CN113980046A - Preparation method of high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer - Google Patents
Preparation method of high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer Download PDFInfo
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- CN113980046A CN113980046A CN202111363125.7A CN202111363125A CN113980046A CN 113980046 A CN113980046 A CN 113980046A CN 202111363125 A CN202111363125 A CN 202111363125A CN 113980046 A CN113980046 A CN 113980046A
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- -1 isooctyl monomethyltrimercaptoacetate tin Chemical compound 0.000 title claims abstract description 34
- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 59
- 238000005191 phase separation Methods 0.000 claims description 23
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 17
- 239000012074 organic phase Substances 0.000 claims description 16
- JHHJZXAFNAJSCA-UHFFFAOYSA-N methyl(oxo)tin Chemical compound C[Sn]=O JHHJZXAFNAJSCA-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- PTKKDFBMUZCTDJ-UHFFFAOYSA-N [Sn].SCC(=O)OCCCCCC(C)C Chemical compound [Sn].SCC(=O)OCCCCCC(C)C PTKKDFBMUZCTDJ-UHFFFAOYSA-N 0.000 claims 2
- RZBBHEJLECUBJT-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS RZBBHEJLECUBJT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 22
- 239000007787 solid Substances 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- OMIJTRCJFMNALR-UHFFFAOYSA-N methoxymethane;tin Chemical compound [Sn].COC OMIJTRCJFMNALR-UHFFFAOYSA-N 0.000 description 7
- ABSPNAAFFZPAFF-UHFFFAOYSA-O CC(C)CCCCCOC(C(S)[S+](C)C)=O.[Sn] Chemical compound CC(C)CCCCCOC(C(S)[S+](C)C)=O.[Sn] ABSPNAAFFZPAFF-UHFFFAOYSA-O 0.000 description 6
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 4
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- SUESAPXHZISTMR-UHFFFAOYSA-N SC(C(=O)OCCCCCC(C)C)S Chemical compound SC(C(=O)OCCCCCC(C)C)S SUESAPXHZISTMR-UHFFFAOYSA-N 0.000 description 3
- NJURIYSLCWOESR-UHFFFAOYSA-L SC(C(=O)[O-])S.C[Sn+2]C.SC(C(=O)[O-])S Chemical compound SC(C(=O)[O-])S.C[Sn+2]C.SC(C(=O)[O-])S NJURIYSLCWOESR-UHFFFAOYSA-L 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2296—Purification, stabilisation, isolation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A preparation method of a high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer is characterized in that a methyltin chloride aqueous solution, an alkali liquor and isooctyl mercaptoacetate are used as reaction raw materials and are prepared by two steps, wherein dimethyl tin dichloride in the methyltin chloride aqueous solution is removed firstly, and then the isooctyl monomethyltrimercaptoacetate tin heat stabilizer is prepared secondly. The method disclosed by the invention is mild in reaction conditions, simple and convenient to operate and high in conversion rate, and can be used for preparing the high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer with the purity of 90-99.5%, and the product quality is stable.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic tin heat stabilizers, and particularly relates to a preparation method of a high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer.
Background
The methyl tin mercaptide heat stabilizer is a chemical product with the best performance in an organic tin heat stabilizer, is widely applied to various products such as PVC extrusion, calendering, blow molding, injection molding and the like, has excellent initial colorability, transparency and thermal stability, and is a key auxiliary agent in the PVC plastic processing process. The preparation method generally comprises the following steps: the tin metal simple substance is subjected to alkylation reaction with methyl chloride and tin tetrachloride under the action of a catalyst at high temperature and high pressure to generate a methyl tin chloride intermediate, then an aqueous solution of methyl tin chloride is subjected to reaction with isooctyl thioglycolate, alkali liquor is used for neutralization, and finally the crude product is subjected to reduced pressure distillation and filtration to remove impurities, so that the methyl tin mercaptide can be prepared. The commercially available methyltin mercaptide is mainly a mixture of isooctyl monomethyltrimercaptoacetate tin (hereinafter referred to as "monomethyltin") and isooctyl dimethyldimercaptoacetate tin (hereinafter referred to as "dimethyltin"), and the mass ratio of the two is generally 20: 80 or 30: 70. during the processing, the first stage of the action of the first part is mainly shown by excellent stability in the early stage, and the second stage of the action of the second part is mainly shown by better stability in the later stage.
In recent years, with the continuous development of plastic processing industry, a small number of manufacturers put higher requirements on the proportion of the first component and the second component in the methyl tin heat stabilizer, and a part of plastic products require excellent transparency, while the stability in the later period of the processing process can be weakened, so that the requirements of higher content of the first component and higher content of the methyl tin product are put forward, that is, the higher purity of the isooctyl monomethyltrithioglycolate tin is better.
At present, most of methyl tin products used in domestic markets have a methyl content of 20-35%, although the methyl in the products can be regulated and controlled by adjusting the using amount of tin tetrachloride in the reaction process of preparing a methyl tin chloride intermediate, the more the tin tetrachloride is used, the larger the proportion of the methyl tin trichloride is, the higher the methyl content in the finally obtained methyl tin products is, but in the actual reaction process, the larger the input amount of the tin tetrachloride is, the longer the required reaction time is, and the conversion rate is not high enough, so that the methyl in the products is low and generally less than 80%, and the use requirements of part of customers cannot be met.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a preparation method of a high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer, which has the advantages of mild reaction conditions, simple and convenient operation, high content of first-class products, high purity of more than 90 percent, and stable quality.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer is characterized in that a methyltin chloride aqueous solution, an alkali liquor and isooctyl mercaptoacetate are used as reaction raw materials and are prepared by a two-step method, wherein a dimethyl tin dichloride component in the methyltin chloride aqueous solution is removed firstly, and then the isooctyl monomethyltrimercaptoacetate tin heat stabilizer is prepared, and the method comprises the following steps:
the method comprises the following steps: firstly, putting a methyl tin chloride aqueous solution obtained by mixing methyl tin trichloride and dimethyl tin dichloride into a reaction kettle, starting stirring, then dropwise adding alkali liquor to react, controlling the reaction temperature within 5-30 ℃, reacting for 0.5-2 hours, controlling the end-point pH value between 7.5-9, and reacting to obtain solid-phase dimethyl tin oxide and monomethyl tin oxide; after the reaction is finished, centrifugal filtration is carried out by a centrifugal machine, and solid-phase substances and liquid-phase substances are separated; the alkali liquor is ammonia water or sodium hydroxide solution or potassium hydroxide solution;
step two: transferring the separated liquid phase into another reaction kettle, and then adding isooctyl thioglycolate at one time; starting stirring, stirring for 3-5 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase splitting; and (3) after phase separation, carrying out reduced pressure distillation on the organic phase, cooling, and filtering to obtain the high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer with the purity of 90-99%.
Furthermore, the invention can also react the mixture of the dimethyltin oxide and the monomethyl tin oxide obtained in the step one with isooctyl thioglycolate to prepare the dimethyl tin dimercaptoacetate heat stabilizer with the purity of not less than 93 percent.
The solute in the methyl tin chloride aqueous solution comprises methyl tin trichloride and dimethyl tin dichloride, and the invention creatively adopts a method of firstly removing the dimethyl tin dichloride in the solution and then preparing the isooctyl monomethylmercaptoacetate tin heat stabilizer with higher purity by using the residual methyl tin trichloride in the solution. The thermal stabilizer of isooctyl monomethyltrimercaptoacetate tin is mainly suitable for PVC tape-casting products with high transparency and higher requirements on early-stage stability. The method for removing the dimethyltin dichloride is to add alkali liquor for reaction to generate dimethyltin oxide solid. In the reaction with alkali liquor, dimethyl tin dichloride can react to produce dimethyl tin oxide, and monomethyl tin trichloride can also react to produce the other product, namely monomethyl tin oxide. Under the technical conditions of the invention, the generation amount of the oxidized monomethyl tin is effectively controlled, so that a large amount of monomethyl tin trichloride is still dissolved in a water phase, and the high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer is further prepared. The invention further reacts the mixture of the dimethyltin oxide and the monomethyl tin oxide with the isooctyl thioglycolate to prepare the other dimethyl tin dimercaptoacetate heat stabilizer with higher purity, which does not cause raw material waste.
The preparation method of the high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer provided by the invention has the advantages of mild reaction conditions, simple and convenient operation, higher content of isooctyl monomethyltrimercaptoacetate tin in the product, high product purity and stable quality. The dimethyl tin isooctyl dimercaptoacetate heat stabilizer prepared further has the same higher purity, and the raw material waste is not caused.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Firstly, putting 2000kg of 30/70 type methyl tin chloride aqueous solution with 24.69% of tin and 16.81% of chlorine into a reaction kettle, starting stirring, then dropwise adding ammonia water to react, controlling the reaction temperature to be 30 ℃, the end-point pH value to be 7.5, reacting for 0.5 hour, and after the reaction is finished, carrying out centrifugal filtration by using a centrifugal machine to obtain 685.4kg of white solid methyl tin oxide and 2050.5kg of filtrate;
transferring all the filtrate into a reaction kettle, adding 697.6kg of isooctyl thioglycolate, starting stirring, stirring for 5 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase splitting. And after phase separation is finished, carrying out reduced pressure distillation on the organic phase, wherein the distillation pressure is-87 kPa, then cooling to normal temperature, and filtering to finally obtain 837.3kg of a high-purity isooctyl monomethyltrimercaptoacetate tin product (also called a methyl tin mercaptide product), wherein the content of the isooctyl monomethyltrimercaptoacetate tin is 98.18%. Is mainly suitable for PVC casting products with high transparency and higher requirements on the stability in the early stage
In addition, 1279.4kg of isooctyl thioglycolate is added into another reaction kettle, stirring is started, 685.4kg of white solid tin methyl oxide obtained by centrifugation is added at a constant speed, stirring is stopped after the reaction is finished, and the mixture is kept stand for phase separation. After the phase separation is finished, the organic phase is distilled under reduced pressure, cooled to normal temperature and filtered to prepare 1711.7kg of isooctyl dimethyldimercaptoacetate tin heat stabilizer with the purity of 96.73 percent.
Example 2
Firstly, putting 1850kg of 32/68 type methyl tin chloride aqueous solution with 25.23 percent of tin and 17.33 percent of chlorine into a reaction kettle, starting stirring, then dropwise adding sodium hydroxide solution for reaction, controlling the reaction temperature at 25 ℃, controlling the end-point pH value at 8.0, reacting for 2 hours, and centrifugally filtering by using a centrifugal machine after the reaction is finished to obtain 612.7kg of white solid methyl tin oxide and 1936.1kg of filtrate;
transferring all the filtrate into a reaction kettle, adding 675.3kg of isooctyl thioglycolate, starting stirring, stirring for 3 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase splitting. And after the phase separation is finished, carrying out reduced pressure distillation on the organic phase, wherein the distillation pressure is-86 kPa, then cooling and filtering to finally obtain 811.4kg of a high-purity isooctyl monomethyltrimercaptoacetate tin product, wherein the content of the isooctyl monomethyltrimercaptoacetate tin is 97.29%.
In addition, 1210.0kg of isooctyl thioglycolate is added into another reaction kettle, stirring is started, 612.7kg of white solid tin methyl oxide obtained by centrifugation is added at a constant speed, stirring is stopped after the reaction is finished, and the mixture is kept stand for phase separation. After the phase separation is finished, the organic phase is distilled under reduced pressure, cooled to normal temperature and filtered to prepare 1613.2kg of isooctyl dimethyldimercaptoacetate tin heat stabilizer with the purity of 93.82 percent.
Example 3
Firstly, 1900kg of 29/71 type methyl tin chloride aqueous solution with 25.74 percent of tin and 17.50 percent of chlorine is put into a reaction kettle, the stirring is started, then ammonia water is dripped for reaction, the reaction temperature is 20 ℃, the end point pH value is controlled at 9.0, the reaction is carried out for 1.5 hours, and after the reaction is finished, a centrifugal machine is used for carrying out centrifugal filtration to obtain 654.6kg of white solid methyl tin oxide and 1970.2kg of filtrate;
transferring all the filtrate into a reaction kettle, adding 666.0kg of isooctyl thioglycolate, starting stirring, stirring for 4 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase splitting. And after phase separation is finished, carrying out reduced pressure distillation on the organic phase, wherein the distillation pressure is-87 kPa, then cooling and filtering to finally obtain 802.1kg of a high-purity isooctyl monomethyltrimercaptoacetate tin product, wherein the content of the isooctyl monomethyltrimercaptoacetate tin is 95.05%.
In addition, 1289.2kg of isooctyl thioglycolate is added into another reaction kettle, stirring is started, 654.6kg of white solid tin methyl oxide obtained by centrifugation is added at constant speed, stirring is stopped after the reaction is finished, and the mixture is kept stand to separate phases. After the phase separation is finished, the organic phase is distilled under reduced pressure, cooled to normal temperature and filtered to prepare 1720.0kg of isooctyl dimethyldimercaptoacetate tin heat stabilizer with the purity of 94.33 percent.
Example 4
Firstly, putting 2000kg of 21/79 type methyl tin chloride aqueous solution with 24.97% of tin and 16.36% of chlorine into a reaction kettle, starting stirring, then dropwise adding potassium hydroxide solution for reaction, controlling the reaction temperature to be 5 ℃ and the end-point pH value to be 8.0, reacting for 1 hour, and after the reaction is finished, carrying out centrifugal filtration by using a centrifugal machine to obtain 744.8kg of white solid methyl tin oxide and 1968.3kg of filtrate;
transferring all the filtrate into a reaction kettle, adding 477.3kg of isooctyl thioglycolate, starting stirring, stirring for 4 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase splitting. And after phase separation is finished, carrying out reduced pressure distillation on the organic phase, wherein the distillation pressure is-85 kPa, then cooling and filtering to finally obtain 575.0kg of a high-purity isooctyl monomethyltrimercaptoacetate tin product, wherein the content of the isooctyl monomethyltrimercaptoacetate tin is 94.92%.
In addition, 1446.7kg of isooctyl thioglycolate is added into another reaction kettle, stirring is started, 744.8kg of white solid tin methyl oxide obtained by centrifugation is added at a constant speed, stirring is stopped after the reaction is finished, and the mixture is kept stand for phase separation. After the phase separation is finished, the organic phase is distilled under reduced pressure, cooled to normal temperature and filtered to prepare 1934.3kg of dimethyl tin isooctyl dimercaptoacetate with the purity of 96.12 percent.
Example 5
Firstly, 1900kg of 20/80 type methyl tin chloride aqueous solution with 24.48 percent of tin and 15.97 percent of chlorine is put into a reaction kettle, the stirring is started, then ammonia water is dripped for reaction, the reaction temperature is 10 ℃, the end point pH value is controlled at 8.5, the reaction is carried out for 1.5 hours, and after the reaction is finished, a centrifugal machine is used for carrying out centrifugal filtration to obtain 701.8kg of white solid methyl tin oxide and 1860.5kg of filtrate;
transferring all the filtrate into a reaction kettle, adding 422.2kg of isooctyl thioglycolate, starting stirring, stirring for 3.5 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase separation. And after the phase separation is finished, carrying out reduced pressure distillation on the organic phase, wherein the distillation pressure is-87 kPa, then cooling and filtering to finally obtain 508.2kg of a high-purity isooctyl monomethyltrimercaptoacetate tin product, wherein the content of the isooctyl monomethyltrimercaptoacetate tin is 95.68%.
In addition, 1362.0kg of isooctyl thioglycolate is added into another reaction kettle, stirring is started, 701.8kg of white solid tin methyl oxide obtained by centrifugation is added at a constant speed, stirring is stopped after the reaction is finished, and the mixture is kept stand for phase separation. After the phase separation is finished, the organic phase is distilled under reduced pressure, cooled to normal temperature and filtered to prepare 1821.7kg of dimethyl tin isooctyl dimercaptoacetate heat stabilizer with the purity of 96.46%.
Example 6
Firstly, 1900kg of 20/80 type methyl tin chloride aqueous solution with 24.81 percent of tin and 16.22 percent of chlorine is put into a reaction kettle, the stirring is started, then sodium hydroxide solution is dripped to carry out the reaction, the reaction temperature is 15 ℃, the end point pH value is controlled at 8.0, the reaction is carried out for 1.5 hours, and after the reaction is finished, a centrifugal machine is used for carrying out centrifugal filtration to obtain 707.2kg of white solid methyl tin oxide and 1868.8kg of filtrate;
transferring all the filtrate into a reaction kettle, then adding 449.3kg of isooctyl thioglycolate, starting stirring, stirring for 5 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase splitting. And after phase separation is finished, carrying out reduced pressure distillation on the organic phase, wherein the distillation pressure is-86 kPa, then cooling and filtering to finally obtain 539.1kg of a high-purity isooctyl monomethyltrimercaptoacetate tin product, wherein the content of the isooctyl monomethyltrimercaptoacetate tin is 98.94%.
In addition, 1362.8kg of isooctyl thioglycolate is added into another reaction kettle, stirring is started, 707.2kg of white solid tin methyl oxide obtained by centrifugation is added at a constant speed, stirring is stopped after the reaction is finished, and the mixture is kept stand for phase separation. After the phase separation is finished, the organic phase is distilled under reduced pressure, cooled to normal temperature and filtered to prepare 1826.0kg of isooctyl dimethyldimercaptoacetate tin heat stabilizer with the purity of 97.88 percent.
Example 7
Firstly, putting 2000kg of 40/60 type methyl tin chloride aqueous solution with 25.89 percent of tin and 18.47 percent of chlorine into a reaction kettle, starting stirring, then dropwise adding ammonia water for reaction, controlling the reaction temperature to be 20 ℃, the end-point pH value to be 9.0, reacting for 2 hours, and after the reaction is finished, carrying out centrifugal filtration by using a centrifugal machine to obtain 601.6kg of white solid methyl tin oxide and 2205.6kg of filtrate;
transferring all the filtrate into a reaction kettle, adding 986.8kg of isooctyl thioglycolate, starting stirring, stirring for 4 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase splitting. And after phase separation is finished, carrying out reduced pressure distillation on the organic phase, wherein the distillation pressure is-86 kPa, then cooling, and filtering to finally obtain 1183.4kg of a high-purity isooctyl monomethyltrimercaptoacetate tin product, wherein the content of the isooctyl monomethyltrimercaptoacetate tin is 99.11%.
In addition, 1185.4kg of isooctyl thioglycolate is added into another reaction kettle, stirring is started, 601.6kg of white solid tin methyloxide obtained by centrifugation is added at a constant speed, stirring is stopped after the reaction is finished, and standing is carried out for phase separation. After the phase separation is finished, the organic phase is distilled under reduced pressure, cooled to normal temperature and filtered to prepare 1580.1kg of isooctyl dimethyldimercaptoacetate tin heat stabilizer with the purity of 93.67 percent.
The percentages stated in the present invention are percentages by mass, unless otherwise stated.
Claims (2)
1. A preparation method of a high-purity isooctyl thioglycolate tin heat stabilizer is characterized in that a methyl tin chloride aqueous solution, alkali liquor and isooctyl thioglycolate are used as reaction raw materials and are prepared by a two-step method, wherein a dimethyl tin dichloride component in the methyl tin chloride aqueous solution is removed firstly in the first step, and then the isooctyl thioglycolate tin heat stabilizer is prepared in the second step, and the method comprises the following steps:
the method comprises the following steps: firstly, putting a methyl tin chloride aqueous solution obtained by mixing methyl tin trichloride and dimethyl tin dichloride into a reaction kettle, starting stirring, then dropwise adding alkali liquor to react, controlling the reaction temperature within 5-30 ℃, reacting for 0.5-2 hours, controlling the end-point pH value between 7.5-9, and reacting to obtain solid-phase dimethyl tin oxide and monomethyl tin oxide; after the reaction is finished, centrifugal filtration is carried out by a centrifugal machine, and solid-phase substances and liquid-phase substances are separated; the alkali liquor is ammonia water or sodium hydroxide solution or potassium hydroxide solution;
step two: transferring the separated liquid phase into another reaction kettle, and then adding isooctyl thioglycolate at one time; starting stirring, stirring for 3-5 hours at normal temperature, stopping stirring after the stirring is finished, and standing for phase splitting; and (3) after phase separation, carrying out reduced pressure distillation on the organic phase, cooling, and filtering to obtain the high-purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer with the purity of 90-99%.
2. The method for preparing a high purity isooctyl monomethyltrimercaptoacetate tin heat stabilizer according to claim 1, wherein the dimethyl isooctyl dimercaptoacetate tin heat stabilizer having a purity of not less than 93% is prepared by reacting the mixture of dimethyltin oxide and monomethyltin oxide obtained in the above step one with isooctyl thioglycolate.
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