percent, which is higher than the traditional methyl tin by 19 percent.

The high-tin-content lauric acid reverse mercaptan methyl tin heat stabilizer provided by the invention is non-toxic and safe, has better lubricating property and excellent heat stability, and is suitable for the fields of high-end PVC processing and CPVC processing. In the fields with lower requirements, the high-tin-content lauric acid reverse ester methyl tin mercaptide heat stabilizer provided by the invention can be compounded with other plastic processing aids to reduce the tin content, the heat stability of the compounded product is superior to that of the traditional methyl tin with the same tin content, and the production cost is greatly reduced. The stabilizer of the invention has better application prospect in both high-tin field and low-tin field. The preparation method of the stabilizer is simple, mild in reaction condition, easy in process control, easy in raw material obtaining and suitable for industrial large-scale batch production.

Detailed Description

The present invention is further illustrated by the following examples.