CN115651178A - Synthesis method of polyester with siloxane side group - Google Patents
Synthesis method of polyester with siloxane side group Download PDFInfo
- Publication number
- CN115651178A CN115651178A CN202211212341.6A CN202211212341A CN115651178A CN 115651178 A CN115651178 A CN 115651178A CN 202211212341 A CN202211212341 A CN 202211212341A CN 115651178 A CN115651178 A CN 115651178A
- Authority
- CN
- China
- Prior art keywords
- siloxane
- polyester
- epoxide
- groups
- group
- 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
- 229920000728 polyester Polymers 0.000 title claims abstract description 66
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000001308 synthesis method Methods 0.000 title abstract description 13
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims abstract description 49
- 150000002118 epoxides Chemical class 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- -1 carboxylate salt Chemical class 0.000 claims description 19
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000002329 infrared spectrum Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 2
- 238000009795 derivation Methods 0.000 claims description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- FBNXYLDLGARYKQ-UHFFFAOYSA-N methoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(C)CCCOCC1CO1 FBNXYLDLGARYKQ-UHFFFAOYSA-N 0.000 claims description 2
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 abstract description 14
- 230000032050 esterification Effects 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000013008 moisture curing Methods 0.000 abstract description 5
- 208000012839 conversion disease Diseases 0.000 abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 16
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000007142 ring opening reaction Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 235000011056 potassium acetate Nutrition 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical group CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- LWAMAEOQFTYZCQ-UHFFFAOYSA-N 2-(2-phenylphenyl)-3-[[3-(2-phenylphenyl)oxiran-2-yl]methoxymethyl]oxirane Chemical compound O1C(C=2C(=CC=CC=2)C=2C=CC=CC=2)C1COCC1OC1C1=CC=CC=C1C1=CC=CC=C1 LWAMAEOQFTYZCQ-UHFFFAOYSA-N 0.000 description 1
- AYHLPQOWRMPEKH-UHFFFAOYSA-N 2-(6-methylheptoxymethyl)oxirane Chemical compound CC(C)CCCCCOCC1CO1 AYHLPQOWRMPEKH-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 description 1
- RJNVSQLNEALZLC-UHFFFAOYSA-N 2-[(2-methoxyphenoxy)methyl]oxirane Chemical compound COC1=CC=CC=C1OCC1OC1 RJNVSQLNEALZLC-UHFFFAOYSA-N 0.000 description 1
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 description 1
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 description 1
- WYAFQPYCJBLWAS-UHFFFAOYSA-N 2-[(3-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC(OCC2OC2)=C1 WYAFQPYCJBLWAS-UHFFFAOYSA-N 0.000 description 1
- AVWGFHZLPMLKBL-UHFFFAOYSA-N 2-[(4-methoxyphenoxy)methyl]oxirane Chemical compound C1=CC(OC)=CC=C1OCC1OC1 AVWGFHZLPMLKBL-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- SAQSTQBVENFSKT-UHFFFAOYSA-M TCA-sodium Chemical compound [Na+].[O-]C(=O)C(Cl)(Cl)Cl SAQSTQBVENFSKT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HXWGXXDEYMNGCT-UHFFFAOYSA-M decyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)C HXWGXXDEYMNGCT-UHFFFAOYSA-M 0.000 description 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical group CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical group CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- CHWKGJOTGCSFNF-UHFFFAOYSA-N norbornene anhydride Chemical compound C1CC2C3C(=O)OC(=O)C3=C1C2 CHWKGJOTGCSFNF-UHFFFAOYSA-N 0.000 description 1
- XCOHAFVJQZPUKF-UHFFFAOYSA-M octyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)C XCOHAFVJQZPUKF-UHFFFAOYSA-M 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NOWVDELPZQQGIG-UHFFFAOYSA-N oxiran-2-ylmethyl 4-tert-butylbenzoate Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)OCC1OC1 NOWVDELPZQQGIG-UHFFFAOYSA-N 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- YNLZKJXZEZFHDO-UHFFFAOYSA-M potassium;2,2,2-trichloroacetate Chemical compound [K+].[O-]C(=O)C(Cl)(Cl)Cl YNLZKJXZEZFHDO-UHFFFAOYSA-M 0.000 description 1
- AHGFDQXBCIASJK-UHFFFAOYSA-M potassium;2,2,3,3,3-pentafluoropropanoate Chemical compound [K+].[O-]C(=O)C(F)(F)C(F)(F)F AHGFDQXBCIASJK-UHFFFAOYSA-M 0.000 description 1
- LBOHISOWGKIIKX-UHFFFAOYSA-M potassium;2-methylpropanoate Chemical compound [K+].CC(C)C([O-])=O LBOHISOWGKIIKX-UHFFFAOYSA-M 0.000 description 1
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- SCWLIHXXYXFUFV-UHFFFAOYSA-M sodium;2,2,3,3,3-pentafluoropropanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)F SCWLIHXXYXFUFV-UHFFFAOYSA-M 0.000 description 1
- TWEGKFXBDXYJIU-UHFFFAOYSA-M sodium;2-methylpropanoate Chemical compound [Na+].CC(C)C([O-])=O TWEGKFXBDXYJIU-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical group CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- AQZSPJRLCJSOED-UHFFFAOYSA-M trimethyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)C AQZSPJRLCJSOED-UHFFFAOYSA-M 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention relates to a method for synthesizing polyester with siloxane side group. The synthesis method of the polyester with the siloxane side group comprises a polymerization process of esterifying dicarboxylic anhydride and epoxide by the action of a composite catalyst, wherein the epoxide comprises epoxide with siloxane groups, and the composite catalyst comprises carboxylic acid metal salt and amphiphilic quaternary ammonium salt. The synthesis method of the polyester with the siloxane side group does not generate water molecules, does not influence the stability of the siloxane side group, and can introduce the siloxane side group into the polyester synthesis according to the invention. The amphiphilic quaternary ammonium salt is adopted to assist the carboxylate metal salt to be used as a synergistic catalyst, so that the esterification polymerization efficiency of the epoxide and the dicarboxylic anhydride is obviously improved, the reaction temperature is reduced, the reaction conversion rate is obviously improved, the obtained polyester is an alternate polyester structure of dicarboxylic acid and dihydric alcohol, and the obtained polyester product has the moisture curing characteristic.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a synthesis method of polyester with siloxane side groups.
Background
Medium and low molecular weight polyesters with molecular weights of hundreds to thousands are commonly used as host resins for various coatings, inks, adhesives, composites. The curing method of polyester is various, and comprises the steps of introducing siloxane groups into a polyester molecular chain to form siloxane modified polyester resin, and then performing hydrolytic condensation on the siloxane groups under the action of moisture to finally realize resin curing. The siloxane modified polyester can be applied to cement floor coatings, ceramic tile coatings, glass coatings, metal coatings, building adhesives, glass adhesives, mortar adhesives and other formulas, and siloxane groups in the resin can realize moisture crosslinking and curing, can realize anchoring effect with the surface of a substrate and can enhance the adhesive force of a coating. Although the siloxane groups on polyester resins may also gel during storage of the resin and formulation due to inadvertent moisture absorption, the prior art formulations are effective in inhibiting this unfavorable process.
There are also many conventional methods for introducing siloxane groups onto polyester molecules, such as introducing mercaptosiloxanes onto polyester chains via mercapto-ene addition onto polyesters with C = C double bonds; or amino siloxane is introduced into the siloxane by amino-maleate double bond addition. However, these methods all require that the polyester resin system be free of water and acid catalysts, otherwise the siloxane groups are susceptible to premature hydrolytic condensation, gelling, and premature failure of the silicone polyester. The general polyester synthesis is based on direct catalytic esterification polymerization synthesis of carboxylic acid and polyhydric alcohol, wherein most of the catalysts are sulfonic acid, organic tin Lewis acid and the like, the catalysts also remain in a resin system after the esterification is finished, and are unfavorable for siloxane introduced in the later period, so that the introduced siloxane is hydrolyzed, condensed and crosslinked in a short time, and the polyester resin is invalid.
For example, monohydric alcohol or polyhydric alcohol is reacted with acid anhydride and epoxide, and weak base catalyst is used, that is, hydroxy opening anhydride is used for esterification, the generated carboxylic acid is opened with ring oxygen for esterification, and the generated hydroxy is opened with acid anhydride for esterification. The polyester synthesis method has industrialized cases, and water molecules cannot be generated in the synthesis reaction process. According to the method, an epoxy silane coupling agent can be designed to participate in the polymerization reaction to introduce siloxane, but a large amount of carboxyl generated in the reaction process can also accelerate the hydrolytic condensation of siloxane groups under the action of a weak alkaline catalyst, so that resin gel is caused, and the synthesis fails. It is also possible to design unsaturated anhydride to react according to the above three components, and after obtaining unsaturated polyester, add C = C double bond on polyester molecular chain with mercapto or amino silane coupling agent, and introduce siloxane group. However, the method is a two-step method, and a certain polyaddition reaction may exist in the addition process of the sulfydryl or the amino and the double bond, the viscosity is increased, and in severe cases, the gel may be generated. And thus are not a very desirable route for the synthesis of silicone-pendant polyesters.
Disclosure of Invention
Based on this, the invention aims to provide a method for synthesizing a polyester with siloxane side groups, which does not generate water molecules and influence the stability of the siloxane side groups, and can introduce the siloxane side groups at the same time of synthesizing the polyester. The amphiphilic quaternary ammonium salt is adopted to assist the carboxylic acid metal salt as a synergistic catalyst, so that the esterification polymerization efficiency of the epoxide and the dicarboxylic anhydride is remarkably improved, the reaction temperature is reduced, the reaction conversion rate is remarkably improved, the obtained polyester is an alternating polyester structure of dicarboxylic acid and dihydric alcohol, and the obtained polyester product has the moisture curing characteristic.
A process for the synthesis of a polyester having pendent siloxane groups comprising a polymerisation process in which a dicarboxylic acid anhydride is esterified with an epoxide comprising an epoxide having siloxane groups by the action of a complex catalyst comprising a metal carboxylate salt and an amphiphilic quaternary ammonium salt.
According to the synthesis method of the polyester with the siloxane side group, the composite catalyst is used for ring-opening epoxy groups in the epoxide with the siloxane groups, and the ring-opening esterification reaction is continuously carried out on the epoxy groups and dicarboxylic anhydride, so that the siloxane groups are introduced, and the polyester with the siloxane side group is generated. The composite catalyst adopts the carboxylate metal salt and the amphiphilic quaternary ammonium salt, wherein the carboxylate metal salt has the function of attacking an epoxy group by carboxylate anions after entering a liquid phase, further catalytically guiding alkoxy anions to attack the dicarboxylic acid anhydride, and polymerizing to form the polyester with siloxane side groups according to the circulation. However, under normal conditions, the carboxylate metal salt has poor solubility in the organic phase, and it is difficult to independently form a high catalytic effect. The amphiphilic quaternary ammonium salt can promote the catalytic action of the carboxylate metal salt, is regarded as a synergistic catalyst, has the main effect of coordinating with the carboxylate metal salt, and can carry the transferred carboxylate anions to be transferred from a solid phase to a liquid phase according to a phase transfer catalysis mechanism, so that the carboxylate anions have a ring-opening action on epoxy groups, and subsequent and continuous ring-opening esterification reaction is started.
The polyester obtained by the synthesis method of the polyester with the siloxane side group has an alternating polyester structure of dibasic acid and dihydric alcohol, and the siloxane group is introduced into the obtained polyester product to enable the polyester product to have moisture curing characteristics. Compared with the prior art, the synthesis method of the polyester with the siloxane side group does not generate water molecules, does not influence the stability of the siloxane side group, and can introduce the siloxane side group into the polyester at the same time of synthesizing the polyester according to the invention. The amphiphilic quaternary ammonium salt is adopted to assist the carboxylate metal salt to serve as a synergistic catalyst, so that the esterification polymerization efficiency of the epoxide and the dicarboxylic anhydride is remarkably improved, the reaction temperature is reduced, and the reaction conversion rate is remarkably improved.
Further, the epoxide with siloxane group is a siloxane coupling agent containing an epoxy group and a siloxane group, wherein the epoxy group comprises a glycidyl group (the structure of which is shown in formula I, and an asterisk indicates the position of an external group) or an epoxidized cyclohexene group (the structure of which is shown in formula II, and an asterisk indicates the position of an external group); the siloxane group comprises a silicon group containing 1-3 methoxyl groups (the structure of the silicon group is shown in a formula III, and an asterisk indicates the position of an external group) or a silicon group containing 1-3 ethoxyl groups for connection (the structure of the silicon group is shown in a formula IV, and an asterisk indicates the position of an external group).
The glycidyl group or the epoxidized cyclohexene group facilitates subsequent ring-opening esterification reactions, and the siloxane group containing 1-3 methoxy groups or 1-3 ethoxy-linked silicon groups facilitates subsequent moisture curing of the synthesized polyester. Preferably, the siloxane group is at least one of trimethoxy silicon group, triethoxy silicon group, dimethoxy methyl silicon group, diethoxy methyl silicon group, methoxy dimethyl silicon group and methyl diethoxy silicon group.
Further, the molar ratio of the dicarboxylic anhydride, the epoxide, the carboxylic acid metal salt, and the amphiphilic quaternary ammonium salt is n (the dicarboxylic anhydride): n (the epoxide): n (the carboxylic acid metal salt): n (the amphiphilic quaternary ammonium salt) =1: (1-1.1): (0.01-0.05): (0.01-0.05). The molar ratio is favorable for improving the conversion rate of the acid anhydride and fully utilizing raw materials.
Further, the epoxides also include epoxides without siloxane groups in a molar ratio of epoxides with siloxane groups to epoxides without siloxane groups of n (the epoxides with siloxane groups): n (the epoxide without siloxane group) =1: (0 to 9). The addition of the epoxide without siloxane groups favours the ring-opening esterification of the epoxide groups.
Further, the metal carboxylate is a potassium or sodium salt of a fatty acid having 2 to 4 carbon atoms; the amphiphilic quaternary ammonium salt is chlorinated or brominated quaternary ammonium salt with three methyl groups and one alkyl group with 7-16 carbon atoms connected to an N atom. Preferably, the potassium or sodium salt of a fatty acid is at least one of potassium acetate, sodium acetate, potassium propionate, sodium propionate, potassium acrylate, sodium acrylate, potassium n-butyrate, sodium n-butyrate, potassium isobutyrate, sodium isobutyrate, potassium trifluoroformate, sodium trifluoroformate, potassium trichloroacetate, sodium trichloroacetate, potassium perfluoropropionate, and sodium perfluoropropionate. The amphiphilic quaternary ammonium salt requires to have certain affinity for high-polarity salt and low-polarity organic monomer (liquid epoxide) at the same time, so that quaternary ammonium salt with multi-carbon alkyl and trimethyl substitution is selected as a synergistic catalyst, and the basic structural characteristic of the quaternary ammonium salt is chlorinated or brominated quaternary ammonium salt of which N atom is connected with three methyl groups and one alkyl group with 7-16 carbon atoms. Preferably, the amphiphilic quaternary ammonium salt is at least one of benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, octyltrimethylammonium chloride, octyltrimethylammonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride and hexadecyltrimethylammonium bromide.
Further, the dicarboxylic acid anhydride is a dicarboxylic acid anhydride having 4 to 10 carbon atoms. Preferably, the dicarboxylic anhydride is at least one of maleic anhydride, succinic anhydride, phthalic anhydride (abbreviated as phthalic anhydride in the industry), tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, norbornene anhydride, methylnadic anhydride and chlorendic anhydride.
Further, the epoxide with siloxane group is at least one of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane; or the epoxide with siloxane group is at least one of other siloxane containing epoxy group which is obtained by self-synthesis derivation based on mercaptosiloxane, aminosiloxane, methacrylate siloxane, vinyl siloxane, peroxide siloxane and the like.
Further, the epoxide without siloxane groups is a glycidyl ether or ester. The epoxide compound having no siloxane group is glycidyl ether or glycidyl ester which is a glycidyl structure, and preferably, it may be at least one of a hydrocarbyl glycidyl ether composed of a hydrocarbyl group having 3 to 12 carbon atoms and a glycidyl group, or may be glycidyl versatate or glycidyl 4-t-butylbenzoate. The hydrocarbyl glycidyl ether is preferably at least one of isopropyl glycidyl ether, allyl glycidyl ether, n-butyl glycidyl ether, tert-butyl glycidyl ether, phenyl glycidyl ether, 2-methylphenyl glycidyl ether, 3-methylphenyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, 2-methoxyphenyl glycidyl ether, benzyl glycidyl ether, isooctyl glycidyl ether, and 2-biphenyl glycidyl ether.
Further, the reaction temperature of the polymerization is 80-120 ℃. Preferably, the reaction temperature of the polymerization is 90 to 100 ℃. By adopting the composite catalyst, namely the carboxylic acid metal salt and the amphiphilic quaternary ammonium salt are combined to catalyze the ring-opening esterification reaction of the dicarboxylic anhydride and the epoxide, the polymerization reaction temperature can be reduced to 90-100 ℃, and the monomer polymerization conversion rate is nearly complete.
The synthesis method of the polyester with the silicone side group further comprises the step of carrying out infrared spectrum detection on the polyester in the polymerization process. The polyester resin product obtained by the synthesis method of the polyester with the silicone-oxygen side group is detected by infrared spectroscopy, and the dicarboxylic anhydride is 1800cm -1 The nearby characteristic absorption peak completely disappears, the polyester synthesis reaction is complete, the dicarboxylic anhydride structure is different, and the specific wavenumber of the characteristic absorption peak is different. The time of the synthesis reaction of the polyester is determined by the time of the complete disappearance of the characteristic absorption peak of the infrared spectrum dicarboxylic anhydride of the reaction system. 912cm of corresponding raw material epoxy group in infrared spectrum of product polyester resin -1 The near characteristic absorption peak essentially disappeared, indicating that the epoxide feed conversion was nearly complete. The infrared spectrum of the product polyester resin is 1740cm -1 And a strong characteristic absorption peak appears nearby, which indicates that a polymerization product has a large number of ester bond characteristic structures. The molecular weight of the product resin is detected by a gel permeation chromatography GPC method, and the number average molecular weight M of the product resin n Most of them are 1400 to 2600.
The polyester resin obtained by the synthesis method of the polyester with the silicone-oxygen side group is coated with a film after 1% (w/w) dibutyl tin dilaurate DBTL curing accelerator is added, can be cured within 24 hours, can be used as a coating and an adhesive, and has good adhesion to silicate material substrate materials or metal substrate materials.
Detailed Description
Example 1
1.00mol of maleic anhydride (dicarboxylic anhydride), 1.05mol of 3-glycidyl ether oxypropyltrimethoxysilane (epoxide with siloxane groups), 0.01mol of potassium acetate (carboxylic acid metal salt) and 0.01mol of benzyl trimethyl ammonium chloride (amphiphilic quaternary ammonium salt) are added into a dry three-neck flask provided with a mechanical stirring device, a reflux condenser tube and an oil bath heating device, and a moisture isolation device is arranged in a reaction system. Stirring, rapidly heating to about 95 deg.C, timing to dissolve a large amount of anhydride solid, increasing viscosity, sampling every 1hr, performing infrared spectrum detection, and detecting the concentration of maleic anhydride in the reaction system at 1783cm -1 The characteristic infrared absorption signal completely disappears, and then the original condition reaction is continued for 1hr, and the reaction is finished to obtain the polyester product, and the product is sealed and stored. In the whole reaction process, the maleic anhydride and the 3-glycidyl ether oxypropyl trimethoxy silane are completely converted, no post-treatment is performed in the middle, and the actual yield is 100%. GPC determined the product molecular weight M n ＝2600，M w ＝3100。
Example 2
1.00mol of maleic anhydride (dicarboxylic anhydride), 1.05mol of 3-glycidyl ether oxypropyltrimethoxysilane (epoxide with siloxane groups), 0.05mol of potassium acetate (carboxylic acid metal salt) and 0.05mol of benzyltrimethylammonium chloride (amphiphilic quaternary ammonium salt) are added into a dry three-neck flask provided with a mechanical stirring device, a reflux condenser tube and an oil bath heating device, and a moisture isolation device is arranged in a reaction system. Stirring, rapidly heating to about 95 deg.C, timing to dissolve a large amount of anhydride solid, increasing viscosity, sampling every 1hr, detecting by infrared spectroscopy, and detecting by 1783cm of maleic anhydride originally belonging to the reaction system after 11hr -1 The characteristic infrared absorption signal completely disappears, and then the original condition reaction is continued for 1hr, and the reaction is finished to obtain the polyester product, and the product is sealed and stored. GPC determined the product molecular weight M n ＝2450，M w ＝3050。
Comparative example 1
1.00mol of maleic anhydride, 1.05mol of 3-glycidoxypropyltrimethoxysilane and 0.05mol of potassium acetate are added into a dry three-necked flask provided with a mechanical stirring device, a reflux condenser tube and an oil bath heating device, and a moisture isolation device is arranged in a reaction system. Stirring, rapidly heating to about 95 deg.C, timing to dissolve a large amount of maleic anhydride solid, increasing viscosity, sampling every 1hr, and detecting by infrared spectroscopy to obtain 18hr sample of 1783cm of maleic anhydride originally belonging to the reaction system -1 The characteristic infrared absorption signal does not disappear, and the maleic anhydride residue is more, so that the synthesis reaction is regarded as failure.
Comparative example 2
1.00mol of maleic anhydride, 1.05mol of 3-glycidyl ether oxypropyltrimethoxysilane, 0.05mol of potassium acetate and 0.05mol of tetrabutylammonium bromide are added into a dry three-neck flask provided with a mechanical stirring device, a reflux condenser tube and an oil bath heating device, and a moisture isolation device is arranged in a reaction system. Stirring, rapidly heating to about 95 deg.C, timing to dissolve a large amount of maleic anhydride solid, increasing viscosity, sampling every 1hr, and detecting by infrared spectroscopy to obtain 18hr sample of 1783cm of maleic anhydride originally belonging to the reaction system -1 The characteristic infrared absorption signal does not disappear, and the maleic anhydride residue is more, so that the synthesis reaction is regarded as failure.
Examples 3 to 18
The molar amounts charged and the operating conditions of examples 3 to 18 were the same as in example 2, and the parameters of the type of dibasic acid anhydride, the type of epoxide having a siloxane group, the type of metal salt of carboxylic acid, the type of amphiphilic quaternary ammonium salt, the time for completion of the acid anhydride reaction, the molecular weight of the product, etc. were varied as shown in Table 1.
TABLE 1 EXAMPLES 3-18 parameters
Example 19
1.00mol of maleic anhydride (dicarboxylic anhydride), 0.105mol of 3-glycidyloxypropyltriethoxysilane (epoxide with siloxane groups), 0.945mol of isopropyl glycidyl ether (epoxide without siloxane groups), 0.05mol of potassium acetate (metal carboxylate), 0.05mol of dodecyltrimethylammonium bromide (amphiphilic quaternary ammonium salt) are added into a dry three-necked flask equipped with a mechanical stirring device, a reflux condenser and an oil bath heating device, and a moisture isolation device is installed in the reaction system. Stirring, rapidly heating to about 95 deg.C, timing, dissolving a large amount of anhydride solid in the reaction system, increasing viscosity, sampling every 1hr, performing infrared spectrum detection, and detecting to obtain 1783cm of maleic anhydride after 6hr -1 The characteristic infrared absorption signal completely disappears, and then the original condition reaction is continued for 1hr, and the reaction is finished to obtain the polyester product, and the product is sealed and stored. GPC determines the product molecular weight M n ＝1910，M w ＝2350。
Examples 20 to 25
The molar amounts charged and the operating conditions of examples 20 to 35 are the same as in example 19, with variation of the epoxide type without siloxane groups, the time to completion of the anhydride reaction, the molecular weight of the product, etc., see Table 2.
TABLE 2 examples 20-25 parameters
Compared with the prior art, the synthesis method of the polyester with the siloxane side group does not generate water molecules, does not influence the stability of the siloxane side group, and can introduce the siloxane side group into the polyester at the same time of synthesizing the polyester according to the invention. The amphiphilic quaternary ammonium salt is adopted to assist the carboxylate metal salt to be used as a synergistic catalyst, so that the esterification polymerization efficiency of the epoxide and the dicarboxylic anhydride is obviously improved, the reaction temperature is reduced, the reaction conversion rate is obviously improved, the obtained polyester is an alternate polyester structure of dicarboxylic acid and dihydric alcohol, and the obtained polyester product has the moisture curing characteristic.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that numerous changes and modifications can be made by those skilled in the art without departing from the inventive concepts and it is intended that such changes and modifications be covered by the present invention.
Claims (10)
1. A method for synthesizing a polyester with siloxane side groups is characterized by comprising the following steps: comprising a polymerization process in which a dicarboxylic anhydride is esterified with an epoxide comprising an epoxide with siloxane groups by the action of a complex catalyst comprising a metal carboxylate salt and an amphiphilic quaternary ammonium salt.
2. The method of synthesizing a polyester with pendent siloxane groups according to claim 1, wherein: the epoxide with siloxane group is a siloxane coupling agent containing one epoxy group and one siloxane group, wherein the epoxy group comprises glycidyl group or cyclohexene oxide group; the siloxane groups include silicon groups containing 1 to 3 methoxy or 1 to 3 ethoxy linkages.
3. A method of synthesizing a polyester with pendent siloxane groups according to claim 1 or 2, wherein: the molar ratio of the dicarboxylic acid anhydride, the epoxide, the carboxylic acid metal salt, and the amphiphilic quaternary ammonium salt is n (the dicarboxylic acid anhydride): n (the epoxide): n (the carboxylic acid metal salt): n (the amphiphilic quaternary ammonium salt) =1: (1-1.1): (0.01-0.05): (0.01-0.05).
4. A method of synthesizing a polyester with pendent siloxane groups according to claim 3, wherein: the epoxides also include epoxide without siloxane groups in a molar ratio n (the epoxide with siloxane groups): n (the epoxide without siloxane group) =1: (0 to 9).
5. The process for the synthesis of polyesters bearing pendant silicone groups according to any of claims 1 to 4, characterized in that: the metal carboxylate is potassium salt or sodium salt of fatty acid with 2-4 carbon atoms; the amphiphilic quaternary ammonium salt is chlorinated or brominated quaternary ammonium salt with three methyl groups and one alkyl group with 7-16 carbon atoms connected to an N atom.
6. The process of synthesizing a polyester with pendant silicone groups according to any of claims 1 to 4, wherein: the dicarboxylic acid anhydride is a dicarboxylic acid anhydride having 4 to 10 carbon atoms.
7. The process for the synthesis of polyesters bearing pendant silicone groups according to any of claims 1 to 4, characterized in that: the epoxide with siloxane groups comprises at least one of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane; or the epoxide with siloxane groups comprises at least one of other siloxane containing epoxy groups which is obtained by self-synthesis derivation based on mercaptosiloxane, aminosiloxane, methacrylate siloxane, vinyl siloxane, peroxide siloxane and the like.
8. The method of synthesizing a polyester with pendent siloxane groups according to claim 4, wherein: the epoxide without siloxane groups is a glycidyl ether or ester.
9. The method of synthesizing a polyester with pendant silicone groups of any of claims 1-8, wherein: the reaction temperature of the polymerization is 80-120 ℃.
10. The method of synthesizing a polyester with pendant silicone groups of any of claims 1-8, wherein: the method also comprises the step of carrying out infrared spectrum detection on the polyester in the polymerization process.
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| JPH03203952A (en) * | 1989-12-29 | 1991-09-05 | Kanegafuchi Chem Ind Co Ltd | Curable resin composition |
| JPH10306148A (en) * | 1997-05-06 | 1998-11-17 | Toyo Ink Mfg Co Ltd | Production of aqueous polyester dispersion |
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| CN116836525A (en) * | 2023-08-09 | 2023-10-03 | 东莞市泰彩色料有限公司 | Environment-friendly degradable color master batch and preparation method thereof |
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