CN108219141A - A kind of ester group functional poly siloxanes and preparation method and application - Google Patents
A kind of ester group functional poly siloxanes and preparation method and application Download PDFInfo
- Publication number
- CN108219141A CN108219141A CN201711384771.5A CN201711384771A CN108219141A CN 108219141 A CN108219141 A CN 108219141A CN 201711384771 A CN201711384771 A CN 201711384771A CN 108219141 A CN108219141 A CN 108219141A
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- China
- Prior art keywords
- alkyl
- preparation
- ester group
- acid
- ester
- Prior art date
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- 125000004185 ester group Chemical group 0.000 title claims abstract description 38
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- -1 polysiloxanes Polymers 0.000 claims description 48
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 235000011056 potassium acetate Nutrition 0.000 claims description 18
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- CRHBFSSHXLHHRO-UHFFFAOYSA-N 2-(3-chloropropyl)-2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(CCCCl)O[Si](C)(C)O1 CRHBFSSHXLHHRO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- SGLLRHDXBOJGPF-UHFFFAOYSA-N 2-(3-chloropropyl)-2,4,4,6,6-pentamethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(CCCCl)O1 SGLLRHDXBOJGPF-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 239000004300 potassium benzoate Substances 0.000 claims description 3
- 235000010235 potassium benzoate Nutrition 0.000 claims description 3
- 229940103091 potassium benzoate Drugs 0.000 claims description 3
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 claims description 3
- 239000004331 potassium propionate Substances 0.000 claims description 3
- 235000010332 potassium propionate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 claims description 3
- 239000004324 sodium propionate Substances 0.000 claims description 3
- 235000010334 sodium propionate Nutrition 0.000 claims description 3
- 229960003212 sodium propionate Drugs 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- VLQZJOLYNOGECD-UHFFFAOYSA-N 2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[SiH]1O[SiH](C)O[SiH](C)O1 VLQZJOLYNOGECD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QHAWELQTGVDPLX-UHFFFAOYSA-N [Cl].[Si](O)(O)(O)O Chemical compound [Cl].[Si](O)(O)(O)O QHAWELQTGVDPLX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Chemical group 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229930195733 hydrocarbon Chemical group 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 claims 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 claims 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000011033 desalting Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 17
- 238000009833 condensation Methods 0.000 description 16
- 230000005494 condensation Effects 0.000 description 16
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 15
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 13
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000005292 vacuum distillation Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 7
- 229940090181 propyl acetate Drugs 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000011067 equilibration Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 3
- SNYNNFDVNITLRQ-UHFFFAOYSA-N 2,2,4,4,6,6,8-heptamethyl-1,3,5,7,2,4,6,8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 SNYNNFDVNITLRQ-UHFFFAOYSA-N 0.000 description 2
- RDXQEAWKWHWOHG-UHFFFAOYSA-N 2-(3-chloropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound ClCCC[SiH]1O[SiH2]O[SiH2]O1 RDXQEAWKWHWOHG-UHFFFAOYSA-N 0.000 description 2
- KDACIXJUXOJZLX-UHFFFAOYSA-N 2-(chloromethyl)-2,4,4,6,6,8,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(CCl)O[Si](C)(C)O1 KDACIXJUXOJZLX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000035935 pregnancy Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- CLTMUXYRYKDGOK-UHFFFAOYSA-N 2,2,4,4,6,6,8-heptamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical class C[SiH]1O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 CLTMUXYRYKDGOK-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- LCGWAVDNPZNKHQ-UHFFFAOYSA-N C(CC)OC(C)=O.NC(=N)N Chemical compound C(CC)OC(C)=O.NC(=N)N LCGWAVDNPZNKHQ-UHFFFAOYSA-N 0.000 description 1
- IJAAVDUFBXLLQL-UHFFFAOYSA-N CCO[SiH](CCCCl)OCC Chemical compound CCO[SiH](CCCCl)OCC IJAAVDUFBXLLQL-UHFFFAOYSA-N 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- SWEYNHYBJHPVJL-UHFFFAOYSA-N butanoic acid;sodium Chemical compound [Na].CCCC(O)=O SWEYNHYBJHPVJL-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- CAXZYJLKQUXPBS-UHFFFAOYSA-N dichloro(3-chloropropyl)silane Chemical compound ClCCC[SiH](Cl)Cl CAXZYJLKQUXPBS-UHFFFAOYSA-N 0.000 description 1
- VOVKNAOBZXBVMN-UHFFFAOYSA-N dichloro(3-chloropropyl)silicon Chemical compound ClCCC[Si](Cl)Cl VOVKNAOBZXBVMN-UHFFFAOYSA-N 0.000 description 1
- VFUGMTAIQWBRCM-UHFFFAOYSA-N dihydroxy-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(O)O VFUGMTAIQWBRCM-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- HJIGRHPMRXZAEJ-UHFFFAOYSA-M potassium;pyridine-2-carboxylate Chemical compound [K+].[O-]C(=O)C1=CC=CC=N1 HJIGRHPMRXZAEJ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000005401 siloxanyl group Chemical group 0.000 description 1
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 description 1
- 229940046307 sodium thioglycolate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KAKFZMMRKBQABS-UHFFFAOYSA-N trimethyl(silyloxysilyloxy)silane Chemical class C[Si](C)(C)O[SiH2]O[SiH3] KAKFZMMRKBQABS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention relates to a kind of ester group functional poly siloxanes and preparation method and application, which has structural formula shown in formula (I).Using chloro-hydrocarbons cyclosiloxane monomer and carboxylate as raw material, solvent is added in, temperature reaction in atmospheric conditions except desalting and solvent, obtains ester-containing cyclosiloxane monomer;It is mixed using prepared ester-containing cyclosiloxane monomer as raw material or by it with methyl cyclosiloxane monomer, adds in acid catalyst, temperature reaction is to get ester group functional poly siloxanes in atmospheric conditions.Ester group functional poly siloxanes preparation method of the present invention is simple, and without using noble metal catalyst, production cost reduces, and prepared product is stablized, and yield is high.
Description
Technical field
The present invention relates to a kind of polysiloxanes and preparation method and application, more particularly to a kind of ester group functional poly silicon
Oxygen alkane and preparation method and application belongs to functional polymer research field.
Background technology
Organosilicon polymer due to having the special molecular structure and composition of Si-O-Si main chains and organic side chain, tool simultaneously
There are unique excellent properties, such as resistance to oxidation, chemicals-resistant, electrical isolation, radiation hardness, weather-proof, hydrophobic, fire-retardant, salt spray resistance, mould proof
Deng;The characteristics of having high molecular material easy processing concurrently simultaneously can be made according to different requirements and meet product for various purposes.
Polysiloxanes achieves very rapid development in recent years, and a series of functional polyorganosiloxanes with special construction exist
Great success is all achieved in laboratory research and industrial production.It is original that functional polyorganosiloxane not only remains polysiloxane
Excellent properties, while impart again other special natures that it is brought by functional group or using functional group activity with it is other
New material is constructed in compound reaction.
Ester group functional group is introduced in polysiloxane molecule chain so that polysiloxanes has parent CO2Property, CO can be used as2's
Emulsifier is used for overcritical field;Or prepare organosilicon luminescent material using the carbonyl in ester group and rare-earth ion coordination.
In the prior art, the preparation method in relation to ester group functional polyorganosiloxane mainly has:E.J.Beckman etc., which is utilized, to be contained
With the compound simultaneously containing vinyl and ester group under chloroplatinic acid catalyst hydrosilylation occurs for the polysiloxanes of silicon hydrogen-based,
Be made functional polyorganosiloxane containing ester group (referring to R.Fink, D.Hancu, R.Valentine, and E.J.Beckman,
J.Phys.Chem.B 1999,103:6441-6444);Haifeng Lu are using the polysiloxanes of hydrosilyl group-containing with containing second simultaneously
Under chloroplatinic acid catalyst hydrosilylation occurs for the compound of alkenyl and ester group, be made ester group functional polyorganosiloxane (referring to
Haifeng Lu,J.Appl.Polym.Sci.2012,123:1884–1888).But in these class methods, that uses urges
Agent chloroplatinic acid is expensive, and can remain in the product, can not only cause production cost excessively high, and can be to the property of product
Damage can be generated;In addition, micro platinum catalyst used is very sensitive to some elements (such as S, P, N), it is easily formed containing coordination
The compound of base reduces catalytic activity or even failure so as to cause catalyst " poisoning ";Particularly, it has been used in this reaction big
Toluene to be measured, causes very big environmental pollution, and the reaction time is longer, production cost greatly improves, thus, greatly limit it
Application range.Yujing Zuo are utilized and are deposited containing vinyl polysiloxane and the compound simultaneously containing sulfydryl and ester group in photoinitiator
In lower generation sulfydryl-double bond reaction, be made ester group functional polyorganosiloxane (referring to Yujing Zuo, Chem.Eur.J.2014,20,
12924-12932), using the method, during light-initiated, there is the generation of side reaction, the product of silicone product can be influenced
Matter.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of ester group functional poly siloxanes and preparation method thereof with answering
With.
Technical scheme is as follows:
A kind of ester group functional poly siloxanes has structural formula shown in formula (I):
In formula (I), m=0~7000, n=1~400, m, n are all integer, and the integer of x >=1, R is for alkyl or containing hetero atom
Alkyl.
, according to the invention it is preferred to, in formula (I), m=0~400, n=1~200;X=1~10, the alkyl are alkane
Base, aryl, aralkyl or alkylene;The alkyl containing hetero atom is the alkyl containing O, N, S, P or Si.
It is further preferred that in R, the alkyl is C1~C12Alkyl, the aryl be C7~C16Aryl, institute
The aralkyl stated is C8~C12Aralkyl, the alkylene be C3~C12Alkylene;The alkyl containing hetero atom is
Alkyl containing carbonyl, hydroxyl alkyl, alkyl containing pyridyl group, alkyl containing sulfydryl or silane-group containing alkyl.
, according to the invention it is preferred to, the number-average molecular weight of the ester group functional poly siloxanes is 1 × 103~2 ×
105。
According to the present invention, the preparation method of above-mentioned ester group functional poly siloxanes is as follows including step:
(1) preparation of ester-containing cyclosiloxane monomer
Using chloro-hydrocarbons cyclosiloxane monomer and carboxylate as raw material, solvent is added in, it is warming up to 50 in atmospheric conditions~
130 DEG C of 2~10h of reaction after reaction, filter out salt, and distillation removes solvent to get ester-containing cyclosiloxane;
(2) it mixes, adds using prepared ester-containing cyclosiloxane monomer as raw material or by it with methyl cyclosiloxane monomer
Enter acid catalyst, be warming up to 90-110 in atmospheric conditions and react 6-8h to get ester group functional poly siloxanes.
Preparation in accordance with the present invention, it is preferred that chloro-hydrocarbons cyclosiloxane and carboxylate described in step (1)
Proportioning is by ranging from r >=1 of carboxylate radical and the molar ratio r of chlorocarbon base, further preferred 1.1-2.
Preparation in accordance with the present invention, it is preferred that the addition quality and solvent of chloro-hydrocarbons cyclosiloxane in step (1)
The ratio between addition volume be 1:(0.5~10) g/mL.
It is further preferred that the addition quality of chloro-hydrocarbons cyclosiloxane and the ratio between the addition volume of solvent are 1:(1~5)
g/mL。
Preparation in accordance with the present invention, it is preferred that chloro-hydrocarbons cyclosiloxane described in step (1) is seven first of chloropropyl
Basic ring tetrasiloxane, four chloropropyl tetramethyl-ring tetrasiloxanes, chloropropyl pentamethyl cyclotrisiloxane or trichlorine oxypropyl trimethyl
Cyclotrisiloxane.
According to the present invention, the chloro-hydrocarbons cyclosiloxane monomer described in step (1) can be obtained by prior art preparation.
It can refer to following document:
(1) Xiao Manchao, Wen Xiaoyao, Du Zuodong, macromolecule notification, 1984,5:363-368.
(2)Witold Fortuniak,Julian Chojnowski,Georges Sauvet,
Macromol.Chem.Phys.2001,202:2306-2313.
(3) Feng Shengyu, Zhang Jie, Li Meijiang, Zhu Qingzeng, organosilicon macromolecule and its application, 2007.
Preparation in accordance with the present invention, it is preferred that carboxylate described in step (1) is the knot shown in formula (II)
Structure:
MOOCR
(II),
In formula (II), the meaning of R is identical with R in formula (I), M Li, Na, K, Mg, Ca, Sr, Ba or NH4;
It is further preferred that the carboxylate is:Potassium acetate, sodium acetate, sodium propionate, potassium propionate, potassium butyrate, butyric acid
Sodium, Potassium Benzoate, sodium benzoate, potassium acrylate or sodium acrylate.
Preparation in accordance with the present invention, it is preferred that reaction temperature described in step (1) is 60~100 DEG C.
Preparation in accordance with the present invention, it is preferred that solvent described in step (1) is n,N-Dimethylformamide, diformazan
Base sulfoxide, acetonitrile, 1,3- dimethyl-2-imidazolinones, tetrahydrofuran alcohol mixed solvent or tetrahydrofuran methanol mixing it is molten
Agent;It is further preferred that the solvent is n,N-Dimethylformamide.
Preparation in accordance with the present invention, it is preferred that ester-containing cyclosiloxane described in step (1) has formula (III) institute
The structure shown:
In formula (III), the integer of x >=1, the meaning of R is identical with R in formula (I).
Preparation in accordance with the present invention, it is preferred that methyl cyclosiloxane monomer described in step (2) is prestox ring four
Siloxanes or hexamethyl cyclotrisiloxane.
Preparation in accordance with the present invention, it is preferred that acid catalyst described in step (2) is trifluoromethane sulfonic acid, acidity
Carclazyte, cation exchange resin, the concentrated sulfuric acid, solid super-strong acid TiO2/SO4 2-, hydrochloric acid, nitric acid, pyrophosphoric acid, boric acid, alkyl sulphur
One of acid, aryl sulfonic acid, fluorine hydrocarbyl sulfonic, chlorine silicic acid or lewis acid.
According to the present invention, above-mentioned ester group functional poly siloxanes can be used as CO2Emulsifier be used for overcritical field;Also may be used
Fluorescence luminescent material is used to prepare by the coordination between ester group and rare earth ion;Also other functional groups can be passed through chlorocarbon base
It is introduced into polysiloxanes with carboxylic acid reactant salt, expands its application range.
The principle of the present invention:
By the way that nucleophilic substitution occurs between the chlorocarbon base and carboxylate in chloro-hydrocarbons cyclosiloxane monomer, chlorine is taken off
Compound obtains the cyclosiloxane containing ester group;Then by the ester-containing cyclosiloxane monomer of synthesis or by itself and methyl cyclosiloxane
Under acidic catalyst cationic ring-opening polymerization occurs for monomer, and ester group functional poly siloxanes is made.
Beneficial effects of the present invention:
1st, ester-containing cyclosiloxane of the present invention, product are stablized, and yield is high, and yield is up to more than 95.0%.
2nd, ester group functional poly siloxanes preparation method of the present invention is simple, without using noble metal catalyst, production
Cost reduction, prepared product are stablized, and yield is high, and for yield up to more than 85.0%, post processing is simple.
3rd, reaction route of the invention avoids the generation of side reaction, the ester group functional poly siloxanes purity being prepared
Height, purity is more than 98.0%.
4th, the present invention can obtain the controllable functional poly siloxanes of ester group content by controlling the dosage of raw material.
5th, gained ester group functional poly siloxanes can be used as CO2Emulsifier be used for overcritical field;Also it can pass through ester group
Coordination between rare earth ion is used to prepare fluorescence luminescent material;Also other functional groups can be passed through chlorocarbon base and carboxylate
Reaction is introduced into polysiloxanes, expands its application range.
Description of the drawings
Fig. 1 is the infrared spectrogram of seven methyl acetic acid propyl ester basic ring tetrasiloxane monomers made from the embodiment of the present invention 1.
Fig. 2 is the hydrogen nuclear magnetic spectrogram of seven methyl acetic acid propyl ester basic ring tetrasiloxane monomers made from the embodiment of the present invention 1.
Fig. 3 is the proton magnetic of poly- (dimethyl siloxane-methyl propyl acetate radical siloxane) made from the embodiment of the present invention 1
Spectrogram.
Specific embodiment
For a better understanding of the present invention, technical scheme of the present invention is described further with reference to embodiment, but
Institute's protection domain of the present invention is not limited to the range of embodiment statement.
In embodiment it is raw materials used unless otherwise specified, be conventional commercial products.
Embodiment 1
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer, ratio 1 is measured by chlorocarbon base and carboxylate radical mole:1.1
Ratio, add in 15.09g chloropropyls heptamethylcyclotetrasiloxanes, 4.54g potassium acetates, 75ml n,N-Dimethylformamide, magnetic
Power stirring is uniformly mixed three, is to slowly warm up to 100 DEG C, reacts 6 hours, and reaction finishes, and system is cooled to room temperature, filtering
Salt is removed, solvent is removed in vacuum distillation, is dried in vacuo 8 hours, is obtained seven methyl acetic acid propyl ester basic ring tetrasiloxane monomers, yield
It is 95.3%, purity 97.2%.
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer and agitating device, 42.57g prestoxs ring four is added in
Siloxanes, 3.83g methyl acetic acid propyl ester basic rings tetrasiloxane, 0.46g Purolite CT-175, agitating and heating, slow heating
To 100 DEG C, equilibration reaction 8h, de- low boiling is evaporated under reduced pressure, catalyst is removed by filtration, obtains poly- (dimethyl siloxane-methyl second
Propyl propionate radical siloxane).
Seven methyl acetic acid propyl ester basic ring tetrasiloxane structural formulas are as follows made from the present embodiment:
(dimethyl siloxane-methyl propyl acetate radical siloxane) structural formula poly- made from the present embodiment is as follows:
γ-chloropropyl heptamethylcyclotetrasiloxane described in the present embodiment is prepared as follows obtaining:
γ-chloropropyl diethoxy silane and dimethyl diethoxysilane in acid condition to that hydrolysis contracting occur
Reaction is closed, synthesizes γ-chloropropyl heptamethylcyclotetrasiloxane.
Embodiment 2
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer, ratio 1 is measured by chlorocarbon base and carboxylate radical mole:1.1
Ratio, add in 15.09g γ-chloropropyl heptamethylcyclotetrasiloxane, 4.54g potassium acetates, 75ml n,N-Dimethylformamide,
Magnetic agitation is uniformly mixed three, is to slowly warm up to 100 DEG C, reacts 6 hours, reaction finishes, and system is cooled to room temperature, mistake
Salt is filtered out, solvent is removed in vacuum distillation, is dried in vacuo 8 hours, is obtained seven methyl acetic acid propyl ester basic ring tetrasiloxane monomers, is produced
Rate is 95.3%, purity 97.2%.
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer and agitating device, seven methyl acetic acids third of 5.35g are added in
Ester group cyclotetrasiloxane, 0.05g Purolite CT-175, agitating and heating are heated slowly to 100 DEG C, and equilibration reaction 8h subtracts
The de- low boiling of pressure distillation, is removed by filtration catalyst, obtains poly- (dimethyl siloxane-methyl propyl acetate radical siloxane).
γ described in the present embodiment-the preparation method is the same as that of Example 1 for chloropropyl heptamethylcyclotetrasiloxane.
Embodiment 3
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer, ratio 1 is measured by chlorocarbon base and carboxylate radical mole:1.1
Ratio, add in 18.50g tetra- chloropropyl tetramethyl-ring tetrasiloxanes, 4.54g potassium acetates, 75ml n,N-Dimethylformamide,
Magnetic agitation is uniformly mixed three, is to slowly warm up to 100 DEG C, reacts 6 hours, reaction finishes, and system is cooled to room temperature, mistake
Salt is filtered out, solvent is removed in vacuum distillation, is dried in vacuo 8 hours, is obtained tetramethyl tetrem propyl propionate basic ring tetrasiloxane monomer,
Yield is 95.3%, purity 97.2%.
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer and agitating device, 20.15g prestoxs ring four is added in
Siloxanes, 1.07g tetramethyl tetrem propyl propionate basic rings tetrasiloxane, 0.22g Purolite CT-175, agitating and heating, slowly
100 DEG C, equilibration reaction 8h are heated to, de- low boiling is evaporated under reduced pressure, is removed by filtration catalyst, obtains poly- (dimethyl siloxane-first
Guanidine-acetic acid propyl ester radical siloxane).
Tetramethyl tetrem propyl propionate basic ring tetrasiloxane structural formula is as follows made from the present embodiment:
Four chloropropyl tetramethyl-ring tetrasiloxanes described in the present embodiment are prepared as follows obtaining:
Hydrosilylation in the presence of platinum catalyst is occurred into for tetramethyl-ring tetrasiloxane and allyl chloride, synthesizes tetrachloro
Propyl tetramethyl-ring tetrasiloxane.
Embodiment 4
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer, ratio 1 is measured by chlorocarbon base and carboxylate radical mole:1.1
Ratio, add in 12.13g γ-chloropropyl pentamethyl cyclotrisiloxane, 4.54g potassium acetates, 75ml n,N-Dimethylformamide,
Magnetic agitation is uniformly mixed three, is to slowly warm up to 100 DEG C, reacts 6 hours, reaction finishes, and system is cooled to room temperature, mistake
Salt is filtered out, solvent is removed in vacuum distillation, is dried in vacuo 8 hours, is obtained pentamethyl propyl acetate basic ring trisiloxanes monomer, is produced
Rate is 95.7%, purity 98.2%.
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer and agitating device, 25.15g pregnancy basic ring three is added in
Siloxanes, 2.05g pentamethyl propyl acetate basic rings trisiloxanes, 0.27g Purolite CT-175, agitating and heating slowly add
Heat is evaporated under reduced pressure de- low boiling, is removed by filtration catalyst, obtains poly- (dimethyl-methyl acetic acid third to 100 DEG C, equilibration reaction 8h
Ester group siloxanes).
Pentamethyl propyl acetate basic ring trisiloxanes structural formula is as follows made from the present embodiment:
Pentamethyl chloropropyl cyclotrisiloxane described in the present embodiment is prepared as follows obtaining:
It is anti-that hydrolytic condensation is occurred into acid condition for tetramethyl dihydroxy disiloxane and chloropropyl dichlorosilane
Should, synthesize pentamethyl chloropropyl cyclotrisiloxane.
Embodiment 5
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer, ratio 1 is measured by chlorocarbon base and carboxylate radical mole:1.1
Ratio, add in three chloropropyl cyclotrisiloxane of 18.36g trimethyls, 4.54g potassium acetates, 75ml n,N-Dimethylformamide,
Magnetic agitation is uniformly mixed three, is to slowly warm up to 100 DEG C, reacts 6 hours, reaction finishes, and system is cooled to room temperature, mistake
Salt is filtered out, solvent is removed in vacuum distillation, is dried in vacuo 8 hours, is obtained trimethyl triacetic acid propyl ester basic ring trisiloxanes monomer,
Yield is 96.5%, purity 97.9%.
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer and agitating device, 35.15g pregnancy basic ring three is added in
Siloxanes, 3.15g trimethyl triacetic acid propyl ester basic rings trisiloxanes, 0.38g Purolite CT-175, agitating and heating, slowly
100 DEG C, equilibration reaction 8h are heated to, de- low boiling is evaporated under reduced pressure, is removed by filtration catalyst, obtains poly- (dimethyl siloxane-first
Guanidine-acetic acid propyl ester radical siloxane).
Trimethyl triacetic acid propyl ester basic ring trisiloxanes structural formula is as follows made from the present embodiment:
Three chloropropyl cyclotrisiloxane of trimethyl described in the present embodiment is prepared as follows obtaining:
Hydrolytic condensation in ether solvent is occurred into for γ-chloropropyl dichlorosilane, synthesizes three chloropropyl ring of trimethyl
Trisiloxanes.
Embodiment 6
1 step of embodiment is repeated, the difference is that chloropropyl heptamethylcyclotetrasiloxane is changed to seven methyl ring four of chloromethyl
Siloxanes obtains poly- (dimethyl siloxane-methyl methyl acetate radical siloxane).
Chloromethyl heptamethylcyclotetrasiloxane described in the present embodiment is prepared as follows obtaining:
Using octamethylcy-clotetrasiloxane as raw material, it is passed through chlorine under ultra violet lamp, after vacuum fractionation, obtains chloromethyl
Heptamethylcyclotetrasiloxane.
Embodiment 7
1 step of embodiment is repeated, the difference is that potassium acetate is changed to sodium acetate, obtains poly- (dimethyl siloxane-methyl second
Propyl propionate radical siloxane).
Embodiment 8
2 step of embodiment is repeated, the difference is that potassium acetate is changed to potassium propionate, obtains poly- (dimethyl siloxane-methyl third
Propyl propionate radical siloxane).
Embodiment 9
3 step of embodiment is repeated, the difference is that potassium acetate is changed to potassium acrylate, obtains poly- (dimethyl siloxane-methyl
Methyl acrylate radical siloxane).
Embodiment 10
4 step of embodiment is repeated, the difference is that potassium acetate is changed to Potassium Benzoate, obtains poly- (dimethyl siloxane-methyl
Propyl benzoate radical siloxane).
Embodiment 11
1 step of embodiment is repeated, the difference is that potassium acetate is changed to somsanit, obtains poly- (dimethyl silica
Alkane-methyl gamma-hydroxybutyric acid propyl ester radical siloxane).
Embodiment 12
1 step of embodiment is repeated, the difference is that potassium acetate is changed to potassium pyridine-2-carboxylate, obtains poly- (dimethyl silica
Alkane-methylpicolinic acid's propyl ester radical siloxane).
Embodiment 13
1 step of embodiment is repeated, the difference is that potassium acetate is changed to sodium thioglycolate, obtains poly- (dimethyl siloxane-first
Base thioacetic acid propyl ester radical siloxane).
Embodiment 14
1 step of embodiment is repeated, the difference is that potassium acetate is changed to silantriol sodium propionate, obtains poly- (dimethyl silica
Alkane-methyl-monosilane triol propyl propionate radical siloxane).
Comparative example 1 (the preparing solvent difference of ester-containing cyclosiloxane monomer)
As described in Example 1, in three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer, by chlorocarbon base and carboxylate radical
Mole metering ratio 1:1.1 ratio adds in 15.09g chloropropyls heptamethylcyclotetrasiloxane, 4.54g potassium acetates, 75ml ethyl alcohol,
Magnetic agitation is uniformly mixed three, is to slowly warm up to 100 DEG C, reacts 6 hours, reaction finishes, and system is cooled to room temperature, mistake
Filter out salt, solvent is removed in vacuum distillation, is dried in vacuo 8 hours, and gained monomer is chloropropyl heptamethylcyclotetrasiloxane, seven first
Guanidine-acetic acid propyl ester basic ring tetrasiloxane monomer yield is 0%.
Comparative example 2 (the preparation reaction temperature of ester-containing cyclosiloxane monomer is different)
As described in Example 1, in three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer, by chlorocarbon base and carboxylate radical
Mole metering ratio 1:1 ratio adds in 10g methyl Chloropropylpolysiloxanes, 2.62g potassium acetates, 50ml N, N- dimethyl formyls
Amine, magnetic agitation are uniformly mixed three, are to slowly warm up to 40 DEG C, react 8 hours, and reaction finishes, and system is cooled to room temperature,
It is removed by filtration salt, solvent is removed in vacuum distillation, is dried in vacuo 8 hours, and gained monomer is chloropropyl heptamethylcyclotetrasiloxane, and seven
Methyl acetic acid propyl ester basic ring tetrasiloxane monomer yield is 0%.
Comparative example 3 (the preparing catalyst difference of ester group functional poly siloxanes)
As described in Example 1, in three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer, by chlorocarbon base and carboxylate radical
Mole metering ratio 1:1.1 ratio adds in 15.09g chloropropyls heptamethylcyclotetrasiloxane, 4.54g potassium acetates, 75ml N, N-
Dimethylformamide, magnetic agitation are uniformly mixed three, are to slowly warm up to 100 DEG C, react 6 hours, reaction finishes, by system
It is cooled to room temperature, is removed by filtration salt, solvent is removed in vacuum distillation, is dried in vacuo 8 hours, is obtained seven methyl acetic acid propyl ester basic rings four
Siloxanyl monomers, yield 95.3%, purity 97.2%.
In three mouthfuls of reaction bulbs equipped with spherical condensation tube, thermometer and agitating device, 42.57g prestoxs ring four is added in
Siloxanes, 3.83g methyl acetic acid propyl ester basic rings tetrasiloxane, 0.46g tetramethylammonium hydroxide alkali glue, agitating and heating slowly add
Heat finds no apparent polymerism, poly- (dimethyl siloxane-methyl propyl acetate base silicon to 100 DEG C, equilibration reaction 8h
Oxygen alkane) yield be 0%.
Claims (10)
1. a kind of ester group functional poly siloxanes, which is characterized in that the polysiloxanes has structural formula shown in formula (I):
In formula (I), m=0~7000, n=1~400, m, n are all integer, and the integer of x >=1, R is alkyl or hydrocarbon containing hetero atom
Base.
2. ester group functional poly siloxanes according to claim 1, which is characterized in that in formula (I), m=0~400, n=1
~200;X=1~10, the alkyl are alkyl, aryl, aralkyl or alkylene;The alkyl containing hetero atom be containing O,
N, the alkyl of S, P or Si;
In R, the alkyl is C1~C12Alkyl, the aryl be C7~C16Aryl, the aralkyl be C8~
C12Aralkyl, the alkylene be C3~C12Alkylene;The alkyl containing hetero atom is alkyl containing carbonyl, hydroxyl
Alkyl, alkyl containing pyridyl group, alkyl containing sulfydryl or silane-group containing alkyl;
Preferably, the number-average molecular weight of the ester group functional poly siloxanes is 1 × 103~2 × 105。
3. the preparation method of the ester group functional poly siloxanes described in claims 1 or 2, as follows including step:
(1) preparation of ester-containing cyclosiloxane monomer
Using chloro-hydrocarbons cyclosiloxane monomer and carboxylate as raw material, solvent is added in, is warming up to 50~130 DEG C in atmospheric conditions
2~10h is reacted, after reaction, filters out salt, distillation removes solvent to get ester-containing cyclosiloxane;
(2) it is mixed using prepared ester-containing cyclosiloxane monomer as raw material or by it with methyl cyclosiloxane monomer, adds in acid
Catalyst is warming up to 90-110 and reacts 6-8h to get ester group functional poly siloxanes in atmospheric conditions.
4. preparation method according to claim 3, which is characterized in that the chloro-hydrocarbons cyclosiloxane described in step (1)
Ranging from r >=1 of the molar ratio r of carboxylate radical and chlorocarbon base is pressed with the proportioning of carboxylate.
5. preparation method according to claim 3, which is characterized in that the addition of chloro-hydrocarbons cyclosiloxane in step (1)
The ratio between quality and the addition volume of solvent are 1:(0.5~10) g/mL.
6. preparation method according to claim 3, which is characterized in that chloro-hydrocarbons cyclosiloxane is described in step (1)
Chloropropyl heptamethylcyclotetrasiloxane, four chloropropyl tetramethyl-ring tetrasiloxanes, chloropropyl pentamethyl cyclotrisiloxane or trichlorine
Oxypropyl trimethyl cyclotrisiloxane.
7. preparation method according to claim 3, which is characterized in that carboxylate described in step (1) is with formula (II)
Shown structure:
MOOCR
(II),
In formula (II), the meaning of R is identical with R in formula (I), M Li, Na, K, Mg, Ca, Sr, Ba or NH4;
Preferably, the carboxylate is:Potassium acetate, sodium acetate, sodium propionate, potassium propionate, potassium butyrate, sodium butyrate, Potassium Benzoate,
Sodium benzoate, potassium acrylate or sodium acrylate;
Preferably, reaction temperature described in step (1) is 60~100 DEG C.
Preferably, solvent described in step (1) is n,N-Dimethylformamide, dimethyl sulfoxide (DMSO), acetonitrile, 1,3- dimethyl -2-
Imidazolone, tetrahydrofuran alcohol mixed solvent or tetrahydrofuran methanol mixed solvent.
8. preparation method according to claim 3, which is characterized in that methyl cyclosiloxane monomer is described in step (2)
Octamethylcy-clotetrasiloxane or hexamethyl cyclotrisiloxane.
9. preparation method according to claim 3, which is characterized in that acid catalyst described in step (2) is trifluoromethyl
Sulfonic acid, Emathlite, cation exchange resin, the concentrated sulfuric acid, solid super-strong acid TiO2/SO4 2-, hydrochloric acid, nitric acid, pyrophosphoric acid, boron
One of acid, alkyl sulfonic acid, aryl sulfonic acid, fluorine hydrocarbyl sulfonic, chlorine silicic acid or lewis acid.
10. the ester group functional poly siloxanes described in claims 1 or 2 is as CO2Emulsifier be used for overcritical field;Alternatively,
Fluorescence luminescent material is used to prepare by the coordination between ester group and rare earth ion.
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Cited By (2)
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CN114653345A (en) * | 2022-05-24 | 2022-06-24 | 苏州硒诺唯新新材料科技有限公司 | Functional silica gel material and preparation method and application thereof |
CN116874789A (en) * | 2023-08-03 | 2023-10-13 | 西南石油大学 | Supercritical carbon dioxide thickener with branched structure and preparation method thereof |
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US2793223A (en) * | 1954-05-20 | 1957-05-21 | Dow Corning | Acryloxy methyl siloxanes |
CN103314056A (en) * | 2010-10-19 | 2013-09-18 | 爱博斯迪科化学(上海)有限公司 | Hybrid silicone composition for light emitting device |
CN104892944A (en) * | 2015-05-06 | 2015-09-09 | 山东大学 | Preparation method of (methyl)acryloyloxy methyl-terminiated polysiloxanes |
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US2793223A (en) * | 1954-05-20 | 1957-05-21 | Dow Corning | Acryloxy methyl siloxanes |
CN103314056A (en) * | 2010-10-19 | 2013-09-18 | 爱博斯迪科化学(上海)有限公司 | Hybrid silicone composition for light emitting device |
CN104892944A (en) * | 2015-05-06 | 2015-09-09 | 山东大学 | Preparation method of (methyl)acryloyloxy methyl-terminiated polysiloxanes |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114653345A (en) * | 2022-05-24 | 2022-06-24 | 苏州硒诺唯新新材料科技有限公司 | Functional silica gel material and preparation method and application thereof |
CN116874789A (en) * | 2023-08-03 | 2023-10-13 | 西南石油大学 | Supercritical carbon dioxide thickener with branched structure and preparation method thereof |
CN116874789B (en) * | 2023-08-03 | 2023-11-24 | 西南石油大学 | Supercritical carbon dioxide thickener with branched structure and preparation method thereof |
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