CN107033183A - The preparation technology and its product of Methyl stannum mercaptide, application - Google Patents
The preparation technology and its product of Methyl stannum mercaptide, application Download PDFInfo
- Publication number
- CN107033183A CN107033183A CN201710318842.5A CN201710318842A CN107033183A CN 107033183 A CN107033183 A CN 107033183A CN 201710318842 A CN201710318842 A CN 201710318842A CN 107033183 A CN107033183 A CN 107033183A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- stannum mercaptide
- methyl stannum
- aminoethyls
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Methyl stannum Chemical compound 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000005516 engineering process Methods 0.000 title claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 63
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 32
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000026030 halogenation Effects 0.000 claims abstract description 20
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 20
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 19
- 238000006073 displacement reaction Methods 0.000 claims abstract description 18
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 108
- 238000006243 chemical reaction Methods 0.000 claims description 100
- 239000003054 catalyst Substances 0.000 claims description 95
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 38
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 claims description 34
- 229920001661 Chitosan Polymers 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 25
- 239000004800 polyvinyl chloride Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 19
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims description 19
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 17
- 235000014121 butter Nutrition 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 5
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 5
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- QICVZJNIJUZAGZ-UHFFFAOYSA-N benzene;phosphorous acid Chemical compound OP(O)O.C1=CC=CC=C1 QICVZJNIJUZAGZ-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical class CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical class CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- AVYPEYYPGYMFDO-UHFFFAOYSA-N 1,3,5-tributylbenzene Chemical class CCCCC1=CC(CCCC)=CC(CCCC)=C1 AVYPEYYPGYMFDO-UHFFFAOYSA-N 0.000 description 1
- DYULYMCXVSRUPB-UHFFFAOYSA-N 1,4-bis(phenylmethoxy)benzene Chemical class C=1C=CC=CC=1COC(C=C1)=CC=C1OCC1=CC=CC=C1 DYULYMCXVSRUPB-UHFFFAOYSA-N 0.000 description 1
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical class CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- OTJZMNIBLUCUJZ-UHFFFAOYSA-N 2,4-diphenyl-1,3,5-triazine Chemical compound C1=CC=CC=C1C1=NC=NC(C=2C=CC=CC=2)=N1 OTJZMNIBLUCUJZ-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical class CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- HVRGFWZLHOKCGE-UHFFFAOYSA-N 2,6-dibutyl-4-ethylphenol Chemical class CCCCC1=CC(CC)=CC(CCCC)=C1O HVRGFWZLHOKCGE-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical class CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- FANGQVKSFHFPBY-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FANGQVKSFHFPBY-UHFFFAOYSA-N 0.000 description 1
- SGHSRBYSXCNJLP-UHFFFAOYSA-N 2-methyl-4,6-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC(C)=C(O)C(CCCCCCCCC)=C1 SGHSRBYSXCNJLP-UHFFFAOYSA-N 0.000 description 1
- 150000004786 2-naphthols Chemical class 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical class CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical class CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical class CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- VYIBCOSBNVFEIW-UHFFFAOYSA-N 3-phenylpropanamide Chemical compound NC(=O)CCC1=CC=CC=C1 VYIBCOSBNVFEIW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
- DBOSBRHMHBENLP-UHFFFAOYSA-N 4-tert-Butylphenyl Salicylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O DBOSBRHMHBENLP-UHFFFAOYSA-N 0.000 description 1
- YEQHNTCMAVPEKP-UHFFFAOYSA-N 6-methylheptyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCC(C)C)OC1=CC=CC=C1 YEQHNTCMAVPEKP-UHFFFAOYSA-N 0.000 description 1
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 240000003291 Armoracia rusticana Species 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical class [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- ZUOAYNYBICLREW-UHFFFAOYSA-N chloromethane;tin Chemical compound [Sn].ClC ZUOAYNYBICLREW-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 1
- POWRQOUEUWZUNQ-UHFFFAOYSA-N didecyl phosphite Chemical compound CCCCCCCCCCOP([O-])OCCCCCCCCCC POWRQOUEUWZUNQ-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 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 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical class [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to preparation technology and its product, the application of a kind of preparation method of organic tin material, more particularly to a kind of Methyl stannum mercaptide.The preparation technology of Methyl stannum mercaptide is specifically disclosed, is at least comprised the following steps：Step 1：Alkane halogenation；Step 2：Displacement reaction；Step 3：Esterification；Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；Mol ratio between the metallic tin powder, monochloro methane, isooctyl thioglycolate is：1：(1.2~1.5)：5.
Description
Technical field
The present invention relates to a kind of preparation method of organic tin material, more particularly to a kind of preparation technology of Methyl stannum mercaptide
And its product, application.
Background technology
The method of production organotin mainly has Grignard, Wu Zifa, alkyl aluminum method and direct iodine method, grignard both at home and abroad at present
Fado is used with American-European countries, and military hereby method has realized industrialized production in the U.S. and East Germany, and alkyl aluminum method is also adopted in East Germany
With.Direct iodine method is in Japanese extensive use.Grignard advantage is that product form can be controlled at any time, but step is more, and grignard
React for exothermic reaction, solvent boiling point is very low, thus must Cautious control temperature and reaction speed, to avoid blast；Though iodine method
Right step is few compared with grignard, but must enter the recovery of professional etiquette, and two methods have in common that magnesium metal, iodine and feed metal tin
Price is all more expensive, and wherein organic tin chloride toxicity is higher, therefore the method for not using iodide is sought in general industry production.ke
Commissioning
Methyl tin is short due to its carbochain, no tertiary carbon, quaternary carbon atom, is difficult to be alkylated reaction or bar using the above method
Part is extremely harsh, and the not scale application in actual production.Current industrial method mainly uses chemical raw material 1 and metal
Tin direct alkylation reaction generation methyl chloride tin under high temperature, high pressure, catalysts conditions.This method has process simple, straight
The advantage connect, but there is reaction controlling difficulty greatly, high shortcoming is required to reactor.ke Commissioning ke Commissioning
In organic tin heat stabilizer, conventional has tin octylate, butyl tin, ester group tin, methyl tin, although four kinds organic
Tin respectively has its feature and advantage, but by contrast, methyl tin has distinctive feature:During with prominent suppression PVC product processing
Early stage tinctorial property, remarkable UV resistant and long-time stability；With good mobility, color and luster retentivity during processing
It is good, product excellent transparency；Particularly its photo and thermal stability is reached the international leading level, and can effectively realize that secondary operation is recycled
Use；Because it does not have toxicity, consumption is few, and thermal stability is excellent, and compatibility is strong, good processability.In polyvinyl chloride resin only
Add 1% or so amount, so that it may so that PVC product become water white transparency, it is sparkling and crystal-clear bright, therefore, use methyl tin used as stabilizers
PVC sheet be widely used in the packaging of food, medicine and beverage.
Thiol methyl tin production technology is to add catalyst one-step synthesis production technology.Experimental studies have found that, use S class chemical combination
Thing makees catalyst and there is problems with：Firstth, catalytic effect is not high, and a collection of reaction more than hour will could be completed at 8 substantially；
Secondth, usage cycles are too short, fail too fast, general with one month or so, catalyst failure, it is necessary to remove bed material, cause tin
A large amount of losses of material.Meanwhile, methyl tin (SM501) in the domestic market mainly contains the 20% trisulfides second of monomethyl tin
The different monooctyl ester of acid and 80% stannous methide curing 2-ethyl hexyl ethanoate, need to adjust tri-thiol 2-ethyl hexyl ethanoate according to different situations
The content of methyl tin and dimercapto 2-ethyl hexyl ethanoate stannous methide.For above-mentioned situation, it is necessary to the catalyst that selection is more applicable,
Could preferably it solve the above problems.ke Commissioning
The content of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides the preparation technology of Methyl stannum mercaptide, extremely
Comprise the following steps less：
Step 1：Alkane halogenation：Metallic tin powder, the first catalyst are added in reactor, then led into reactor
Enter monochloro methane, rise reaction temperature carries out alkane 5~10h of halogenation, obtain dimethyltin chloride to 150~180 DEG C；
Step 2：Displacement reaction：Butter of tin is added into step 1, rise reaction temperature is forced into 220~230 DEG C
0.5MPa, enters line replacement reaction, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl tri-chlorination
Tin and the dimethyltin chloride aqueous solution；
Step 3：Esterification：The monomethyl tin trichloride obtained in step 2 and the dimethyltin chloride aqueous solution are added
Enter to sequentially add the second catalyst, isooctyl thioglycolate, 5~20min of stirring reaction in the case where reaction temperature is 20~30 DEG C, so
After add N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, the stirring reaction 20 at 30~50 DEG C
~60min, and it is 7 to adjust the pH value of reaction, then at 40 DEG C, 4~5h of stirring reaction, static, cooling, layering；Isolate
Organic layer, water-filling of going forward side by side is washed 1~3 time；Second catalyst is TBAB, bi-tristearin, dimethyl Asia
The mixture of sulfone；
Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；
Mol ratio between the metallic tin powder, monochloro methane, isooctyl thioglycolate is：1：(1.2~1.5)：5.
As a kind of preferred technical scheme of the present invention, first catalyst is hexadecyltrimethylammonium chloride and shell
The weight ratio of glycan compound, hexadecyltrimethylammonium chloride and chitosan is 10：1.
As a kind of preferred technical scheme of the present invention, the metallic tin powder and the weight ratio of the first catalyst are：100：
(0.1~5).
As a kind of preferred technical scheme of the present invention, in second catalyst, TBAB, double stearic acid are sweet
Weight ratio between grease, the mixture of dimethyl sulfoxide (DMSO) is：1：(1~5)：(10~15).
As a kind of preferred technical scheme of the present invention, the isooctyl thioglycolate and N- (2- aminoethyls) -3- ammonia third
Weight ratio between base trimethoxy silane improved silica is 100：(1~8).
As a kind of preferred technical scheme of the present invention, N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes change
Property silica in, weight ratios of the N- (2- aminoethyls) between -3- aminopropyl trimethoxysilanes and silica for (1~
10)：3.
As a kind of preferred technical scheme of the present invention, N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes change
Weight ratio between property silica and the second catalyst is：1：(0.1~1).
The second aspect of the invention provides Methyl stannum mercaptide, is obtained using above-mentioned preparation method.
The third aspect of the invention provides environment-friendly type PVC, and the environment-friendly type PVC in parts by weight, at least includes,
100 parts of polyvinyl chloride resin；
0.1~0.5 part of Methyl stannum mercaptide；
0.1~0.5 part of auxiliary agent；
The fourth aspect of the invention provides application of the Methyl stannum mercaptide in rubber, plastics, catalyst field.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this public affairs can be more easily understood
Open content.A large amount of terms can be referred in description below and claims, these terms are defined as following meanings.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device." optionally " or " optionally " refer to describe thereafter
Item or event may or may not occur, and the description includes the situation and the situation that does not occur of event that event occurs.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
In order to solve the above-mentioned technical problem, the first aspect of the invention provides the preparation technology of Methyl stannum mercaptide, extremely
Comprise the following steps less：
Step 1：Alkane halogenation：Metallic tin powder, the first catalyst are added in reactor, then led into reactor
Enter monochloro methane, rise reaction temperature carries out alkane 5~10h of halogenation, obtain dimethyltin chloride to 150~180 DEG C；
Step 2：Displacement reaction：Butter of tin is added into step 1, rise reaction temperature is forced into 220~230 DEG C
0.5MPa, enters line replacement reaction, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl tri-chlorination
Tin and the dimethyltin chloride aqueous solution；
Step 3：Esterification：The monomethyl tin trichloride obtained in step 2 and the dimethyltin chloride aqueous solution are added
Enter to sequentially add the second catalyst, isooctyl thioglycolate, 5~20min of stirring reaction in the case where reaction temperature is 20~30 DEG C, so
After add N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, the stirring reaction 20 at 30~50 DEG C
~60min, and it is 7 to adjust the pH value of reaction, then at 40 DEG C, 4~5h of stirring reaction, static, cooling, layering；Isolate
Organic layer, water-filling of going forward side by side is washed 1~3 time；Second catalyst is TBAB, bi-tristearin, dimethyl Asia
The mixture of sulfone；
Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；
Mol ratio between the metallic tin powder, monochloro methane, isooctyl thioglycolate is：1：(1.2~1.5)：5.
Step 1
The step 1 of the present invention is carries out alkane halogenation, and detailed process is：
Metallic tin powder, the first catalyst are added in reactor, monochloro methane is then passed through into reactor, rise is anti-
Temperature is answered to 150~180 DEG C, alkane 5~10h of halogenation is carried out, obtains dimethyltin chloride；
In the application, the metallic tin powder can be different shape, can be tin flower, or glass putty；Preferably tin
Powder.
In the application, first catalyst is hexadecyltrimethylammonium chloride and chitosan complexes；
Term " hexadecyltrimethylammonium chloride and chitosan complexes " refers to be grafted cetyl front three on chitosan
Ammonium chloride, obtained compound.
In a preferred embodiment, the preparation side of the hexadecyltrimethylammonium chloride and chitosan complexes
Method comprises the following steps：
100g water, 1g chitosans are added in a kettle., after stirring at room temperature, add 10g cetyl front threes
Ammonium chloride, controlling reaction temperature be 20~45 DEG C, then add 0.1g sodium hydroxide, at 30~60 DEG C react 5~
After 12 hours, neutralized and used after ethanol cyclic washing with hydrobromic acid, suction filtration and dry hexadecyltrimethylammonium chloride and shell
Glycan compound.
In first catalyst, the weight ratio of hexadecyltrimethylammonium chloride and chitosan is 10：1.
The chitosan refers to the chitosan that deacetylation is 80%.
In a preferred embodiment, the metallic tin powder and the weight ratio of the first catalyst are：100：0.1.
The specific chemical reaction occurred in step 1 is：
Inventor has found that the first catalyst of the application can improve the conversion ratio of metallic tin powder, to improve metallic tin powder
Utilization rate, meanwhile, the present inventor is found surprisingly that, by adjust the first catalyst usage amount can adjust monomethyl trichlorine
Change the weight ratio of tin and dimethyltin chloride, with the increase of the usage amount of the first catalyst, dimethyltin chloride contains
Amount increase, and then the trisulfides 2-ethyl hexyl ethanoate of monomethyl tin and diformazan of product can be controlled by the usage amount of the first catalyst
Base tin curing 2-ethyl hexyl ethanoate ratio.Meanwhile, it can also suppress side reaction using the first catalyst：Sn+SnCl4→2SnCl2
Generation.
Step 2
The step 2 of the present invention is that, into line replacement reaction, detailed process is：
Butter of tin is added into step 1, rise reaction temperature is forced into 0.5MPa, enters line replacement to 220~230 DEG C
Reaction, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl tin trichloride and dimethyl dichloride
The tin aqueous solution；
The specific chemical reaction occurred in step 2 is：
(CH3)2SnCl2+SnCl4→2CH3SnCl3。
In the step 2 of the application, will not substantially occur side reaction, will not especially occur Sn+SnCl4→2 SnCl2,
Substantially increase the utilization rate of raw material.
Step 3
The step 3 of the present invention is carries out esterification, and detailed process is：
The monomethyl tin trichloride obtained in step 2 and the addition of the dimethyltin chloride aqueous solution are sequentially added second and urged
Agent, isooctyl thioglycolate, 5~20min of stirring reaction in the case where reaction temperature is 20~30 DEG C, then add N- (2- ammonia
Ethyl) -3- aminopropyl trimethoxysilane improved silicas, 20~60min of stirring reaction at 30~50 DEG C, and adjust anti-
The pH value answered is 7, then at 40 DEG C, 4~5h of stirring reaction, static, cooling, layering；Organic layer is isolated, water-filling of going forward side by side is washed
1~3 time；Second catalyst is TBAB, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)；
Term " N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes improved silica " refer to N- (2- aminoethyls) -
3- aminopropyl trimethoxysilanes are to silica surface graft modification.In the application, N- (2- aminoethyls) -3- aminopropyls are added
In the esterification reaction, one side can interact trimethoxy silane improved silica with the second catalyst, improve
The service life of second catalyst, the number of times that increase repetitive cycling is used, plays a part of co-catalysis；Second aspect can be carried
The catalytic efficiency of high second catalyst, improves the conversion ratio of monomethyl tin trichloride and dimethyltin chloride, while can inhale
The hydrogen chloride produced in reaction system is received, promotes reaction forward to carry out.
In a preferred embodiment, N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes are modified dioxy
The preparation process of SiClx comprises the following steps：
In the reactor, solvent 100ml toluene and 1g nano silicons, ultrasonic disperse 10min are added, N- is then added
(2- aminoethyls) -3- aminopropyl trimethoxysilanes, add the triethylamine solution that volumetric concentration is 10%, are flowed back at 100 DEG C
2h is reacted, filtering, ethanol is washed 3 times, be dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes and be modified titanium dioxide
Silicon.
In a preferred embodiment, the isooctyl thioglycolate and N- (2- aminoethyls) -3- aminopropyl front threes
Weight ratio between TMOS improved silica is 100：(1~8).
In a preferred embodiment, N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes are modified dioxy
In SiClx, the weight ratio between amino silicane coupling agent and silica is (1~10)：3.
In a preferred embodiment, in second catalyst, TBAB, bi-tristearin,
Weight ratio between the mixture of dimethyl sulfoxide (DMSO) is：1：(1~5)：(10~15)；Preferably, in second catalyst, four
Weight ratio between butylammonium bromide, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO) is：1：(2~4)：(12~14)；
Most preferably, in second catalyst, between TBAB, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)
Weight ratio be：1：3：13.
In a preferred embodiment, N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes are modified dioxy
Weight ratio between SiClx and the second catalyst is：1：(0.1~1).
The specific chemical reaction occurred in step 3 is：
(CH3)2SnCl2+2HSCH2COOC8H17→(CH3)2Sn(SCH2COOC8H17)2+2HCl；
2CH3SnCl3+3HSCH2COOC8H17→CH3Sn(SCH2COOC8H17)3+3HCl。
Finally Methyl stannum mercaptide is obtained through the distillation in step 4, drying process；
Mol ratio between the metallic tin powder, monochloro methane, isooctyl thioglycolate is：1：(1.2~1.5)：5.
The second aspect of the invention provides Methyl stannum mercaptide, is obtained using above-mentioned preparation method.
The third aspect of the invention provides environment-friendly type PVC, and the environment-friendly type PVC in parts by weight, at least includes,
100 parts of polyvinyl chloride resin；
0.1~0.5 part of Methyl stannum mercaptide；
0.1~0.5 part of auxiliary agent；
In the application, described Methyl stannum mercaptide synthesizes what is obtained using above-mentioned preparation method.
In the application, what described auxiliary agent can be enumerated has：Antioxidant, plasticizer, fire retardant, filler, ultraviolet radiation absorption
Agent, antiseptic, pigment, enter delustering agent, weather resisting agent, antistatic agent, anti-coloring agent etc..
What the antioxidant can be enumerated has：Phenolic antioxidant, phosphite ester kind antioxidant, containing in sulphur ester antioxidant
It is at least one.
Phenolic antioxidant can be enumerated：1- hydroxy-3-methyl -4- cumenes, 2,6- DI-tert-butylphenol compounds, the uncles of 2,6- bis-
Butyl -4- ethyl -phenols, BHT, 2,6- di-t-butyl -4- normal-butyls phenol, 4- methylols -2,6- bis-
Tert-butyl phenol, butylhydroxy anisole, 2- (1- methylcyclohexyls) -4,6- xylenols, the tertiary fourths of 2,4- dimethyl -6-
Base phenol, 2- methyl -4,6- dinonyl phenol, 2,6- di-t-butyls-alpha, alpha-dimethyl amino-p-cresol, 2,4,6- tri-butyl benzenes
Double (the octylsulfo) -1,3,5-triazines of phenol, 6- (4- hydroxyl -3,5- di-tert-butyls amido) -2,4-, 4,6- it is double (4- hydroxyl -3,
5- di-t-butyls phenoxy group) -2- n-octylthios -1,3,5-triazines, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid first
Ester, β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, styrenated phenol, 4,4 '-dihydroxy connection
Benzene, butylated octylated phenol, butylated stytrene cresols, 2,2 '-methylene bis (4- methyl-6-tert-butylphenols) or 2,
2 '-methylene bis (the 6- tert-butyl group -4- cresols), 2,2 '-methylene bis (4- ethyl -6- tert-butyl phenols), 2,2 '-methylene bis (4- first
Base -6- cyclohexylphenols), 4,4 '-methylene bis (2,6- DI-tert-butylphenol compounds), 2, (6- α-methylbenzyls are to first for 2 '-methylene bis
Phenol), 1,1- double (4- hydroxy benzenes) hexamethylene, 2,2 '-methylene bis (4- methyl -6- (Alpha-Methyl cyclohexyl) phenol) or 2,2 '-two
Hydroxyl -3,3 '-two (Alpha-Methyl cyclohexyl) -5,5 '-dimethyl diphenylmethane, 1,3,5- trimethyls -2,4,6- tri- (3,5- bis-
Tertiary butyl-4-hydroxy benzyl) benzene, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, four (3- (3 ' 5 '-two uncles
Butyl -4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols) or 4,4 '-thio
Double (6- tert-butyl-m-cresols), 4,4 '-thiobis (2- methyl-6-tert-butylphenols) or 4,4 '-thiobis (6- tert-butyl o first
Phenol), 2, the double (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid of 2 '-thiobis (4- methyl-6-tert-butylphenols), hexylene glycol
Ester), 2,2 '-thiobis (3 ,-(3,5- di-tert-butyl-hydroxy phenyl) ethyl propionate), N, double (3,5- bis- uncles of N '-hexamethylene
Butyl-4- hydroxyls hydrocinnamamide), 1,3,5- tri- (the 4- tert-butyl group-3- hydroxyls-2,6- dimethyl benzyls) 1,3,5-triazine-2,4,
6- (1H, 3H, 5H)-triketone, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) guanamines, 4,6- (1H, 3H, 5H) three
Ketone or isocyanuric acid three (3,5- di-tert-butyl-4-hydroxyl benzyl ester), [β-(3,5- di-t-butyl -4- hydroxy benzenes of isocyanuric acid three
Base) propionyloxy ethyl ester], double [3,3- double (3 '-tert-butyl group -4 '-hydroxy phenyl) butyric acid] glycol esters, 1,1 '-thiobis (2-
Naphthols), double (3,5- di-tert-butyl-4-hydroxyl benzyl) thioethers, 2,5- di-tert-butyl hydroquinones, the tertiary pentyls of 2,5- bis- are to benzene two
Phenol, 3,5- di-tert-butyl-4-hydroxyl benzyls di(2-ethylhexyl)phosphate (18) ester, 3,5- di-tert-butyl-4-hydroxyl benzyls diethyl phosphate, three
One kind in glycol double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester, hydroquinone dibenzyl ethers.
Phosphite ester kind antioxidant can be enumerated：Triphenyl phosphite, phosphorous acid three (nonyl phenyl ester), phosphorous acid three are different pungent
Ester, triisodecyl phosphite ester, the isodecyl ester of phosphorous acid benzene two, trilauryl trithiophosphite, trilauryl phosphite, phosphorous acid
Three (octadecyl esters), the isodecyl ester of diphosphorous acid pentaerythrite two, diphosphorous acid pentaerythrite distearyl alcohol ester, 4,4 '-fourth fork are double (sub-
Phosphoric acid (3- methyl-6-tert butyl phenyl) two (tridecyl) esters), isooctyl diphenyl phosphite, phosphorous acid benzene di-isooctyl, Asia
Diphenyl octyl phosphate, phosphorous acid hexichol isodecyl ester, dioctyl phosphite, phosphorous acid dilauryl, dimethylphosphite, phosphorous acid
Double 13 esters of two oleyl alcohol esters, didecyl phosphite, dibutyl phosphite, phosphorous acid, phosphorous acid double 14 esters, phosphorous triethylenetetraminehexaacetic acids
Ester, tributyl phosphite, triisopropyl phosphite, the monooctyl ester of phosphorous acid three or phosphorous acid three (2- ethylhexyls), phosphorous acid-benzene are double
One kind in (nonyl benzene) ester, phosphorous acid hexichol nonyl phenyl ester, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
It can be enumerated containing sulphur ester antioxidant：Dilauryl thiodipropionate, thio-2 acid 2 stearyl ester or thio
Dipropionic acid two (octadecyl ester), β, β '-thio two butyric acid two (18) ester, thio-2 acid bay octadecyl ester, thio-2 acid two
(13) ester, thio-2 acid two (14) ester are medium.
The plasticizer can be enumerated：Dioctyl phthalate, diisooctyl phthalate, terephthalic acid (TPA) two are pungent
One or more in ester, trioctyl trimellitate (TOTM) or di-n-octyl sebacate.And then preferred cold resistant plasticizer DOS (decanedioic acid
Dioctyl ester) or DOP (dioctyl phthalate) etc..
The fire retardant can be enumerated：It is brominated organic based flame retardant, phosphoric acid based flame retardant, antimony trioxide, magnesium hydroxide, red
Phosphorus etc..
The filler can be enumerated：Silica, aluminum oxide, kaolinite, wollastonite, mica, talcum, clay, sericite,
Magnesium carbonate, magnesium sulfate, calcium oxide, carborundum, antimony trisulphide, artificial gold, copper sulfide, iron sulfide, bismuth sulfide, zinc sulphide, metal
Powder, glass powder, glass flake, montmorillonite, glass microballoon etc..
What the ultra-violet absorber can be enumerated has：2- (2- hydroxy-5-methyl bases phenyl) BTA, 2- (2- hydroxyls-
5- butyl phenyls) BTA, 2- (2- hydroxyl -5- octyl phenyls) BTA, 2- (the 3- tert-butyl group -2- hydroxy-5-methyl base benzene
Base) the enumerate BTA system ultra-violet absorber such as -5- chlorobenzotriazoles, 2- (3,5- bis- tertiary pentyl -2- hydroxy phenyls) BTA；
The benzophenone series ultra-violet absorbers such as ESCALOL 567,2- hydroxyl -4- n-octyl epoxide benzophenone；
2- [4,6- double (2,4- 3,5-dimethylphenyl) -1,3,5-triazines -2- bases] -5- (octyl group epoxide) phenol, 2- (4,6- diphenyl -1,
3,5- triazine -2- bases) the triazine system ultra-violet absorber such as -5- (hexyl epoxide) phenol；P-t-butylphenyl salicylate, salicylic acid
The salicylate such as phenyl ester system ultra-violet absorber etc..
What the antiseptic can be enumerated has：Silver ion class antiseptic, zinc oxide, cupric oxide, ammonium dihydrogen phosphate, carbonic acid
Lithium, anilid class, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, double croak classes, phenols formic acid, sorbic acid, have
Machine iodine, nitrile, sulphur cyanogen, copper agent, three halogenation allyl compounds, organic nitrogen sulfur compound, chitin, mustard, castor oil, horseradish
Deng.
In a preferred embodiment, the preparation method of the environment-friendly type PVC, comprises the following steps：
By the polyvinyl chloride resin, Methyl stannum mercaptide, auxiliary agent of corresponding parts by weight, melting mixing is carried out at 140~190 DEG C, through screw rod
Extruder for shaping.
In the application, the thermally-stabilised principle of Methyl stannum mercaptide is divided into lower two steps, first step reaction：The tin of organic tin stabilizer is former
With polyvinyl chloride molecule unstable chlorine atom ligand complex occurs for son, while the sulphur atom carbon corresponding with PVC in organotin
Atom is complexed；Second step reacts：The sulphur atom of organotin is replaced with unstable chlorine atom in ligand, is deposited when there is HC1
When, coordinate bond divides, and sulfydryl is securely joined with carbon atom in PVC molecules, thus inhibit further take off HCl formed
The reaction of double bond.
The fourth aspect of the invention provides application of the Methyl stannum mercaptide in rubber, plastics, catalyst field.
The present invention is specifically described below by embodiment.It is necessarily pointed out that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used be all it is commercially available,
Embodiment 1：
The present embodiment 1 provides a kind of Methyl stannum mercaptide, and the preparation technology of the Methyl stannum mercaptide comprises the following steps：
Step 1：Alkane halogenation：Metallic tin powder, the first catalyst are added in reactor, then led into reactor
Enter monochloro methane, rise reaction temperature carries out alkane halogenation 8h, obtain dimethyltin chloride to 150 DEG C；Described first urges
Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2：Displacement reaction：Butter of tin is added into step 1, rise reaction temperature is forced into 220 DEG C
0.5MPa, after entering line replacement reaction 3 hours, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl
Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3：Esterification：The monomethyl tin trichloride obtained in step 2 and the dimethyltin chloride aqueous solution are added
Enter to sequentially add the second catalyst, isooctyl thioglycolate, the stirring reaction 5min in the case where reaction temperature is 30 DEG C, then add
N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, the stirring reaction 20min at 30 DEG C, and adjust anti-
The pH value answered is 7, then at 40 DEG C, stirring reaction 1h, static, cooling, layering；Organic layer is isolated, water-filling of going forward side by side washes 3
It is secondary；
Second catalyst is chitosan, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)；
Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；
Mol ratio between the metallic tin powder, monochloro methane, butter of tin, isooctyl thioglycolate is：1：1.2：2：
5。
The metallic tin powder and the weight ratio of the first catalyst are：100：0.1；
The preparation process of first catalyst is as follows：
100g water, 1g chitosans are added in a kettle., after stirring at room temperature, add 10g cetyl front threes
Ammonium chloride, controlling reaction temperature is 45 DEG C, then adds 0.1g sodium hydroxide, after being reacted 5 hours at 30 DEG C, uses hydrogen
Bromic acid is neutralized simultaneously to be washed after 3 times with ethanol, suction filtration and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, between TBAB, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)
Weight ratio is：1：1：10.
The preparation method of second catalyst is as follows：At 50 DEG C, TBAB is dissolved in dimethyl sulfoxide (DMSO),
After stirring, bi-tristearin is added in dimethyl sulfoxide (DMSO), the second catalyst is uniformly mixing to obtain.
The preparation process of N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas is as follows：Add
Then solvent 100ml toluene and 3g nano silicons, ultrasonic disperse 10min add 1g N- aminoethyl -3- aminopropyltriethoxies
Dimethoxysilane, adds 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second
Alcohol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas.The silica
It is purchased from extra large moral foundation (Beijing) bio tech ltd；
In N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, N- (2- aminoethyls) -3- ammonia
Weight ratio between propyl trimethoxy silicane and silica is 1：3.
Weight of the N- (2- aminoethyls) between -3- aminopropyl trimethoxysilanes improved silica and the second catalyst
Measuring ratio is：1：0.1.
Between isooctyl thioglycolate and N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas
Weight ratio be 100：1.
Embodiment 2：
The present embodiment 2 provides a kind of Methyl stannum mercaptide, and the preparation technology of the Methyl stannum mercaptide comprises the following steps：
Step 1：Alkane halogenation：Metallic tin powder, the first catalyst are added in reactor, then led into reactor
Enter monochloro methane, rise reaction temperature carries out alkane halogenation 8h, obtain dimethyltin chloride to 150 DEG C；Described first urges
Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2：Displacement reaction：Butter of tin is added into step 1, rise reaction temperature is forced into 220 DEG C
0.5MPa, after entering line replacement reaction 3 hours, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl
Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3：Esterification：The monomethyl tin trichloride obtained in step 2 and the dimethyltin chloride aqueous solution are added
Enter to sequentially add the second catalyst, isooctyl thioglycolate, the stirring reaction 5min in the case where reaction temperature is 30 DEG C, then add
N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, the stirring reaction 20min at 30 DEG C, and adjust anti-
The pH value answered is 7, then at 40 DEG C, stirring reaction 1h, static, cooling, layering；Organic layer is isolated, water-filling of going forward side by side washes 3
It is secondary；
Second catalyst is chitosan, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)；
Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；
Mol ratio between the metallic tin powder, monochloro methane, butter of tin, isooctyl thioglycolate is：1：1.2：2：
5。
The metallic tin powder and the weight ratio of the first catalyst are：100：0.3；
The preparation process of first catalyst is as follows：
100g water, 1g chitosans are added in a kettle., after stirring at room temperature, add 10g cetyl front threes
Ammonium chloride, controlling reaction temperature is 45 DEG C, then adds 0.1g sodium hydroxide, after being reacted 5 hours at 30 DEG C, uses hydrogen
Bromic acid is neutralized simultaneously to be washed after 3 times with ethanol, suction filtration and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, between TBAB, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)
Weight ratio is：1：1：10.
The preparation method of second catalyst is as follows：At 50 DEG C, TBAB is dissolved in dimethyl sulfoxide (DMSO),
After stirring, bi-tristearin is added in dimethyl sulfoxide (DMSO), the second catalyst is uniformly mixing to obtain.
The preparation process of N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas is as follows：Add
Then solvent 100ml toluene and 3g nano silicons, ultrasonic disperse 10min add 1g N- aminoethyl -3- aminopropyltriethoxies
Dimethoxysilane, adds 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second
Alcohol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas.The silica
It is purchased from extra large moral foundation (Beijing) bio tech ltd；
In N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, N- (2- aminoethyls) -3- ammonia
Weight ratio between propyl trimethoxy silicane and silica is 1：3.
Weight of the N- (2- aminoethyls) between -3- aminopropyl trimethoxysilanes improved silica and the second catalyst
Measuring ratio is：1：0.1.
Between isooctyl thioglycolate and N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas
Weight ratio be 100：1.
Embodiment 3：
The present embodiment 3 provides a kind of Methyl stannum mercaptide, and the preparation technology of the Methyl stannum mercaptide comprises the following steps：
Step 1：Alkane halogenation：Metallic tin powder, the first catalyst are added in reactor, then led into reactor
Enter monochloro methane, rise reaction temperature carries out alkane halogenation 6h, obtain dimethyltin chloride to 180 DEG C；Described first urges
Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2：Displacement reaction：Butter of tin is added into step 1, rise reaction temperature is forced into 220 DEG C
0.5MPa, after entering line replacement reaction 3 hours, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl
Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3：Esterification：The monomethyl tin trichloride obtained in step 2 and the dimethyltin chloride aqueous solution are added
Enter to sequentially add the second catalyst, isooctyl thioglycolate, the stirring reaction 5min in the case where reaction temperature is 30 DEG C, then add
N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, the stirring reaction 20min at 30 DEG C, and adjust anti-
The pH value answered is 7, then at 40 DEG C, stirring reaction 1h, static, cooling, layering；Organic layer is isolated, water-filling of going forward side by side washes 3
It is secondary；
Second catalyst is chitosan, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)；
Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；
Mol ratio between the metallic tin powder, monochloro methane, butter of tin, isooctyl thioglycolate is：1：1.2：2：
5。
The metallic tin powder and the weight ratio of the first catalyst are：100：0.5；
The preparation process of first catalyst is as follows：
100g water, 1g chitosans are added in a kettle., after stirring at room temperature, add 10g cetyl front threes
Ammonium chloride, controlling reaction temperature is 45 DEG C, then adds 0.1g sodium hydroxide, after being reacted 5 hours at 30 DEG C, uses hydrogen
Bromic acid is neutralized simultaneously to be washed after 3 times with ethanol, suction filtration and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, between TBAB, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)
Weight ratio is：1：1：10.
The preparation method of second catalyst is as follows：At 50 DEG C, TBAB is dissolved in dimethyl sulfoxide (DMSO),
After stirring, bi-tristearin is added in dimethyl sulfoxide (DMSO), the second catalyst is uniformly mixing to obtain.
The preparation process of N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas is as follows：Add
Then solvent 100ml toluene and 3g nano silicons, ultrasonic disperse 10min add 1g N- aminoethyl -3- aminopropyltriethoxies
Dimethoxysilane, adds 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second
Alcohol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas.The silica
It is purchased from extra large moral foundation (Beijing) bio tech ltd；
In N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, N- (2- aminoethyls) -3- ammonia
Weight ratio between propyl trimethoxy silicane and silica is 1：3.
Weight of the N- (2- aminoethyls) between -3- aminopropyl trimethoxysilanes improved silica and the second catalyst
Measuring ratio is：1：0.1.
Between isooctyl thioglycolate and N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas
Weight ratio be 100：1.
Embodiment 4：
The present embodiment 4 provides a kind of Methyl stannum mercaptide, and the preparation technology of the Methyl stannum mercaptide comprises the following steps：
Step 1：Alkane halogenation：Metallic tin powder, the first catalyst are added in reactor, then led into reactor
Enter monochloro methane, rise reaction temperature carries out alkane halogenation 6h, obtain dimethyltin chloride to 180 DEG C；Described first urges
Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2：Displacement reaction：Butter of tin is added into step 1, rise reaction temperature is forced into 220 DEG C
0.5MPa, after entering line replacement reaction 3 hours, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl
Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3：Esterification：The monomethyl tin trichloride obtained in step 2 and the dimethyltin chloride aqueous solution are added
Enter to sequentially add the second catalyst, isooctyl thioglycolate, the stirring reaction 5min in the case where reaction temperature is 30 DEG C, then add
N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, the stirring reaction 20min at 30 DEG C, and adjust anti-
The pH value answered is 7, then at 40 DEG C, stirring reaction 1h, static, cooling, layering；Organic layer is isolated, water-filling of going forward side by side washes 3
It is secondary；
Second catalyst is chitosan, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)；
Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；
Mol ratio between the metallic tin powder, monochloro methane, butter of tin, isooctyl thioglycolate is：1：1.2：2：
5。
The metallic tin powder and the weight ratio of the first catalyst are：100：0.7；
The preparation process of first catalyst is as follows：
100g water, 1g chitosans are added in a kettle., after stirring at room temperature, add 10g cetyl front threes
Ammonium chloride, controlling reaction temperature is 45 DEG C, then adds 0.1g sodium hydroxide, after being reacted 5 hours at 30 DEG C, uses hydrogen
Bromic acid is neutralized simultaneously to be washed after 3 times with ethanol, suction filtration and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, between TBAB, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)
Weight ratio is：1：1：10.
The preparation method of second catalyst is as follows：At 50 DEG C, TBAB is dissolved in dimethyl sulfoxide (DMSO),
After stirring, bi-tristearin is added in dimethyl sulfoxide (DMSO), the second catalyst is uniformly mixing to obtain.
The preparation process of N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas is as follows：Add
Then solvent 100ml toluene and 3g nano silicons, ultrasonic disperse 10min add 1g N- aminoethyl -3- aminopropyltriethoxies
Dimethoxysilane, adds 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second
Alcohol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas.The silica
It is purchased from extra large moral foundation (Beijing) bio tech ltd；
In N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, N- (2- aminoethyls) -3- ammonia
Weight ratio between propyl trimethoxy silicane and silica is 1：3.
Weight of the N- (2- aminoethyls) between -3- aminopropyl trimethoxysilanes improved silica and the second catalyst
Measuring ratio is：1：0.1.
Between isooctyl thioglycolate and N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas
Weight ratio be 100：1.
Embodiment 5：
The present embodiment 5 provides a kind of Methyl stannum mercaptide, and the preparation technology of the Methyl stannum mercaptide comprises the following steps：
Step 1：Alkane halogenation：Metallic tin powder, the first catalyst are added in reactor, then led into reactor
Enter monochloro methane, rise reaction temperature carries out alkane halogenation 6h, obtain dimethyltin chloride to 180 DEG C；Described first urges
Agent is hexadecyltrimethylammonium chloride and chitosan complexes；
Step 2：Displacement reaction：Butter of tin is added into step 1, rise reaction temperature is forced into 220 DEG C
0.5MPa, after entering line replacement reaction 3 hours, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl
Tin trichloride (boiling point is 148 DEG C) and dimethyltin chloride (188-190 DEG C) aqueous solution；
Step 3：Esterification：The monomethyl tin trichloride obtained in step 2 and the dimethyltin chloride aqueous solution are added
Enter to sequentially add the second catalyst, isooctyl thioglycolate, the stirring reaction 5min in the case where reaction temperature is 30 DEG C, then add
N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, the stirring reaction 20min at 30 DEG C, and adjust anti-
The pH value answered is 7, then at 40 DEG C, stirring reaction 1h, static, cooling, layering；Organic layer is isolated, water-filling of going forward side by side washes 3
It is secondary；
Second catalyst is chitosan, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)；
Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；
Mol ratio between the metallic tin powder, monochloro methane, butter of tin, isooctyl thioglycolate is：1：1.2：2：
5。
The metallic tin powder and the weight ratio of the first catalyst are：100：1；
The preparation process of first catalyst is as follows：
100g water, 1g chitosans are added in a kettle., after stirring at room temperature, add 10g cetyl front threes
Ammonium chloride, controlling reaction temperature is 45 DEG C, then adds 0.1g sodium hydroxide, after being reacted 5 hours at 30 DEG C, uses hydrogen
Bromic acid is neutralized simultaneously to be washed after 3 times with ethanol, suction filtration and dry hexadecyltrimethylammonium chloride and chitosan complexes.
In second catalyst, between TBAB, bi-tristearin, the mixture of dimethyl sulfoxide (DMSO)
Weight ratio is：1：1：10.
The preparation method of second catalyst is as follows：At 50 DEG C, TBAB is dissolved in dimethyl sulfoxide (DMSO),
After stirring, bi-tristearin is added in dimethyl sulfoxide (DMSO), the second catalyst is uniformly mixing to obtain.
The preparation process of N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas is as follows：Add
Then solvent 100ml toluene and 3g nano silicons, ultrasonic disperse 10min add 1g N- aminoethyl -3- aminopropyltriethoxies
Dimethoxysilane, adds 10% triethylamine solution that volumetric concentration is 10ml, the back flow reaction 2h at 100 DEG C, filtering, second
Alcohol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas.The silica
It is purchased from extra large moral foundation (Beijing) bio tech ltd；
In N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, N- (2- aminoethyls) -3- ammonia
Weight ratio between propyl trimethoxy silicane and silica is 1：3.
Weight of the N- (2- aminoethyls) between -3- aminopropyl trimethoxysilanes improved silica and the second catalyst
Measuring ratio is：1：0.1.
Between isooctyl thioglycolate and N- (2- the aminoethyls) -3- aminopropyl trimethoxysilane improved silicas
Weight ratio be 100：1.
Comparative example 1：
The detailed process be the same as Example 5 of comparative example 1, difference is, not including the first catalyst in step 1, other portions
Divide be the same as Example 5.
Comparative example 2：
The detailed process be the same as Example 5 of comparative example 2, difference is, the first catalyst in step 1 is changed into cetyl
Trimethyl ammonium chloride, other parts be the same as Example 5.
Comparative example 3：
The detailed process be the same as Example 5 of comparative example 3, difference is, the first catalyst in step 1 is changed into chitosan,
Other parts be the same as Example 5.
Comparative example 4：
The detailed process be the same as Example 5 of comparative example 4, difference is, the first catalyst in step 1 is changed into dimethyl disulfide
Ether, other parts be the same as Example 5.
Comparative example 5：
The detailed process be the same as Example 5 of comparative example 5, difference is, the second catalyst, other portions will not be included in step 2
Divide be the same as Example 5.
Comparative example 6：
The detailed process be the same as Example 5 of comparative example 6, difference is, N- (2- aminoethyls) -3- ammonia will not be included in step 2
Propyl trimethoxy silicane improved silica, other parts be the same as Example 5.
Comparative example 7：
The detailed process be the same as Example 5 of comparative example 7, difference is, by step 2 by N- (2- aminoethyls) -3- aminopropyls
Trimethoxy silane improved silica is changed to N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, and other parts are with real
Apply example 5.
Comparative example 8：
The detailed process be the same as Example 5 of comparative example 8, difference is, N- (2- aminoethyls) -3- ammonia will not be included in step 2
Propyl trimethoxy silicane improved silica is changed to silane coupler kh560 improved silicas, and other parts are with implementation
Example 5.
Method of testing：
1st, using obtaining monomethyl tin trichloride and the dimethyltin chloride aqueous solution in liquid chromatography for measuring step 2
In, the content of monomethyl tin trichloride and dimethyltin chloride, wherein, the condition of liquid chromatogram is：Chromatographic column：C18, flowing
It is mutually methanol, flow velocity is 1mL/min, and 35 DEG C of column temperature, wavelength is 300nm, and sampling volume is 10 microlitres；The model of liquid chromatogram
Agilent 1100；
The standard sample of monomethyl tin trichloride and dimethyltin chloride is prepared respectively, is made standard curve, is measured guarantor
It is 2.689min and 3.581min to stay the time；
The product that 1~embodiment of embodiment 5 and 1~comparative example of comparative example 8 are obtained measures monomethyl tri-chlorination respectively
The content of tin and dimethyltin chloride.
2nd, the presence of stannous chloride is detected according to analysis method specified in HG/T 2526-93.
3rd, the second catalyst repetitive cycling service life number of times is tested, when the conversion ratio of reactant is less than 80%, catalysis
Agent end of life, records the access times of the second catalyst.
The characterization test of table 1
From table 1 it follows that from embodiment 1 into embodiment 5, with the increase of the first catalyst usage amount, step 2
In obtain the percetage by weight increase of dimethyltin chloride, can basis when it is added in PVC plastic as heat stabilizer
Actual conditions adjust the content of different component in Methyl stannum mercaptide.In addition, also found by experiment, N- (2- ammonia second is added
Base) -3- aminopropyl trimethoxysilanes improved silica can greatly improve the service life of the second catalyst.
Embodiment 6
Embodiments herein 6 provide a kind of environment-friendly type PVC resin, the environment-friendly type PVC, in parts by weight, at least
Including,
100 parts of polyvinyl chloride resin；
0.1 part of Methyl stannum mercaptide described in embodiment 5；
2,6- 0.5 part of DI-tert-butylphenol compounds.
The preparation method of the environment-friendly type PVC resin is：By the polyvinyl chloride resin under molten condition, Methyl stannum mercaptide, 2,6- bis-
Tert-butyl phenol is added in screw extruder, extrusion molding.
After polyvinyl chloride resin is placed in into outdoor application 1 year, observation outward appearance does not occur by the transformation of white to yellow, brown,
And hydrogen chloride is not detected.Illustrate that the present invention has good thermostable effect.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim is covered.
Claims (10)
1. a kind of preparation technology of Methyl stannum mercaptide, it is characterised in that at least comprise the following steps：
Step 1：Alkane halogenation：Metallic tin powder, the first catalyst are added in reactor, one is then passed through into reactor
Chloromethanes, rise reaction temperature carries out alkane 5~10h of halogenation, obtains dimethyltin chloride to 150~180 DEG C；
Step 2：Displacement reaction：Butter of tin is added into step 1, rise reaction temperature is forced into 220~230 DEG C
0.5MPa, enters line replacement reaction, obtains replacing reaction solution, then distills displacement reaction solution, obtains monomethyl tri-chlorination
Tin and the dimethyltin chloride aqueous solution；
Step 3：Esterification：By the monomethyl tin trichloride obtained in step 2 and the dimethyltin chloride aqueous solution add according to
The second catalyst of secondary addition, isooctyl thioglycolate, stirring reaction 5~20min, Ran Houzai in the case where reaction temperature is 20~30 DEG C
Add N- (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas, at 30~50 DEG C stirring reaction 20~
60min, and it is 7 to adjust the pH value of reaction, then at 40 DEG C, 4~5h of stirring reaction, static, cooling, layering；Isolate
Machine layer, water-filling of going forward side by side is washed 1~3 time；Second catalyst is TBAB, bi-tristearin, dimethyl sulfoxide (DMSO)
Mixture；
Step 4：Distillation：Methyl stannum mercaptide is obtained by vacuum distillation drying；
Mol ratio between the metallic tin powder, monochloro methane, isooctyl thioglycolate is：1：(1.2~1.5)：5.
2. the preparation technology of Methyl stannum mercaptide as claimed in claim 1, it is characterised in that first catalyst is hexadecane
The weight ratio of base trimethyl ammonium chloride and chitosan complexes, hexadecyltrimethylammonium chloride and chitosan is 10：1.
3. the preparation technology of Methyl stannum mercaptide as claimed in claim 1, it is characterised in that the metallic tin powder and the first catalysis
The weight ratio of agent is：100：(0.1~5).
4. the preparation technology of Methyl stannum mercaptide as claimed in claim 1, it is characterised in that in second catalyst, four fourths
Weight ratio between base ammonium bromide, bi-tristearin, dimethyl sulfoxide (DMSO) is：1：(1~5)：(10~15).
5. the preparation technology of Methyl stannum mercaptide as claimed in claim 1, it is characterised in that the isooctyl thioglycolate and N-
Weight ratio between (2- aminoethyls) -3- aminopropyl trimethoxysilane improved silicas is 100：(1~8).
6. the preparation technology of Methyl stannum mercaptide as claimed in claim 1, it is characterised in that N- (2- the aminoethyls) -3- ammonia
In propyl trimethoxy silicane improved silica, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes and silica it
Between weight ratio be (1~10)：3.
7. the preparation technology of Methyl stannum mercaptide as claimed in claim 1, it is characterised in that N- (2- the aminoethyls) -3- ammonia
Weight ratio between propyl trimethoxy silicane improved silica and the second catalyst is：1：(0.1~1).
8. a kind of Methyl stannum mercaptide, it is characterised in that the Methyl stannum mercaptide is using the methyl mercaptan described in claim 1~7
What the preparation technology of tin was prepared.
9. a kind of environment-friendly type PVC resin, it is characterised in that the environment-friendly type PVC, in parts by weight, at least includes,
100 parts of polyvinyl chloride resin；
0.1~0.5 part of Methyl stannum mercaptide described in claim 8；
0.1~0.5 part of auxiliary agent.
10. application of the Methyl stannum mercaptide in rubber, plastics, catalyst field described in claim 8.
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|---|---|---|---|---|
| CN113816987A (en) * | 2021-10-08 | 2021-12-21 | 广东先导微电子科技有限公司 | Preparation method of dibutyltin oxide |
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| CN102250136A (en) * | 2011-05-13 | 2011-11-23 | 浙江海普顿化工科技有限公司 | Preparation method of methyltin mercaptide |
| CN106008589A (en) * | 2016-06-25 | 2016-10-12 | 安徽升华新奥特化工有限公司 | Green methyl tin mercaptide compound |
| CN106117263A (en) * | 2016-06-25 | 2016-11-16 | 安徽升华新奥特化工有限公司 | A kind of Methyl stannum mercaptide stabilizer of environmental protection |
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| CN1137048A (en) * | 1995-05-27 | 1996-12-04 | 深圳泛胜塑胶助剂有限公司 | PVC resin preparing process using mixture of methyl tin and thiolate as thermal stabilizer |
| CN1270961A (en) * | 1999-04-19 | 2000-10-25 | 张麟 | Preparation of tin methyl mercaptide |
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| CN113816987B (en) * | 2021-10-08 | 2024-05-24 | 广东先导微电子科技有限公司 | Preparation method of dibutyl tin oxide |
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