CN102863467B - A kind of preparation method of high tin high-sulfur thiol methyl tin product - Google Patents
A kind of preparation method of high tin high-sulfur thiol methyl tin product Download PDFInfo
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- CN102863467B CN102863467B CN201210313163.6A CN201210313163A CN102863467B CN 102863467 B CN102863467 B CN 102863467B CN 201210313163 A CN201210313163 A CN 201210313163A CN 102863467 B CN102863467 B CN 102863467B
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Abstract
The present invention relates to a kind of high tin high-sulfur thiol methyl tin preparation method, belong to organotin deep process technology field.Technical solution of the present invention is: first isooctyl mercaptoacetate is put into reactor, the sulfosalt aqueous solution, the methyl chloride tin aqueous solution and basic solution neutralizing agent is dripped again in the ratio of complete reaction, synthesize high tin high-sulfur thiol methyl tin, the volumetric molar concentration ratio of sulfosalt and methyl chloride tin is 1:5 ~ 2:5, temperature of reaction is 20 ~ 40 DEG C, pH value in reaction process is 5.0 ~ 7.0, and the pH value of reaction end is 8.0 ~ 9.0.The molecular weight of the PVC heat stabilizer that present method obtains is large, good stability, and plastic working industry user can be made to reduce environmental pollution in the PVC course of processing.
Description
Technical field
The present invention relates to a kind of high tin high-sulfur thiol methyl tin preparation method, belong to organotin deep process technology field.
Technical background
Thermo-stabilizer is mainly used in the processing of polyvinyl chloride (PVC) and other chloride polymkeric substance.In polyvinyl chloride reprocessing process, just start there is slight degraded when 100 DEG C, when 150 DEG C, degraded aggravation, releases degradation product hydrogen chloride gas.If do not suppress the generation of hydrogenchloride, decomposing can aggravation further.Due to the singularity of PVC structure, inevitably decompose at processing temperatures, make to darken, physical and mechanical properties declines, and even loses use value.Thermo-stabilizer is just in order to head it off is researched and developed.According to the difference of chemical structure, thermo-stabilizer is mainly divided into lead salts, metal soap, organic tin, rare earth class, antimony organic class and organic auxiliary stabilizer etc.In recent years, because PVC industrial development is very fast, environmental requirement is more and more tighter, has driven developing rapidly of methyl tin heat stabilizer industry thus.Existing organo-tin het stabilizer is due to molecular weight, easily evaporate in air at plastic working temperature, cause environmental pollution and affect the healthy of workman, and the thiol methyl tin of high tin high-sulfur is under specific processing condition, sodium sulphite and methyl chloride tin react and form Sn-S key, in system, lengthen reaction chain, thus generate the thiol methyl tin of macromolecular high tin high-sulfur, effectively can suppress the degraded in the polyvinyl chloride course of processing, become " cleaning " type product of odorless.
Summary of the invention
The object of this invention is to provide a kind of preparation method of high tin high-sulfur thiol methyl tin product, its molecular weight be large, good stability, plastic working industry user can be made to reduce environmental pollution in the PVC course of processing.
Realizing the technical scheme that order of the present invention takes is: first isooctyl mercaptoacetate is put into reactor, the sulfosalt aqueous solution, the methyl chloride tin aqueous solution and basic solution neutralizing agent is dripped again in the ratio of complete reaction, synthesize high tin high-sulfur thiol methyl tin, the volumetric molar concentration ratio of sulfosalt and methyl chloride tin is 1:5 ~ 2:5, temperature of reaction is 20 ~ 40 DEG C, pH value in reaction process is 5.0 ~ 7.0, and the pH value of reaction end is 8.0 ~ 9.0.
The sulfosalt aqueous solution of the present invention is sodium sulphite, potassium sulphide or ammonium sulfide; Basic solution neutralizing agent is sodium hydroxide, sodium carbonate or ammoniacal liquor.
The sulfosalt aqueous solution and methyl chloride tin enter in reactor after mixing dropwise reaction to react again; Or the sulfosalt aqueous solution and methyl chloride tin are added drop-wise to respectively in reactor and react.
The invention has the beneficial effects as follows: under specific processing condition, sodium sulphite and methyl chloride tin react and form Sn-S key, reaction chain is lengthened in system, thus generate the thiol methyl tin of macromolecular high tin high-sulfur, effectively can suppress the degraded in the polyvinyl chloride course of processing, become " cleaning " type product of odorless.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Below use the embodiment that three concrete, further illustrate the present invention.
embodiment 1
In the reactor that electric stirring, thermometer, three dropping funnels are housed, add 55.72g isooctyl mercaptoacetate, stir, cool temperature control; The aqueous solution of 22.56g sodium sulphite, the 100g methyl chloride tin aqueous solution, 28.53g ammoniacal liquor are joined in three dropping funnels respectively, first sodium sulfide solution, the methyl chloride tin aqueous solution are slowly added drop-wise in triangular funnel to mix and drip in reactor again, then start to drip ammoniacal liquor, temperature of reaction 25 DEG C ~ 35 DEG C is controlled well in whole process, control well between ph value of reaction 5 ~ 7, dropwise rear dropping ammoniacal liquor to sodium sulfide solution, the methyl chloride tin aqueous solution pH value is transferred to 8.0, reaction completes.Stir and start to be warming up to 50 DEG C after 0.5 hour, insulated and stirred stops after 1 hour to stir standing phase-splitting, separates organic phase.Organic phase is filtered, water-bath underpressure distillation, and refilter and obtain limpid transparent oily liquid 80.8 Ke Gaoxi high-sulfur thiol methyl tin product, direct yield (by Sn) is 92.72%.Product index Sn:26.08%, S:14.43%.
embodiment 2
In the reactor that electric stirring, thermometer, three dropping funnels are housed, add 73.3g isooctyl mercaptoacetate, stir, cool temperature control; The aqueous solution of the aqueous solution of 15.91g potassium sulphide, the 100g methyl chloride tin aqueous solution, 19.31 grams of sodium hydroxide is joined in three dropping funnels respectively, first sodium sulfide solution, the methyl chloride tin aqueous solution are slowly added drop-wise in triangular funnel to mix and drip in reactor again, then start to drip ammoniacal liquor, temperature of reaction 25 DEG C-35 DEG C is controlled well in whole process, control well between pH value in reaction 5-7, slowly drip ammoniacal liquor after dropwising to sodium sulfide solution, the methyl chloride tin aqueous solution pH value is transferred to 8.0, reaction completes.Stir and start to be warming up to 50 DEG C after 0.5 hour, insulated and stirred stops after 1 hour to stir standing phase-splitting, separates organic phase.Organic phase is filtered, water-bath underpressure distillation, and refilter and obtain limpid transparent oily liquid 99.86 grams (high tin high-sulfur thiol methyl tin), direct yield (by Sn) is 94.92%.Product index Sn:25.18%, S:15.16%.
embodiment 3
In the reactor that electric stirring, thermometer, three dropping funnels are housed, add 73.3g isooctyl mercaptoacetate, stir, cool temperature control; The aqueous solution of the aqueous solution of 9.83g ammonium sulfide, the 100g methyl chloride tin aqueous solution, 25.58 grams of sodium carbonate is joined in three dropping funnels respectively, first sodium sulfide solution, the methyl chloride tin aqueous solution are slowly added drop-wise in triangular funnel to mix and drip in reactor again, then start to drip ammoniacal liquor, temperature of reaction 25 DEG C-35 DEG C is controlled well in whole process, control well between pH value in reaction 5-7, slowly drip ammoniacal liquor after dropwising to sodium sulfide solution, the methyl chloride tin aqueous solution pH value is transferred to 8.0, reaction completes.Stir and start to be warming up to 50 DEG C after 0.5 hour, insulated and stirred stops after 1 hour to stir standing phase-splitting, separates organic phase.Organic phase is filtered, water-bath underpressure distillation, and refilter and obtain limpid transparent oily liquid 99.86 grams (high tin high-sulfur thiol methyl tin), direct yield (by Sn) is 94.92%.Product index Sn:25.18%, S:15.16%.
Claims (1)
1. the preparation method of one kind high tin high-sulfur thiol methyl tin, it is characterized in that: first isooctyl mercaptoacetate is put into reactor, the sulfosalt aqueous solution, the methyl chloride tin aqueous solution and basic solution neutralizing agent is dripped again in the ratio of complete reaction, synthesize high tin high-sulfur thiol methyl tin, the volumetric molar concentration ratio of sulfosalt and methyl chloride tin is 1:5 ~ 2:5, temperature of reaction is 20 ~ 40 DEG C, and the pH value in reaction process is 5.0 ~ 7.0, and the pH value of reaction end is 8.0 ~ 9.0;
Sulfosalt is sodium sulphite, potassium sulphide or ammonium sulfide; Basic solution neutralizing agent is sodium hydroxide, sodium carbonate or ammoniacal liquor;
The sulfosalt aqueous solution and methyl chloride tin enter in reactor after mixing dropwise reaction to react again.
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| CN102863467B true CN102863467B (en) | 2016-02-17 |
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| CN109912643B (en) * | 2019-04-04 | 2021-09-03 | 中国人民解放军61699部队 | Method for controlling feeding amount of acid remover in condensation reaction process of methyl tin mercaptide |
| CN111849031B (en) * | 2020-06-30 | 2022-01-18 | 湖北犇星新材料股份有限公司 | High-tin-content powder mercaptan organotin stabilizer and preparation method thereof |
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| US4120845A (en) * | 1974-07-26 | 1978-10-17 | Cincinnati Milacron Chemicals, Inc. | Sulfide containing tin stabilizers |
| CN102079755A (en) * | 2010-11-29 | 2011-06-01 | 杭州天道实业有限公司 | Preparation method of methyl tin heat stabilizer |
| CN102516289A (en) * | 2011-11-22 | 2012-06-27 | 湖北南星化工总厂 | Preparation method of sulfur bridge-containing reverse ester thiol methyltin |
| CN102532188A (en) * | 2011-12-26 | 2012-07-04 | 湖北犇星化工有限责任公司 | Sulfo (bonding) isooctyl thioglycolate tin, and preparation method and application thereof |
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Patent Citations (5)
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|---|---|---|---|---|
| US4120845A (en) * | 1974-07-26 | 1978-10-17 | Cincinnati Milacron Chemicals, Inc. | Sulfide containing tin stabilizers |
| US4120845B1 (en) * | 1974-07-26 | 1990-01-09 | Thiokol Morton Inc | |
| CN102079755A (en) * | 2010-11-29 | 2011-06-01 | 杭州天道实业有限公司 | Preparation method of methyl tin heat stabilizer |
| CN102516289A (en) * | 2011-11-22 | 2012-06-27 | 湖北南星化工总厂 | Preparation method of sulfur bridge-containing reverse ester thiol methyltin |
| CN102532188A (en) * | 2011-12-26 | 2012-07-04 | 湖北犇星化工有限责任公司 | Sulfo (bonding) isooctyl thioglycolate tin, and preparation method and application thereof |
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Effective date of registration: 20200225 Address after: 661099 Metallurgical Material Development Zone, Mengzi economic and Technological Development Zone, Honghe Prefecture, Honghe Hani and Yi Autonomous Prefecture, Yunnan Province Patentee after: Yunnan Tin Industry Tin Chemical Materials Co., Ltd. Address before: 661000 121 Jinhu East Road, Gejiu City, Honghe Hani and Yi Autonomous Prefecture, Yunnan (Yunnan tin industry Limited by Share Ltd) Patentee before: YUNNAN TIN Co.,Ltd. |