CN105924467A - Green and safe methyl tin mercaptide preparation method - Google Patents
Green and safe methyl tin mercaptide preparation method Download PDFInfo
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- CN105924467A CN105924467A CN201610468809.6A CN201610468809A CN105924467A CN 105924467 A CN105924467 A CN 105924467A CN 201610468809 A CN201610468809 A CN 201610468809A CN 105924467 A CN105924467 A CN 105924467A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 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 title abstract 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims abstract description 28
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- -1 Methyl stannum Chemical compound 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 32
- 239000000654 additive Substances 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 26
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 235000014121 butter Nutrition 0.000 claims description 8
- 230000026030 halogenation Effects 0.000 claims description 8
- 238000005658 halogenation reaction Methods 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 208000035126 Facies Diseases 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000002140 halogenating effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000008187 granular material Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 239000011807 nanoball Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012163 sequencing technique Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IRDJCBNSDNPDSA-ZOKJKDLISA-H (Z)-but-2-enedioate methyltin(3+) Chemical compound C[Sn+3].C[Sn+3].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O IRDJCBNSDNPDSA-ZOKJKDLISA-H 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method for organic tin type materials, in particular to a green and safe methyl tin mercaptide preparation method. The green and safe methyl tin mercaptide preparation method comprises the following steps: (1), tin processing: putting metal tin and a first catalyst into a reaction kettle, halogenating after charging methyl chloride, adding a redistribution agent to perform a tin reaction, distilling, receiving fractions with gas temperature of 150-230 DEG C, and using pure water to absorb, thereby obtaining a methyl tin chloride water solution; (2), synthesizing: adding the obtained methyl tin chloride water solution into isooctyl thioglycolate, adding a second catalyst, stirring to react at 5-15 DEG C for 0.2-0.4 hour, adding alkali liquid, continuously stirring to react till a pH value of a reaction system reaches 7-9, heating to 60-70 DEG C, reacting for 1-1.5 hours, standing, cooling down, and layering; (3), rinsing; (4) distilling. According to the green and safe methyl tin mercaptide preparation method, a product has high transparency, weather resistance, compatibility and volatilization precipitation resistance, and has good heat stability and low tin content.
Description
Technical field
The present invention relates to the preparation method of a kind of organic tin material, particularly relate to the Methyl stannum mercaptide of a kind of green safety
Preparation method.
Background technology
Organic tin compound is used in polyvinyl chloride resin and makees stabilizer oneself has many patents, as United States Patent (USP) 3222317,
3396185 etc., mainly butyl tin and tin octylate, because propyl group stannum scent of, and ethyl stannum is poisonous and is replaced.
The main kind of organotin has three series such as monoalkyltin, double tin alkyl and trialkyltin, wherein three alkane
Base stannum series toxicity is the strongest, it is impossible to use as stabilizer;Monoalkyltin has monomethyl stannum, Monobutyltin, single tin octylate etc.;Double
Tin alkyl has stannous methide, dibutyl tin, dioctyl tin etc..At present, the own PVC packed in medicine food through given application of European Union
Material prohibits the use of butyl tin and tin octylate series, and methyl stannum series is still widely used in due to its distinctive character
In various high-grade PVC product.
Methyl stannum (SM501) on market is mainly containing 20% tri-thiol 2-ethyl hexyl ethanoate methyl stannum and 80% 2 at home
Isooctyl thioglycolate stannous methide, its Theil indices is 19. 4, in the actual course of processing, this methyl stannum on market
Can move to surface from the inside of goods, finally separate out from product surface, form speckle flower, have impact on the quality of goods, here it is
So-called ooze out (or weighing up antiperspirant);It addition, in the course of processing, the easy roll banding of batch, release property, lubricity are poor, are unfavorable for
The Continuous maching of product produces.
CN102503972B (2015-6-17) discloses a kind of Methyltin maleate and preparation method thereof, but how
Still have much room for improvement in the preparation method of the Methyl stannum mercaptide preparing the green safety that Theil indices reduces, thermal stability is good.
Summary of the invention
It is an object of the invention to provide the Methyl stannum mercaptide of the green safety that a kind of Theil indices reduces, thermal stability is good
Preparation method.
The above-mentioned technical purpose of the present invention has the technical scheme that the methyl of a kind of green safety
The preparation method of tin mercaptides, comprises the following steps:
(1) stannum: metallic tin and the first catalyst are put in reactor, then passes to chloromethanes and carry out halogenation, add again
Distribution is after agent carries out stannum reaction, distills and accepts gas temperature at 150-230 DEG C of interior fraction, then obtaining by absorbing pure water
Methyl tin chloride aqueous solution；Described methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, in temperature
At spending 5-15 DEG C, stirring reaction 0.2-0.4 hour, adds the continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9,
Then heat to 60-70 DEG C, react 1-1.5 hour, static, lower the temperature, be layered；
Described metallic tin, chloromethanes, reallocation agent, the mol ratio of isooctyl thioglycolate are 1:(1.5-2): (0.2-0.5):
(3-4)；
(3) washing: separate organic facies and wash 1-2 time；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying.
The Methyl stannum mercaptide finally obtained=it is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and CH3Sn
(SCH2CO2C8H17)3The mixture of (monomethyl stannum), wherein the quality accounting of stannous methide is 40-60%.
The present invention uses specific stannum, synthesis technique, especially controls distillation and accepts gas temperature at 150-230 DEG C
Interior fraction, is more beneficial for the carrying out of follow-up synthetic reaction, makes finally prepd Methyl stannum mercaptide material as stabilizer for plastics
Stablizing effect more preferable.
Product of the present invention has high transparent, weatherability, the compatibility and resistance to volatilization precipitation property, and avirulence, high heat stability
Property is good, and low tin content, the thermostable effect of the methyl stannum of this low tin content is better than existing methyl stannum, for final PVC
Goods to reach same stablizing effect, and the addition of Methyltin stabiliser will be less, just can reduce stannum consumption further,
Reduce the production cost of client terminals eventually.
As preferably, described step (1) stannum specifically includes and puts in pressure acid-resistant reacting kettle by metallic tin and catalyst,
Then pass to chloromethanes at a temperature of 150-170 DEG C, heat mix homogeneously, after carrying out halogenation 0.2-0.4h, add and divide again
Ingredients and be warmed up to 235-245 DEG C, be forced into 0.5-0.8MPa carry out stannumization react 1-2 hour.
Use the present invention specific stannum method to be conducive to the carrying out of follow-up synthetic reaction, make finally prepd methyl mercaptan
Stannum material is more preferable as the stablizing effect of stabilizer for plastics.
As preferably, described first catalyst is that quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfide are according to molal weight
Mixture than 1:2-3 composition.
Entering of the employing present invention specific first catalyst beneficially halogenation, stannumization reaction and follow-up synthetic reaction
OK, make finally prepd Methyl stannum mercaptide material more preferable as the stablizing effect of stabilizer for plastics.
As preferably, described second catalyst is that quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide are according to molal weight
Mixture than 1:1-4 composition.
Use the carrying out of the present invention specific second catalyst beneficially synthetic reaction, make finally prepd Methyl stannum mercaptide
Material is more preferable as the stablizing effect of stabilizer for plastics.
As preferably, described quaternary ammonium salt phase catalyst is that tetrabutyl ammonium bromide, tetrabutyl chlorination are by, tetrabutyl hydrogen sulfate
Ammonium or tri-n-octyl methyl ammonium chloride.
As preferably, described reallocation agent is butter of tin.
As preferably, the weight of described first catalyst accounts for the 1-3% of metallic tin weight.
As preferably, the weight of described second catalyst accounts for the 6-9% of isooctyl thioglycolate weight.
As preferably, in described step (2), the mass fraction of alkali liquor is 10-20%.
As preferably, in synthesis step, in the addition continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9,
Then, during heating up, add first solid additive of the 1-3% accounting for isooctyl thioglycolate weight according to sequencing and account for
Second solid additive of the 3-6% of isooctyl thioglycolate weight.
As preferably, the particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for institute
State the 20-40% of the first solid additive gross weight；The granule of 1-2 micron accounts for the 10-30% of described first solid additive gross weight；Remaining
Amount is the granule of 3-5 micron；
Described first solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight divides
Cloth index is 3.1:
I
Described second solid additive be the molybdenum disulfide nano ball of particle diameter 10-20 nanometer with the regulation grain of particle diameter 6-9 micron by
Mixture according to mass ratio 1:2-5 composition.
Different-grain diameter and the first solid additive of kind and the second solid additive increase Methyl stannum mercaptide stability,
While reducing Theil indices, moreover it is possible to give Methyl stannum mercaptide more preferable resistance to volatilization precipitation property.
Detailed description of the invention
Embodiment one
The preparation method of the Methyl stannum mercaptide of green safety, comprises the following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 150 DEG C
Heating mix homogeneously, after carrying out halogenation 0.2h, adds reallocation agent butter of tin and is warmed up to 235 DEG C, is forced into
0.5MPa carries out stannumization and reacts 1 hour, then, distills and accepts gas temperature at 150 DEG C of interior fractions, then using absorbing pure water
Obtain methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst is quaternary ammonium salt phase transfer
The mixture that catalyst and dimethyl sulfide form than 1:2 according to molal weight；The weight of the first catalyst accounts for metallic tin weight
1%.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst,
Stirring reaction 0.2 hour at temperature 5 DEG C, adds the continuously stirred reaction of alkali liquor that mass fraction is 10% until reaction system
PH value reaches 7, then heats to 60 DEG C, reacts 1 hour, static, lower the temperature, be layered；
The mixing that second catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide forms than 1:1 according to molal weight
Thing；The weight of the second catalyst accounts for the 6% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, the mol ratio of isooctyl thioglycolate are 1:1.5:0.2:4；
(3) washing: separate organic facies and wash 1 time；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying.
The Methyl stannum mercaptide finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and CH3Sn
(SCH2CO2C8H17)3The mixture of (monomethyl stannum), wherein the quality accounting of stannous methide is 40-60%.
Quaternary ammonium salt phase catalyst is tetrabutyl ammonium bromide.
Embodiment two
The preparation method of the Methyl stannum mercaptide of green safety, comprises the following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 170 DEG C
Heating mix homogeneously, after carrying out halogenation 0.4h, adds reallocation agent butter of tin and is warmed up to 235-245 DEG C, pressurization
Carry out stannumization to 0.5-0.8MPa to react 2 hours, then, distill and accept gas temperature at 230 DEG C of interior fractions, then with pure
Water absorbs and obtains methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst is quaternary ammonium salt phase transfer
The mixture that catalyst and dimethyl sulfide form than 1:3 according to molal weight；The weight of the first catalyst accounts for metallic tin weight
3%.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst,
Stirring reaction 0.4 hour at temperature 5-15 DEG C, adds the continuously stirred reaction of alkali liquor that mass fraction is 20% until reactant
It is that pH value reaches 7-9, then heats to 70 DEG C, react 1.5 hours, static, lower the temperature, be layered；
The mixing that second catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide forms than 1:1-4 according to molal weight
Thing；The weight of the second catalyst accounts for the 6-9% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, the mol ratio of isooctyl thioglycolate are 1:2:0.5:3；
(3) washing: separate organic facies and wash 2 times；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying.
The Methyl stannum mercaptide finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and CH3Sn
(SCH2CO2C8H17)3The mixture of (monomethyl stannum), wherein the quality accounting of stannous methide is 60%.
Quaternary ammonium salt phase catalyst is tetrabutylammonium chloride.
Embodiment three
The preparation method of the Methyl stannum mercaptide of green safety, comprises the following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes at a temperature of 160 DEG C
Heating mix homogeneously, after carrying out halogenation 0.3h, adds reallocation agent butter of tin and is warmed up to 240 DEG C, is forced into
0.6MPa carries out stannumization and reacts 1.5 hours, then, distills and accepts gas temperature at 200 DEG C of interior fractions, then inhaling with pure water
Gather in the crops to obtain methyl tin chloride aqueous solution；
Methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；First catalyst is quaternary ammonium salt phase transfer
The mixture that catalyst and dimethyl sulfide form than 1:2.5 according to molal weight；The weight of the first catalyst accounts for metallic tin weight
The 2% of amount.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst,
Stirring reaction 0.3 hour at temperature 10 DEG C, adds the continuously stirred reaction of alkali liquor that mass fraction is 15% until reaction system
PH value reaches 8, then heats to 65 DEG C, reacts 1-1.5 hour, static, lower the temperature, be layered；
The mixing that second catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide forms than 1:3 according to molal weight
Thing；The weight of the second catalyst accounts for the 8% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, the mol ratio of isooctyl thioglycolate are 1:1.8:0.3:3.5；
(3) washing: separate organic facies and wash 1 time；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying.
The Methyl stannum mercaptide finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and CH3Sn
(SCH2CO2C8H17)3The mixture of (monomethyl stannum), wherein the quality accounting of stannous methide is 50%.
Quaternary ammonium salt phase catalyst is tri-n-octyl methyl ammonium chloride.
Embodiment four
With embodiment one, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 7, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 1% the first solid additive and
Account for isooctyl thioglycolate weight 6% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 20% of agent gross weight；The granule of 1-2 micron accounts for the 30% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:2 composition.
Embodiment five
With embodiment two, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 9, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 3% the first solid additive and
Account for isooctyl thioglycolate weight 3% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 40% of agent gross weight；The granule of 1-2 micron accounts for the 10% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:5 composition.
Embodiment six
With embodiment three, except for the difference that in synthesis step, adding the continuously stirred reaction of alkali liquor until pH value of reaction system reaches
To 8, then heat up during, according to sequencing add account for isooctyl thioglycolate weight 2% the first solid additive and
Account for isooctyl thioglycolate weight 5% the second solid additive.
The particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for the first solid and adds
Add the 30% of agent gross weight；The granule of 1-2 micron accounts for the 20% of the first solid additive gross weight；Surplus is the granule of 3-5 micron；
First solid additive is following formula I polymer, and wherein Mw is 6.10 × 106, Mn is 2.0 × 106, molecular weight distribution refers to
Number is 3.1:
I
Second solid additive is that the regulation grain of molybdenum disulfide nano ball and the particle diameter 6-9 micron of particle diameter 10-20 nanometer is according to matter
Measure the mixture than 1:3 composition.
Comparative example one
With embodiment one, except for the difference that stannum step distilled and accept gas temperature at 140 DEG C of interior fractions, in synthesis step
Gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, stir at temperature 25 DEG C
React 0.8 hour, add the continuously stirred reaction of alkali liquor until pH value of reaction system reaches 10, then heat to 60 DEG C, react 1
Hour.
Application test contrasts:
Methyl stannum mercaptide comparative example one prepared is applied with the Methyl stannum mercaptide in embodiment one to embodiment six respectively
Carrying out static burn in test in PVC sheet, the amount adding heat stabilizer is 0.8%, and the PVC sheet made is 180 DEG C of guarantors
Temperature, kept sample standby every ten minutes, until all of sheet material all turns yellow, and used time 110 minutes altogether, all samples of sheets are made
Form, obtains aging control experiment data the most intuitively, and its result is as follows:
As can be seen from Table I: the product of developing of the present invention has more excellent thermostable effect, under the conditions of equal consumption,
Than the product xanthochromia time lengthening more than half times of comparative example one, and Theil indices have dropped about 4%.Can significantly drop
The production cost of low PVC producer, reaches cheap purpose.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
The present embodiment can be made after reading this specification by member as required does not has the amendment of creative contribution, but as long as at this
All protected by Patent Law in the right of invention.
Claims (10)
1. the preparation method of the Methyl stannum mercaptide of a green safety, it is characterised in that comprise the following steps:
(1) stannum: metallic tin and the first catalyst are put in reactor, then passes to chloromethanes and carry out halogenation, add again
Distribution is after agent carries out stannum reaction, distills and accepts gas temperature at 150-230 DEG C of interior fraction, then obtaining by absorbing pure water
Methyl tin chloride aqueous solution；Described methyl alkene chloride includes dimethyltin chloride and monomethyl tin trichloride；
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, in temperature
At spending 5-15 DEG C, stirring reaction 0.2-0.4 hour, adds the continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9,
Then heat to 60-70 DEG C, react 1-1.5 hour, static, lower the temperature, be layered；
Described metallic tin, chloromethanes, reallocation agent, the mol ratio of isooctyl thioglycolate are 1:(1.5-2): (0.2-0.5):
(3-4)；
(3) washing: separate organic facies and wash 1-2 time；
(4) distillation: obtain Methyl stannum mercaptide after vacuum distillation drying.
The preparation method of the Methyl stannum mercaptide of a kind of green safety the most according to claim 1, it is characterised in that: described step
Suddenly (1) stannum specifically includes and metallic tin and catalyst is put in pressure acid-resistant reacting kettle, then passes to chloromethanes at 150-170
At a temperature of DEG C heat mix homogeneously, after carrying out halogenation 0.2-0.4h, add reallocation agent and be warmed up to 235-245 DEG C,
It is forced into 0.5-0.8MPa and carries out stannumization reaction 1-2 hour.
The preparation method of the Methyl stannum mercaptide of a kind of green safety the most according to claim 2, it is characterised in that: described
The mixture that one catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfide forms than 1:2-3 according to molal weight.
The preparation method of the Methyl stannum mercaptide of a kind of green safety the most according to claim 3, it is characterised in that: described
The mixture that two catalyst are quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfoxide forms than 1:1-4 according to molal weight.
5. according to the preparation method of the Methyl stannum mercaptide of a kind of green safety described in claim 3 or 4, it is characterised in that: institute
Stating quaternary ammonium salt phase catalyst is tetrabutyl ammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or tricaprylmethyl chlorination
Ammonium.
The preparation method of the Methyl stannum mercaptide of a kind of green safety the most according to claim 5, it is characterised in that: described again
Distribution agent is butter of tin.
The preparation method of the Methyl stannum mercaptide of a kind of green safety the most according to claim 3, it is characterised in that: described
The weight of one catalyst accounts for the 1-3% of metallic tin weight.
The preparation method of the Methyl stannum mercaptide of a kind of green safety the most according to claim 4, it is characterised in that: described
The weight of two catalyst accounts for the 6-9% of isooctyl thioglycolate weight.
The preparation method of the Methyl stannum mercaptide of a kind of green safety the most according to claim 6, it is characterised in that: described step
Suddenly in (2), the mass fraction of alkali liquor is 10-20%.
The preparation method of the Methyl stannum mercaptide of a kind of green safety the most according to claim 6, it is characterised in that: closing
Become in step, in the addition continuously stirred reaction of alkali liquor until pH value of reaction system reaches 7-9, during then heating up, according to first
Rear order adds first solid additive of the 1-3% accounting for isooctyl thioglycolate weight and accounts for isooctyl thioglycolate weight
Second solid additive of 3-6%.
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