CN105885088A - Environment-friendly method for preparing methyl tin mercaptide combinations - Google Patents
Environment-friendly method for preparing methyl tin mercaptide combinations Download PDFInfo
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- CN105885088A CN105885088A CN201610468810.9A CN201610468810A CN105885088A CN 105885088 A CN105885088 A CN 105885088A CN 201610468810 A CN201610468810 A CN 201610468810A CN 105885088 A CN105885088 A CN 105885088A
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- Prior art keywords
- methyl
- weight
- environment
- friendly
- tin
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Links
- 238000000034 method Methods 0.000 title abstract description 7
- 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
- 239000007787 solid Substances 0.000 claims abstract description 49
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 48
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- -1 Methyl stannum Chemical compound 0.000 claims description 53
- 230000000996 additive effect Effects 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 39
- 239000002131 composite material Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims description 14
- 150000002576 ketones Chemical class 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 10
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 10
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- 150000002170 ethers Chemical class 0.000 claims description 10
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 10
- 210000000582 semen Anatomy 0.000 claims description 10
- 150000003568 thioethers Chemical class 0.000 claims description 10
- 229960001124 trientine Drugs 0.000 claims description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 10
- 239000008158 vegetable oil Substances 0.000 claims description 10
- 238000012163 sequencing technique Methods 0.000 claims description 9
- 235000014121 butter Nutrition 0.000 claims description 8
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 230000026030 halogenation Effects 0.000 claims description 6
- 238000005658 halogenation reaction Methods 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- LCNKXFWTHRHHIU-UHFFFAOYSA-N 3-aminocyclopentane-1-thiol Chemical compound NC1CCC(S)C1 LCNKXFWTHRHHIU-UHFFFAOYSA-N 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 208000035126 Facies Diseases 0.000 claims description 5
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 5
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 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
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000539 dimer Substances 0.000 claims description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 claims description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 5
- 239000011807 nanoball Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 235000019198 oils Nutrition 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical group [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims 1
- 244000046052 Phaseolus vulgaris Species 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
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract 5
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 238000004383 yellowing Methods 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 6
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 235000021357 Behenic acid Nutrition 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229940116226 behenic acid Drugs 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 125000004151 quinonyl group Chemical group 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229950000845 politef Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000001384 succinic acid Substances 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 235000021313 oleic acid Nutrition 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- 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
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing organic tin substances, in particular to an environment-friendly method for preparing methyl tin mercaptide combinations. The environment-friendly method includes steps of (1), carrying out tinning treatment; (2), carrying out synthesis, to be more specific, adding methyltin mercaptide chloride aqueous solution into isooctyl thioglycolate, adding second catalysts, alkane diacid and modifiers into the isooctyl thioglycolate, carrying out reaction to obtain reaction products, adding alkali liquor and anti-yellowing agents into the reaction products, continuously carrying out stirring reaction until a pH (potential of hydrogen) value of a reaction system reaches 7-9, then heating the reaction system until the temperature of the reaction system reaches 60-70 DEG C, sequentially adding first solid additives and second solid additives into the reaction system in heating procedures and carrying out reaction; (3), carrying out water washing; (4), carrying out distillation. The weight of the first solid additives accounts for 1-3% of that of the isooctyl thioglycolate, and the weight of the second additives accounts for 3-6% of that of the isooctyl thioglycolate. The modifier include, by weight, 6-9 parts of first compound modifiers, 7-11 parts of second compound modifiers and 8-14 parts of third compound modifiers. The environment-friendly method has the advantages that the methyl tin mercaptide combinations are yellowing-resistant and volatilization-precipitation-resistant and are good in heat stability and low in 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 environment-friendly and green
The preparation method of compound.
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 need to be changed in the preparation method of the Methyl stannum mercaptide compound preparing the environment-friendly and green that Theil indices reduces, thermal stability is good
Enter.
Summary of the invention
The Methyl stannum mercaptide that it is an object of the invention to provide the environment-friendly and green that a kind of Theil indices reduces, thermal stability is good is multiple
Join the preparation method of thing.
The above-mentioned technical purpose of the present invention has the technical scheme that the methyl of a kind of environment-friendly and green
The preparation method of tin mercaptides compound, it comprises the following steps:
(1) stannum: metallic tin and catalyst are put in pressure acid-resistant reacting kettle, then passes to chloromethanes 150-170 DEG C of temperature
Heat mix homogeneously under degree, after carrying out halogenation 0.2-0.4h, add reallocation agent and be warmed up to 235-245 DEG C, pressurization
Carry out stannumization to 0.5-0.8MPa to react after 1-2 hour, distill and accept gas temperature at 150-230 DEG C of interior fraction, then
Methyl tin chloride aqueous solution is obtained by absorbing pure water；Described methyl alkene chloride includes dimethyltin chloride and monomethyl three
Stannic chloride；
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, alkane
Diacid and regulator, stirring reaction 0.2-0.4 hour at temperature 5-15 DEG C, add alkali liquor and the resistance to yellow continuously stirred reaction of agent
Until pH value of reaction system reaches 7-9, then heat to 60-70 DEG C, during intensification, add according to sequencing and account for sulfydryl second
First solid additive of the 1-3% of the different monooctyl ester weight of acid adds with second solid of the 3-6% accounting for isooctyl thioglycolate weight
Agent；React 3-4 hour, static, lower the temperature, be layered；
Described metallic tin, chloromethanes, reallocation agent, regulator, the mol ratio of isooctyl thioglycolate are 1:(1.5-2): (0.2-
0.5): (0.1-0.3): (3-4)；
By mass parts, described regulator includes that first composite regulator 6-9 part, second composite regulator 7-11 part and the 3rd are compound
Regulator 8-14 part；
Described first composite regulator is by tricaprylmethyl ammonium bromide, glycerol and poly-four of the proportioning of 1:3-4:1-2 in mass ratio
Fluorothene forms；
Described second composite regulator is by the diphenylamines of the proportioning of 1:2-4:1-3 in mass ratio, 2,6-di-t-butyl and benzo three nitrogen
Azoles forms；
Described 3rd composite regulator is by the sulfuration Oleum Gossypii semen T404 of the proportioning of 1:0.5-0.8:1.3-1.7 in mass ratio, two (2-mercaptos
Base-4-n-propylamine base-1,3,5-triazine) thioether and two (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition；
(3) washing: separate organic facies and wash 1-2 time；
(4) distillation: obtain Methyl stannum mercaptide compound after vacuum distillation drying.
The Methyl stannum mercaptide compound finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and corrdination type sulfur
Alcohol methyl tin compoundThe mixture of composition, wherein diformazan
The quality accounting of base stannum is 40-60%.
The present invention uses specific stannum, synthesis technique, especially controls distillation and accepts gas temperature at 150-230 DEG C
In fraction, be more beneficial for the carrying out of follow-up synthetic reaction, make steady as stabilizer for plastics of finally prepd methyl stannum material
Determine effect more preferable.There is after regulator proportioning of the present invention dispersion and the stability of excellence；Described second composite regulator
There is after proportioning antioxidation and bright and clean corrosion-resistant function；Two kinds of composite regulators are combined and can be reached Synergistic and make
With；Make methyl stannum material more preferable as the stablizing effect of stabilizer for plastics, increase color inhibition effect.
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 resistance to yellow agent prescription includes, 20-66 part dimer (fatty acid) yl, 5-18 part vegetable oil acid, 5-25 part
Fatty amine, 10-34 part ketone, 5-20 part ethers, 0.01-0.02 part terminator；Described vegetable oil acid is castor oil acid, cotton oil
Acid, the one in Semen Allii Tuberosi oleic acid or behenic acid, described fatty amine is ethylenediamine, diethylenetriamine, triethylene tetramine, four ethylene five
Amine or the one of mixed amine, described mixed amine is mixing two or more in aminoethyl ethanolamine, aminoethyl piperazine or triethylene tetramine,
Described terminator is quinone, nitro polyol, nitroso-group polyol, aryl polyol or the one of boric acid
Kind；
Ketone in described resistance to yellow agent prescription is acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl fourth
One in base ketone or 1-Phenylethanone., described ethers is in ether, butyl cellosolve, ethylene glycol monobutyl ether or ethyl methyl ether
Kind.
As preferably, described resistance to yellow agent is 0.15-0.25:1 with the mol ratio of isooctyl thioglycolate.
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 material more preferable as the stablizing effect of stabilizer for plastics.
As preferably, described second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide compares 1:1-according to molal weight
The mixture of 4 compositions.
Use the carrying out of the present invention specific second catalyst beneficially synthetic reaction, make finally prepd methyl stannum material
Stablizing effect as stabilizer for plastics is more preferable.
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.
In first solid additive, Mw is weight average molecular weight, and Mn is number-average molecular weight.
Different-grain diameter and the first solid additive of kind and the second solid additive are increasing methyl stannum stability, reduction
While Theil indices, moreover it is possible to give methyl stannum more preferable resistance to volatilization precipitation property.
As preferably, described alkane two tart flavour malonic acid or succinic acid or 1,3-propanedicarboxylic acid.
Detailed description of the invention
Embodiment one
The preparation method of the Methyl stannum mercaptide compound of environment-friendly and green, it 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 be tetrabutyl ammonium bromide and
The mixture that dimethyl sulfide forms than 1:2 according to molal weight；The weight of the first catalyst accounts for the 1% of metallic tin weight.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, add the second catalyst,
Regulator and 1,3-propanedicarboxylic acid, stirring reaction 0.2 hour at temperature 5 DEG C, adds alkali liquor that mass fraction is 10% and resistance to yellow agent is held
Continuous stirring reaction, until pH value of reaction system reaches 7, then heats to 60 DEG C, during intensification, adds according to sequencing and accounts for
First solid additive of the 1% of isooctyl thioglycolate weight adds with the second solid of account for isooctyl thioglycolate weight 6%
Add agent；React 3 hours, static, lower the temperature, be layered；1,3-propanedicarboxylic acid weight accounts for the 8% of isooctyl thioglycolate weight；
Resistance to yellow agent is 0.2:1 with the mol ratio of isooctyl thioglycolate.
Resistance to yellow agent prescription includes, 20 parts of dimer (fatty acid) yls, 5 parts of vegetable oil acids, 5 parts of fatty amines, 10 parts of ketones, 5 parts of ethers
Class, 0.02 part of terminator；Vegetable oil acid is castor oil acid, cotton oil acid, the one in Semen Allii Tuberosi oleic acid or behenic acid, and fatty amine is
Ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or the one of mixed amine, mixed amine is aminoethyl ethanolamine, aminoethyl
Mixing two or more in piperazine or triethylene tetramine, terminator is quinone, nitro polyol, nitroso-group polyhydroxy chemical combination
Thing, aryl polyol or the one of boric acid；
Ketone in resistance to yellow agent prescription is acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl butyl ketone
Or the one in 1-Phenylethanone., ethers be the one in ether, butyl cellosolve, ethylene glycol monobutyl ether or ethyl methyl ether.
The mixture that second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide forms than 1:1 according to molal weight；
The weight of the second catalyst accounts for the 6% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, regulator, the mol ratio of isooctyl thioglycolate are 1:1.5:0.2:
0.1:4；
Regulator includes the first composite regulator 6 parts, the second composite regulator 11 parts and the 3rd composite regulator 8 by mass parts
Part；
First composite regulator is by tricaprylmethyl ammonium bromide, glycerol and the politef group of the proportioning of 1:3:2 in mass ratio
Become；
Second composite regulator is made up of the diphenylamines of the proportioning of 1:2:3 in mass ratio, 2,6-di-t-butyl and BTA；
3rd composite regulator is by the sulfuration Oleum Gossypii semen T404 of the proportioning of 1:0.5:1.7 in mass ratio, two (2-sulfydryl-4-n-propylamines
Base-1,3,5-triazine) thioether and two (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition；
(3) washing: separate organic facies and wash 1 time；
(4) distillation: obtain Methyl stannum mercaptide compound after vacuum distillation drying.
The Methyl stannum mercaptide compound finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and corrdination type sulfur
Alcohol methyl tin compoundThe mixture of composition, wherein diformazan
The quality accounting of base stannum is 40%.
Embodiment two
The preparation method of the Methyl stannum mercaptide compound of environment-friendly and green, it 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 be tetrabutylammonium chloride and
The mixture that dimethyl sulfide forms than 1:3 according to molal weight；The weight of the first catalyst accounts for the 3% of metallic tin weight.
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, add the second catalyst,
Regulator and malonic acid, stirring reaction 0.4 hour at temperature 15 DEG C, add alkali liquor and resistance to yellow agent that mass fraction is 20%
Continuously stirred reaction, until pH value of reaction system reaches 9, then heats to 70 DEG C, during intensification, adds according to sequencing
Account for isooctyl thioglycolate weight 3% the first solid additive and account for isooctyl thioglycolate weight 3% the second solid
Additive；React 4 hours, static, lower the temperature, be layered；Malonic acid weight accounts for the 8% of isooctyl thioglycolate weight；
Resistance to yellow agent is 0.15:1 with the mol ratio of isooctyl thioglycolate.
Resistance to yellow agent prescription includes, 66 parts of dimer (fatty acid) yls, 18 parts of vegetable oil acids, 25 parts of fatty amines, 34 parts of ketones, 20 parts
Ethers, 0.01 part of terminator；Vegetable oil acid is castor oil acid, cotton oil acid, the one in Semen Allii Tuberosi oleic acid or behenic acid, and fatty amine is
Ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or the one of mixed amine, mixed amine is aminoethyl ethanolamine, aminoethyl
Mixing two or more in piperazine or triethylene tetramine, terminator is quinone, nitro polyol, nitroso-group polyhydroxy chemical combination
Thing, aryl polyol or the one of boric acid；
Ketone in resistance to yellow agent prescription is acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl butyl ketone
Or the one in 1-Phenylethanone., ethers be the one in ether, butyl cellosolve, ethylene glycol monobutyl ether or ethyl methyl ether.
The mixture that second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide forms than 1:4 according to molal weight；
The weight of the second catalyst accounts for the 9% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, regulator, the mol ratio of isooctyl thioglycolate are 1:2:0.5:
0.2:3；
Regulator includes the first composite regulator 9 parts, the second composite regulator 7 parts and the 3rd composite regulator 14 by mass parts
Part；
First composite regulator is by tricaprylmethyl ammonium bromide, glycerol and the politef of the proportioning of 1:4:1 in mass ratio
Composition；
Second composite regulator is made up of the diphenylamines of the proportioning of 1:4:1 in mass ratio, 2,6-di-t-butyl and BTA；
3rd composite regulator is by the sulfuration Oleum Gossypii semen T404 of the proportioning of 1:0.8:1.3 in mass ratio, two (2-sulfydryl-4-n-propylamines
Base-1,3,5-triazine) thioether and two (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition；
(3) washing: separate organic facies and wash 2 times；
(4) distillation: obtain Methyl stannum mercaptide compound after vacuum distillation drying.
The Methyl stannum mercaptide compound finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and corrdination type sulfur
Alcohol methyl tin compoundThe mixture of composition, wherein diformazan
The quality accounting of base stannum is 60%.
Embodiment three
The preparation method of the Methyl stannum mercaptide compound of environment-friendly and green, it 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 tricaprylmethyl chlorination
The mixture that ammonium and dimethyl sulfide form than 1:2.5 according to molal weight；The weight of the first catalyst accounts for metallic tin weight
2%。
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, add the second catalyst,
Regulator and succinic acid, stirring reaction 0.3 hour at temperature 10 DEG C, add alkali liquor and resistance to yellow agent that mass fraction is 15%
Continuously stirred reaction, until pH value of reaction system reaches 8, then heats to 65 DEG C, during intensification, adds according to sequencing
Account for isooctyl thioglycolate weight 2% the first solid additive and account for isooctyl thioglycolate weight 4% the second solid
Additive；React 3.5 hours, static, lower the temperature, be layered；Succinic acid weight accounts for the 6% of isooctyl thioglycolate weight；
Resistance to yellow agent is 0.25:1 with the mol ratio of isooctyl thioglycolate.
Resistance to yellow agent prescription includes, 46 parts of dimer (fatty acid) yls, 13 parts of vegetable oil acids, 15 parts of fatty amines, 24 parts of ketones, 5-20
Part ethers, 0.015 part of terminator；Vegetable oil acid is castor oil acid, cotton oil acid, the one in Semen Allii Tuberosi oleic acid or behenic acid, fat
Amine is ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or the one of mixed amine, and mixed amine is aminoethyl ethanolamine, ammonia
Mixing two or more in ethyl piperazidine or triethylene tetramine, terminator is quinone, nitro polyol, nitroso-group polyhydroxy
Compound, aryl polyol or the one of boric acid；
Ketone in resistance to yellow agent prescription is acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl butyl ketone
Or the one in 1-Phenylethanone., ethers be the one in ether, butyl cellosolve, ethylene glycol monobutyl ether or ethyl methyl ether.
The mixture that second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide forms than 1:3 according to molal weight；
The weight of the second catalyst accounts for the 8% of isooctyl thioglycolate weight；
Metallic tin, chloromethanes, reallocation agent butter of tin, regulator, the mol ratio of isooctyl thioglycolate are 1:1.8:0.3:
0.3: 3.5；
Regulator includes the first composite regulator 8 parts, the second composite regulator 9 parts and the 3rd composite regulator 12 by mass parts
Part；
First composite regulator is by tricaprylmethyl ammonium bromide, glycerol and the polytetrafluoroethyl-ne of the proportioning of 1:3.5:1.5 in mass ratio
Alkene forms；
Second composite regulator is made up of the diphenylamines of the proportioning of 1:3:2 in mass ratio, 2,6-di-t-butyl and BTA；
3rd composite regulator is by the sulfuration Oleum Gossypii semen T404 of the proportioning of 1:0.6:1.5 in mass ratio, two (2-sulfydryl-4-n-propylamines
Base-1,3,5-triazine) thioether and two (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition；
(3) washing: separate organic facies and wash 1 time；
(4) distillation: obtain Methyl stannum mercaptide compound after vacuum distillation drying.
The Methyl stannum mercaptide compound finally obtained is (CH3)2Sn(SCH2CO2C8H17)2(stannous methide) and corrdination type sulfur
Alcohol methyl tin compoundThe mixture of composition, wherein diformazan
The quality accounting of base stannum is 50%.
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 4% 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:
Product comparative example one prepared is enterprising in PVC sheet with the products application in embodiment one to embodiment six respectively
Row static burn in is tested, and the amount adding heat stabilizer is 0.8%, and the PVC sheet made, 180 DEG C of insulations, was stayed every ten minutes
Sample is standby, until all of sheet material all turns yellow, and used time 110 minutes altogether, all samples of sheets are made form, the most directly perceived
Obtain aging control experiment data, 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 compound of an environment-friendly and green, it is characterised in that it comprises the following steps:
(1) stannum: metallic tin and catalyst are put in reactor, then passes to chloromethanes and heat at a temperature of 150-170 DEG C
Mix homogeneously, after carrying out halogenation 0.2-0.4h, adds reallocation agent and is warmed up to 235-245 DEG C, is forced into 0.5-
0.8MPa carries out stannumization and reacts after 1-2 hour, distills and accepts gas temperature at 150-230 DEG C of interior fraction, then using pure water
Absorb and obtain methyl tin chloride aqueous solution；Described methyl alkene chloride includes dimethyltin chloride and monomethyl tri-chlorination
Stannum；
(2) synthesis: gained methyl tin chloride aqueous solution is added in isooctyl thioglycolate, adds the second catalyst, alkane
Diacid and regulator, stirring reaction 0.2-0.4 hour at temperature 5-15 DEG C, add alkali liquor and the resistance to yellow continuously stirred reaction of agent
Until pH value of reaction system reaches 7-9, then heat to 60-70 DEG C, during intensification, add according to sequencing and account for sulfydryl second
First solid additive of the 1-3% of the different monooctyl ester weight of acid adds with second solid of the 3-6% accounting for isooctyl thioglycolate weight
Agent；React 3-4 hour, static, lower the temperature, be layered；
Described metallic tin, chloromethanes, reallocation agent, regulator, the mol ratio of isooctyl thioglycolate are 1:(1.5-2): (0.2-
0.5): (0.1-0.3): (3-4)；
By mass parts, described regulator includes that first composite regulator 6-9 part, second composite regulator 7-11 part and the 3rd are compound
Regulator 8-14 part；
Described first composite regulator is by tricaprylmethyl ammonium bromide, glycerol and poly-four of the proportioning of 1:3-4:1-2 in mass ratio
Fluorothene forms；
Described second composite regulator is by the diphenylamines of the proportioning of 1:2-4:1-3 in mass ratio, 2,6-di-t-butyl and benzo three nitrogen
Azoles forms；
Described 3rd composite regulator is by the sulfuration Oleum Gossypii semen T404 of the proportioning of 1:0.5-0.8:1.3-1.7 in mass ratio, two (2-mercaptos
Base-4-n-propylamine base-1,3,5-triazine) thioether and two (2-sulfydryl-4-Aminocyclopentane base-1,3,5-triazine) thioether composition；
(3) washing: separate organic facies and wash 1-2 time；
(4) distillation: obtain Methyl stannum mercaptide compound after vacuum distillation drying.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 1, its feature exists
In: described resistance to yellow agent prescription includes, 20-66 part dimer (fatty acid) yl, 5-18 part vegetable oil acid, 5-25 part fatty amine, 10-34 part
Ketone, 5-20 part ethers, 0.01-0.02 part terminator；Described vegetable oil acid is castor oil acid, cotton oil acid, Semen Allii Tuberosi oleic acid or bean
One in oleic acid, described fatty amine is ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or the one of mixed amine,
Described mixed amine is mixing two or more in aminoethyl ethanolamine, aminoethyl piperazine or triethylene tetramine, described terminator be quinone,
Nitro polyol, nitroso-group polyol, aryl polyol or the one of boric acid；
Ketone in described resistance to yellow agent prescription is acetone, butanone, Ketohexamethylene, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, methyl fourth
One in base ketone or 1-Phenylethanone., described ethers is in ether, butyl cellosolve, ethylene glycol monobutyl ether or ethyl methyl ether
Kind.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 2, it is characterised in that:
The mixing that described first catalyst is quaternary ammonium salt-type phase transfer catalyst and dimethyl sulfide forms than 1:2-3 according to molal weight
Thing.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 3, it is characterised in that:
The mixture that described second catalyst is phthalic acid dibutyl ester and dimethyl sulfoxide forms than 1:1-4 according to molal weight.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 3, it is characterised in that:
Described quaternary ammonium salt phase catalyst is tetrabutyl ammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate or tricaprylmethyl chlorine
Change ammonium.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 5, it is characterised in that:
Described reallocation agent is butter of tin.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 3, it is characterised in that:
The weight of described first catalyst accounts for the 1-3% of metallic tin weight.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 4, it is characterised in that:
The weight of described second catalyst accounts for the 6-9% of isooctyl thioglycolate weight.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 6, it is characterised in that:
In described step (2), the mass fraction of alkali liquor is 10-20%.
The preparation method of the Methyl stannum mercaptide compound of a kind of environment-friendly and green the most according to claim 6, its feature exists
In: the particle size range of the first solid additive is 0.8-5 micron；Wherein, the granule of 0.8-1 micron accounts for described first solid interpolation
The 20-40% of agent gross weight；The granule of 1-2 micron accounts for the 10-30% of described first solid additive gross weight；Surplus is 3-5 micron
Granule；
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.
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