CN103113567B - Epoxy-terminated silicon oil modified carboxyl-terminated hyperbranched polyester, and preparation method and application thereof - Google Patents
Epoxy-terminated silicon oil modified carboxyl-terminated hyperbranched polyester, and preparation method and application thereof Download PDFInfo
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- CN103113567B CN103113567B CN201310043488.1A CN201310043488A CN103113567B CN 103113567 B CN103113567 B CN 103113567B CN 201310043488 A CN201310043488 A CN 201310043488A CN 103113567 B CN103113567 B CN 103113567B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 103
- 239000003921 oil Substances 0.000 title claims abstract description 81
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 74
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010703 silicon Substances 0.000 title claims abstract description 72
- 229920006150 hyperbranched polyester Polymers 0.000 title abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 144
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 128
- 229920002545 silicone oil Polymers 0.000 claims description 120
- 238000000576 coating method Methods 0.000 claims description 79
- 239000011248 coating agent Substances 0.000 claims description 76
- 229920001296 polysiloxane Polymers 0.000 claims description 73
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 58
- 239000001301 oxygen Substances 0.000 claims description 58
- 229910052760 oxygen Inorganic materials 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000010792 warming Methods 0.000 claims description 36
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 34
- 238000004821 distillation Methods 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 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 18
- -1 octyloxy tin Chemical compound 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 13
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229960001866 silicon dioxide Drugs 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 235000019439 ethyl acetate Nutrition 0.000 claims description 9
- 150000007521 triprotic acids Chemical class 0.000 claims description 9
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 claims description 5
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000003973 paint Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 2
- 239000004135 Bone phosphate Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 21
- 238000000227 grinding Methods 0.000 description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- 239000004645 polyester resin Substances 0.000 description 18
- 239000012752 auxiliary agent Substances 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 238000001514 detection method Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 229920002050 silicone resin Polymers 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 5
- 238000006735 epoxidation reaction Methods 0.000 description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229920000587 hyperbranched polymer Polymers 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 3
- QEPNERRWNQRFNH-UHFFFAOYSA-N CCCCCCCC[Zn]CCCCCCCC.O Chemical compound CCCCCCCC[Zn]CCCCCCCC.O QEPNERRWNQRFNH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical class [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses epoxy-terminated silicon oil modified carboxyl-terminated hyperbranched polyester, and a preparation method and application thereof. The method comprises the following steps: evenly mixing dibasic alcohol and tribasic acid, then heating to 70-90 DEG C, and adding epoxy-terminated silicon oil and dimethylbenzene; heating at 180-210 DEG C for 1-3 hours, heating up to 220-240 DEG C, and heating for 1-3 hours; cooling to 90 DEG C, and adding organic solvent, an organic silicon low polymer and a crosslinking catalyst; heating to 110-120 DEG C, and heating for 2-3 hours; and cooling to 90 DEG C. The resin prepared through the method can be used for the preparation of high-temperature-resistant low-surface-energy paint. According to the method, the epoxy-terminated silicon oil is added in the carboxyl-terminated hyperbranched polyester synthesis process, so that the heat resistance and flexibility of the polyester are enhanced; and the organic silicon low polymer and the polyester are subjected to crosslinking reaction, so that the heat resistance of the polyester is enhanced. The resin prepared through the method can be used for the preparation of high-temperature-resistant paint.
Description
Technical field
The present invention relates to Hyperbranched Polyester Resin, particularly relate to silicon oil modified end carboxyl super branched polyester of a kind of end ring oxygen and preparation method thereof and application, belong to field of organic polymer compound.
Background technology
Vibrin has excellent metal adhesion, and the high good physical and mechanical properties of hardness and preferably resistance to chemical corrosion, be used widely in coating industry.But vibrin exists resistance toheat difference, the shortcoming of the low and weather resistance difference of water resistance, limits its application in high-temperature resistant coating.In order to improve the resistance to elevated temperatures of vibrin, other resins conventional carry out chemical modification to it.Silicone resin is a kind of You Ji – inorganic hybrid material, has excellent thermotolerance, weathering resistance, water tolerance and lower surface tension.Use silicone resin to carry out modification to vibrin, the resistance toheat of vibrin, water resistance and chemical resistance can be improved.(the Li great Ming such as the large ring of such as Lee, the development of the durable coiled material finishing paint of organosilicon modified polyester type, coatings industry, 2007,37 (12), 30 ?32) by hydroxyl polyester and silicone resin reaction prepare silicone resin modified poly ester, the modified poly ester of acquisition has good ageing resistance, but the snappiness of this modified poly ester is poor, cold-and-heat resistent alternation performance is low.(the Ma Yiwen etc. such as Ma Yiwen, the preparation of epoxy-terminated silicone oil modified polyester resin, plating and covering with paint, 2011,02 phase) in utilize saturated hydroxy silane to be properties-correcting agent, with 1,2 ?propylene glycol and hexanodioic acid carry out polycondensation, prepare acid modified alcoholic type vibrin, the adhesion 1 grade of this modified polyester resin, shock strength 4.5Mpa, hardness 2H; But there is the shortcoming of thermotolerance.(the research of the end carboxyl super branched polyester that high functionality is organic-silicon-modified such as Yao Jiangliu, Shanghai coating, 2007,45 (7), 4 ~ 6) the organic-silicon-modified end carboxyl super branched polyester of design and synthesis, prepares two component coating by this resin and polyurethane curing agent HDI biuret and HDI tripolymer.This coating has excellent weathering resistance, good sticking power and elasticity, but this modified poly ester must and polyurethane curing agent with the use of, exist and use inconvenience shortcoming efficiently.(the Li Huagong etc. such as Li Huagong, the synthesis of organic-silicon-modified hydroxyl telechelic polyester, synthetic resins and plastics, 2012,29 (2): 20 ~ 23) adopt organosilicon performed polymer modification hydroxyl telechelic polyester, improve resistance toheat and the salt water resistance performance of polyester.
Hyperbranched polymer has highly branched structure and a large amount of terminal reactive groups, has high resolution, low viscosity and higher chemical reactivity etc., is widely used in paint field.Low viscosity makes hyperbranched polymer be applicable to being applied to high solid component coating, can reduction system viscosity blended with line polymer coating, improves system mobility; High solvability can reduce the consumption of solvent, reduces costs, and reduces noxious gas emission; Highly branched structure makes hyperbranched polymer molecule inter-chain entanglement less, not easily crystallization, makes coating have good film forming properties; Numerous terminal functionality makes Hyperbranched Polymer have very strong correctability ability, can prepare and be applicable to multi-purpose coating.Such as Chinese patent CN102504293A, by organic-silicon-modified end carboxyl super branched polyester, improves the mechanical property of silicone resin, chemical resistance and water resistance.But the snappiness of the organic-silicon-modified end carboxyl super branched polyester of above-mentioned preparation is poor, can ftracture under high/low temperature alternation condition, limit its application.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of resistance toheat and the silicon oil modified end carboxyl super branched polyester of the good end ring oxygen of snappiness.
The present invention's second technical problem that will solve is to provide the preparation method of the silicon oil modified end carboxyl super branched polyester of described end ring oxygen.
The present invention's the 3rd technical problem that will solve is to provide the coating containing the silicon oil modified end carboxyl super branched polyester of this end ring oxygen.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A preparation method for the end carboxyl super branched polyester that end ring oxygen is silicon oil modified, the method is made up of following steps:
Be that the triprotic acid of dibasic alcohol 1 ~ 1.5 times mixes post-heating to 70 ~ 90 DEG C by dibasic alcohol and molar weight, add the epoxy-terminated silicone oil of dibasic alcohol weight 0.05 ~ 0.1 times and the dimethylbenzene of dibasic alcohol weight 0.02 ~ 0.1 times; Heat 1 ~ 3h at 180 ~ 210 DEG C after, be warming up to 220 ~ 240 DEG C, after heating 1 ~ 3h; Be cooled to 90 DEG C, add the organic solvent of dibasic alcohol weight 1.0 ~ 1.5 times, the silicone oligomer that dibasic alcohol weight is 1.5 ~ 2.0 times and dibasic alcohol weight 1 ~ 5% crosslinking catalyst; Be heated to 110 ~ 120 DEG C, heating 2 ~ 3h; Be cooled to 90 DEG C, finally adding organic solvent adjustment solid content is 60 ~ 70%;
Described dibasic alcohol be neopentyl glycol, 2 ?methyl 1,3 ?propylene glycol and 1,4 ?one in cyclohexanediol or two or more;
Described triprotic acid is 1,2,4 ?benzene tricarboxylic acid and 1,3,5 ?one in benzene tricarboxylic acid or two kinds;
The weight-average molecular weight of described epoxy-terminated silicone oil is 300 ~ 1000, and every 100g epoxy-terminated silicone oil contains 8 ~ 100mmol epoxy group(ing);
Described crosslinking catalyst is tetrabutyl titanate or tetrabutyl titanate;
Described organic solvent is one or more in butanols, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and dipropylene acetic ester.
The weight-average molecular weight of described silicone oligomer is 800 ~ 2000, and containing the methoxy or ethoxy of 2.5 ~ 15w% and the hydroxyl of 3 ~ 20w%.
Described epoxy-terminated silicone oil can be prepared by following methods:
The tetramethyl disiloxane of octamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane weight 0.01 ~ 0.05% and the vitriol oil of octamethylcyclotetrasiloxane weight 2 ~ 6% are added in reactor, nitrogen protection reaction 7 ~ 10h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; To hold hydrogen silicone oil, the glycidyl allyl ether of octamethylcyclotetrasiloxane weight 1 ~ 10%, the toluene of octamethylcyclotetrasiloxane weight 1 ~ 2 and the Platinic chloride of octamethylcyclotetrasiloxane weight 0.01 ~ 0.05% add in reactor; Be warming up to 70 ~ 90 DEG C, nitrogen protection reaction 8 ~ 10h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
Above-mentioned preparation method, wherein said silicone oligomer can be obtained by one or more condensation reactions that are hydrolyzed of siloxanes such as methltriethoxysilone, dimethyldiethoxysilane and phenyl triethoxies, also can be obtained by one or more condensation reactions that are hydrolyzed of siloxanes such as monomethyl Trimethoxy silane, dimethyldimethoxysil,ne and phenyl trimethoxies.Wherein, the condensation reaction that is hydrolyzed of described siloxanes is that the conventional siloxanes in this area is hydrolyzed condensation reaction, and its technique and reaction conditions are the routine techniquess that those skilled in the art should grasp.
Above-mentioned preparation method, wherein said silicone oligomer can also be the KR211 of company of SHIN-ETSU HANTOTAI, KR212, the KR214 of company of SHIN-ETSU HANTOTAI of company of SHIN-ETSU HANTOTAI, the IC836 of KR216, Wa Ke company of company of SHIN-ETSU HANTOTAI, the KR213 of company of SHIN-ETSU HANTOTAI, the KR9218 of company of SHIN-ETSU HANTOTAI, the KR217 of company of SHIN-ETSU HANTOTAI, Dow Corning Corporation 233, Dow Corning Corporation 249, the Z ?6108 of Dow Corning Corporation, Dow Corning Corporation 3074, Dow Corning Corporation 3037 in one or two or more.
Above-mentioned preparation method, wherein,
Wherein crosslinking catalyst is tetrabutyl titanate.
The weight-average molecular weight of described epoxy-terminated silicone oil preferably 300 ~ 800, and every 100g epoxy-terminated silicone oil is better containing 30 ~ 50mmol epoxy group(ing).
Organic-silicon-modified end carboxyl super branched polyester prepared by method of the present invention, has the following advantages:
First dibasic alcohol, triprotic acid and epoxy-terminated silicone oil are carried out the end carboxyl super branched vibrin of reaction preparation, wherein the hydroxyl on dibasic alcohol and the carboxyl on triprotic acid carry out esterification, epoxy group(ing) simultaneously in the hydroxyl of dibasic alcohol and epoxy-terminated silicone oil reacts, flexible silicone segment is embedded in hyper-branched polyester, improve the resistance toheat of polyester, snappiness and film cold-and-heat resistent change performance.
Then end carboxyl super branched vibrin and silicone oligomer reaction are prepared organic-silicon-modified end carboxyl super branched vibrin, hydroxyl wherein on superbrnaching end-hydroxy polyester resin and carboxyl, under crosslinking catalyst effect can with the alkoxyl group on silicone oligomer or silicone hydroxyl generation crosslinking reaction, improve the resistance toheat of vibrin.
The silicon oil modified end carboxyl super branched polyester of end ring oxygen of the present invention can be applied in the high temperature resistant low surface energy coatings of preparation, and this coating has good resistance toheat, snappiness and cold-and-heat resistent change performance.
Coating of the present invention, this coating contains the above-mentioned organic-silicon-modified superbrnaching end-hydroxy polyester resin of 60 ~ 80w%, 10 ~ 20w% is high temperature resistant filler and 5 ~ 20w% high boiling solvent, wherein,
Described high boiling solvent be divalent ester mixture, ethylene glycol ether acetate, butyl acetic ester, isobutyl isobutyrate, Bing Suan ?3 ?one in ether ethyl ester and methyl isoamyl ketone or two or more;
Described filler is the high temperature resistant filler that this area is commonly used, and can be titanium dioxide, silicon-dioxide or silicon carbide.
Also can add the high-temperature resisting pigment that this area is conventional in above-mentioned coating, described high-temperature resisting pigment can be the inorganic high-temperature resistant such as carbon black, iron oxide red pigment, also can be the organic high temperature-resistant pigment such as phthalocyanine blue.
The organosilicon auxiliary agent that this area is conventional can also be added in above-mentioned coating, e.g., play the effects such as levelling, froth breaking, pigment wetting, viscosity adjustment.Above-mentioned organosilicon auxiliary agent can also be silicone oil, organic silicon modified by polyether auxiliary agent, e.g., and the CoatOSil series polyether modified organic silicon auxiliary agent of Mai Tu new high-tech material company limited.Those skilled in the art can according to requiring kind and the consumption of determining organic silicon additive, and the consumption that the present inventor recommends is 1 ~ 5w%.
The preparation method of above-mentioned coating is the conventional preparation method in this area, is mixed to get by the superbrnaching end-hydroxy polyester resin of modification, pigment, filler, organosilicon auxiliary agent and high boiling solvent.
The end carboxyl super branched polyester adopting above-mentioned end ring oxygen silicon oil modified due to coating of the present invention is standby, therefore has high heat resistance energy and good snappiness.
Relative to prior art, tool of the present invention has the following advantages and beneficial effect:
1) dibasic alcohol, triprotic acid and epoxy-terminated silicone oil are carried out the end carboxyl super branched vibrin of reaction preparation by the present invention, wherein the hydroxyl on dibasic alcohol and the carboxyl on triprotic acid carry out esterification, epoxy group(ing) simultaneously in the hydroxyl of dibasic alcohol and epoxy-terminated silicone oil reacts, flexible silicone segment is embedded in hyper-branched polyester, improve the resistance toheat of polyester, snappiness and film cold-and-heat resistent change performance.
2) end carboxyl super branched vibrin and silicone oligomer reaction are prepared organic-silicon-modified end carboxyl super branched vibrin by the present invention, hydroxyl wherein on superbrnaching end-hydroxy polyester resin and carboxyl, under crosslinking catalyst effect can with the alkoxyl group on silicone oligomer or silicone hydroxyl generation crosslinking reaction, improve the resistance toheat of vibrin.
3) coating of the present invention adopts above-mentioned organic-silicon-modified superbrnaching end-hydroxy polyester preparation, therefore has high heat resistance energy and good snappiness.The silicon oil modified end carboxyl super branched polyester of described end ring oxygen can be applied in the high temperature resistant low surface energy coatings of preparation, and this coating has good resistance toheat, snappiness and cold-and-heat resistent change performance.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of the organic-silicon-modified end carboxyl super branched polyester of embodiment 1 gained.
Embodiment
Infared spectrum below about organic-silicon-modified end carboxyl super branched polyester in embodiment is substantially identical with Fig. 1, does not provide one by one.
Embodiment 1
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively by proportioning in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.02g and vitriol oil 4g, nitrogen protection reaction 7h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; By obtained end hydrogen silicone oil, glycidyl allyl ether 2g, toluene 200g and Platinic chloride 0.02g add in reactor; Be warming up to 70 DEG C, nitrogen protection reaction 8h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 1015; Result is that every 100g epoxy-terminated silicone oil contains 8.1mmol epoxy group(ing).
2) preparation of organic-silicon-modified end carboxyl super branched polyester
By dibasic alcohol neopentyl glycol 104g (1mol) and triprotic acid 1,3,5 ?benzene tricarboxylic acid 210g (1mmol) mix post-heating to 70 DEG C, add epoxy-terminated silicone oil 5.1g and dimethylbenzene 2.08g; Heat 1h at 180 DEG C after, be warming up to 240 DEG C, after heating 1h; Be cooled to 90 DEG C, add the organic solvent 1-Methoxy-2-propyl acetate 104g of 1.0 times of dibasic alcohol weight, the silicone oligomer 156g of SHIN-ETSU HANTOTAI silicone resin KR 150 and crosslinking catalyst tetra-n-butyl titanate 1.04g; Be heated to 110 DEG C, heating 2h; Be cooled to 90 DEG C, finally add residue organic solvent 196g, controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.As accompanying drawing 1 middle infrared spectrum display: 3500cm
?1place broad peak Wei ?OH absorption peak, 2950cm
?1chu Wei ?CH
3absorption peak, 1730cm
?1chu Wei ?COO ? absorption peak, 1120cm
?1place for Si ?O ?Si absorption peak, 980cm
?1place is epoxy absorption peak, 1250cm
?1and 800cm
?1place for Si ?CH
3absorption peak.?COO ? the existence of absorption peak show the polyester construction of matrix resin, Si ?O ?Si and Si ?CH
3the existence of absorption peak demonstrates the modification that resin have passed through silicone resin.
The silicon oil modified end carboxyl super branched polyester property detection case of end ring oxygen is as shown in table 1.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 420 DEG C, snappiness 1mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 1 is organic-silicon-modified
1
*solvent resistance detection method: at 25 DEG C, uses butanone wiping 100 times back and forth.
2
*resistance toheat detection method: by test piece after 180 DEG C of baking 2h, put into the Ovenized electric furnace that potentiometer is checked, by 5 DEG C/min raised temperature, start timing with furnace temperature to requirement of experiment temperature, sample, after continuous high temperature, takes out, be chilled to room temperature (25 DEG C), observe coatingsurface situation with magnifying glass, as without be full of cracks, obscission, namely illustrate that coating heat resistance can be good.
3) the coating preparation containing this organic-silicon-modified end carboxyl super branched polyester
By silicon oil modified to filler titanium dioxide 60g, end ring oxygen end carboxyl super branched polyester 100g, silicone oil
the organosilicon auxiliary agent 8g of/350cst, the high boiling solvent 5g of divalent ester mixture (DBE) mix, and add grinding machine for grinding to required particle diameter, both.
The coating property of preparation is as shown in table 2: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 490 DEG C, snappiness 2mm, cold-hot alternation 58 times.
The performance index of table 2 coating
Embodiment 2:
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.02g and vitriol oil 4g, nitrogen protection reaction 7h; Be warming up to 190 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 2g, toluene 200g and Platinic chloride 0.02g are added in reactor; Be warming up to 70 DEG C, nitrogen protection reaction 8.0h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 1015; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 8.1mmol epoxy group(ing).
2) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 62.4g neopentyl glycol, 36g 2 ?Jia Ji ?1,3 propylene glycol, 210g 1,2,4 ?benzene tricarboxylic acid and 105g 1,3,5 ?benzene tricarboxylic acid mix post-heating to 80 DEG C, add epoxy-terminated silicone oil and the 9.84g dimethylbenzene of the above-mentioned preparation of 9.84g; Heat 3h at 200 DEG C after, be warming up to 220 DEG C, after heating 2h; Be cooled to 80 DEG C, add 147g 1-Methoxy-2-propyl acetate, 100g SHIN-ETSU HANTOTAI silicone resin KR150, the KR212 of company of 47.6g SHIN-ETSU HANTOTAI, 49.2g TriMethylolPropane(TMP) glycidyl ether and 4.9g tetra-n-butyl titanate; Be heated to 115 DEG C, heating 3h; Be cooled to 80 DEG C, finally add 23g butanols, controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The silicon oil modified end carboxyl super branched polyester property detection case of end ring oxygen is as shown in table 3.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 420 DEG C, snappiness 1mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 3 end ring oxygen is silicon oil modified
3) coating
Composition: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 160g step 2 preparation, 20g titanium dioxide, 8g silicon-dioxide, 1g silicone oil
/ 350cst, 10g ethylene glycol ether acetate.
Preparation technology: end carboxyl super branched polyester silicon oil modified to filler, end ring oxygen, high boiling solvent, organosilicon auxiliary agent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is as shown in table 4: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 510 DEG C, snappiness 2mm, cold-hot alternation 59 times.
The performance index of table 4 coating
Embodiment 3:
1) preparation of epoxy silicon oil is held
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.06g and vitriol oil 10g, nitrogen protection reaction 8h; Be warming up to 185 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 18g, toluene 350g and Platinic chloride 0.07g are added in reactor; Be warming up to 80 DEG C, nitrogen protection reaction 9h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 492; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 77mmol epoxy group(ing).
2) preparation of silicone oligomer
Prolong is being housed, thermometer, 42.0g monomethyl Trimethoxy silane is added successively by proportioning in the reactor of dropping funnel and agitator, 18.7g dimethyldimethoxysil,ne, after 132.0g mono-phenyltrimethoxysila,e and 4.5mmol hydrochloric acid, start to stir and heat up, homo(io)thermism is kept after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, after dropwising, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules produced in reaction process, cool to room temperature, adjustment solid content is 60%, obtain silicone oligomer 290g.
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 802; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 10.6w%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 7.4w%; R/Si=1.14; Ph/Me=1.04.
3) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 52g neopentyl glycol, 27g 2 ?methyl 1,3 ?propylene glycol, 23.2g 1,4 ?cyclohexanediol and 252g 1,2,4 ?benzene tricarboxylic acid mix post-heating to 85 DEG C, add epoxy-terminated silicone oil and the 7.3g dimethylbenzene of the above-mentioned preparation of 8.2g; Heat 2.5h at 210 DEG C after, be warming up to 235 DEG C, after heating 3h; Be cooled to 85 DEG C, add 158g dipropylene glycol methyl ether acetate, the silicone oligomer of 120g step 2 preparation, 249 of 87.4g Dow Corning Corporation, 4g two ((3,4 ?epoxycyclohexyl) methyl) adipic acid ester, 8g bisphenol-s epoxy resin, 2.9g iso-butyl titanate and 2.0g tetrabutyl titanate; Be heated to 120 DEG C, heating 2.5h; Be cooled to 85 DEG C, finally add 90g dipropylene acetic ester.Controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The end carboxyl super branched polyester property detection case of end epoxy silicon oil and silicone oligomer modification is as shown in table 5.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 410 DEG C, snappiness 2mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 5 is organic-silicon-modified
4) coating
Composition: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 100g step 3 preparation, 20g silicon-dioxide, 10g titanium dioxide, 10g silicon carbide, 4g CoatOSil 7001,6g silicone oil
/ 350cst, 5g butyl acetic ester, 5g N-BUTYL ACETATE.
Preparation technology: end carboxyl super branched polyester silicon oil modified to filler, end ring oxygen, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is as shown in table 6: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 500 DEG C, snappiness 3mm, cold-hot alternation 57 times.
The performance index of table 6 coating
Embodiment 4:
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.04g and vitriol oil 4g, nitrogen protection reaction 7h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 8g, toluene 210g and Platinic chloride 0.04g are added in reactor; Be warming up to 75 DEG C, nitrogen protection reaction 8h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 533; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 41mmol epoxy group(ing).
2) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 63g 2 ?methyl 1,3 ?propylene glycol, 81.2g 1,4 ?cyclohexanediol and 252g1,2,4 ?benzene tricarboxylic acid mix post-heating to 80 DEG C, add epoxy-terminated silicone oil and the 5.76g dimethylbenzene of the preparation of 10g step 1; Heat 2.5h at 220 DEG C after, be warming up to 230 DEG C, after heating 2.5h; Be cooled to 90 DEG C, add 72.8g 1-Methoxy-2-propyl acetate, 100g butanols, 3074 of 50g Dow Corning Corporation, 3037 of 50g Dow Corning Corporation, the KR217 of company of the KR9218 of company of 60g SHIN-ETSU HANTOTAI, 40g SHIN-ETSU HANTOTAI, epoxy resin: 9g two ((3,4 ?epoxycyclohexyl) methyl) adipic acid ester, 12g 3,4 ?epoxidation naphthenic acid, 22g bicyclopentadiene dioxide and 4.32g tetra-n-butyl titanate; Be heated to 110 DEG C, heating 3h; Be cooled to 70 DEG C, finally add dipropylene glycol methyl ether acetate and dipropylene acetic ester.Controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The silicon oil modified end carboxyl super branched polyester property detection case of end ring oxygen is as shown in table 7.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 410 DEG C, snappiness 1mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 7 end ring oxygen is silicon oil modified
3) coating
Composition: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 120g step 2 preparation, 10g silicon carbide, 10g silicon-dioxide, 4g CoatOSil 3500,4g silicone oil
/ 350cst, 20g propionic acid-3-ether ethyl ester.
Preparation technology: end carboxyl super branched polyester silicon oil modified to filler, end ring oxygen, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is as shown in table 8: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 500 DEG C, snappiness 2mm, cold-hot alternation 57 times.
The performance index of table 8 coating
Embodiment 5
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.1g and vitriol oil 12g, nitrogen protection reaction 9h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 20g, toluene 400g and Platinic chloride 0.1g are added in reactor; Be warming up to 90 DEG C, nitrogen protection reaction 10h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 303; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 86mmol epoxy group(ing).
2) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 83.2g neopentyl glycol, 18g 2 ?Jia Ji ?1,3 propylene glycol and 231g 1,3,5 ?benzene tricarboxylic acid mix post-heating to 80 DEG C, add epoxy-terminated silicone oil and the 7g dimethylbenzene of the preparation of 4g step 1; Heat 3h at 190 DEG C after, be warming up to 220 DEG C, after heating 2h; Be cooled to 90 DEG C, add 151g 1-Methoxy-2-propyl acetate, 233 of 21.3g Dow Corning Corporation, 249 of 20g Dow Corning Corporation, the Z of 20g Dow Corning Corporation ?6108, the IC836 of 20g Wa Ke company, the KR9218 of company of the KR213 of company of 10g SHIN-ETSU HANTOTAI, 20g SHIN-ETSU HANTOTAI, the KR217 of company of 20g SHIN-ETSU HANTOTAI, 14g two (2,3 ?epoxycyclopentyl) ether, 12g 3,4-epoxidation naphthenic acid 3 ', 4 '-epoxidation hexanaphthene methyl esters and 3.1g tetra-n-butyl titanate; Be heated to 115 DEG C, heating 3h; Be cooled to 90 DEG C, finally add 34g butanols.Controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The silicon oil modified end carboxyl super branched polyester property detection case of end ring oxygen is as shown in table 9.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 400 DEG C, snappiness 1mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 9 end ring oxygen is silicon oil modified
3) coating
Composition: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 140g step 2 preparation, 25g silicon-dioxide, 10g titanium dioxide, 10g carbon black, 4g CoatOSil 3500,2g CoatOSil 7650,2g methyl isoamyl ketone (MIAK), 4g isobutyl isobutyrate.
Preparation technology: end carboxyl super branched polyester silicon oil modified to pigment, filler, end ring oxygen, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is as shown in table 10: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 500 DEG C, snappiness 2mm, cold-hot alternation 56 times.
The performance index of table 10 coating
Embodiment 6
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.04g and vitriol oil 5g, nitrogen protection reaction 9h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 5g, toluene 240g and Platinic chloride 0.04g are added in reactor; Be warming up to 90 DEG C, nitrogen protection reaction 10h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 833; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 32mmol epoxy group(ing).
2) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 104g neopentyl glycol and 252g 1,2,4 ?benzene tricarboxylic acid mix post-heating to 70 DEG C, add epoxy-terminated silicone oil and the 4.12g dimethylbenzene of the preparation of 9.36g step 1; Heat 1h at 210 DEG C after, be warming up to 220 DEG C, after heating 3h; Be cooled to 85 DEG C, add 135g 1-Methoxy-2-propyl acetate, 27g SHIN-ETSU HANTOTAI silicone resin KR150, the KR211 of company of 30g SHIN-ETSU HANTOTAI, the KR214 of company of the KR212 of company of 40g SHIN-ETSU HANTOTAI, 60g SHIN-ETSU HANTOTAI, the KR21632g bicyclopentadiene dioxide of company of 40g SHIN-ETSU HANTOTAI and 2.8g tetra-n-butyl titanate; Be heated to 120 DEG C, heating 3h; Be cooled to 85 DEG C, finally add 20g dipropylene glycol methyl ether acetate and 10g dipropylene acetic ester.Controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The silicon oil modified end carboxyl super branched polyester property detection case of end ring oxygen is as shown in table 3.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 400 DEG C, snappiness 2mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 11 end ring oxygen is silicon oil modified
3) coating
Composition: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 120g step 2 preparation; 25g silicon-dioxide; 5g titanium dioxide; 5g iron oxide red; 4g CoatOSil 3500; 2g CoatOSil 7510; 4g silicone oil
/ 350cst; 12g isobutyl isobutyrate
Preparation technology:
End carboxyl super branched polyester silicon oil modified to pigment, filler, end ring oxygen, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is as shown in table 12: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 510 DEG C, snappiness 3mm, cold-hot alternation 57 times.
The performance index of table 12 coating
Embodiment 7
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.07g and vitriol oil 7g, nitrogen protection reaction 8h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 16g, toluene 310g and Platinic chloride 0.05g are added in reactor; Be warming up to 80 DEG C, nitrogen protection reaction 8h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 653; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 67mmol epoxy group(ing).
2) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 104g neopentyl glycol and 294g 1,2,4 ?benzene tricarboxylic acid mix post-heating to 75 DEG C, add epoxy-terminated silicone oil and the 6.4g dimethylbenzene of the preparation of 7.3g step 1; Heat 1h at 180 DEG C after, be warming up to 240 DEG C, after heating 1h; Be cooled to 85 DEG C, add 156g 1-Methoxy-2-propyl acetate, 160g SHIN-ETSU HANTOTAI silicone resin KR150, the IC836 of 100g Wa Ke company, 11g TriMethylolPropane(TMP) glycidyl ether, 13g 3,4 ?epoxidation naphthenic acid 3 ', 4 ’ ?epoxidation hexanaphthene methyl esters, 10g bisphenol-s epoxy resin, 2.12g tetra-n-butyl titanate and 1.0g dioctyl zinc oxide; Be heated to 110 DEG C, heating 2h; Be cooled to 90 DEG C, finally add 25g butanols.Controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The silicon oil modified end carboxyl super branched polyester property detection case of end ring oxygen is as shown in table 13.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 410 DEG C, snappiness 2mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 13 end ring oxygen is silicon oil modified
3) coating
Composition: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 110g step 2 preparation; 15g silicon-dioxide; 5g titanium dioxide; 8g phthalocyanine blue; Isobutyl isobutyrate 60g.
Preparation technology: end carboxyl super branched polyester silicon oil modified to pigment, filler, end ring oxygen, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is as shown in table 4: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 510 DEG C, snappiness 3mm, cold-hot alternation 55 times.
The performance index of table 14 coating
Embodiment 8
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.1g and vitriol oil 10g, nitrogen protection reaction 9h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 20g, toluene 360g and Platinic chloride 0.08g are added in reactor; Be warming up to 90 DEG C, nitrogen protection reaction 10h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 313; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 98mmol epoxy group(ing).
2) preparation of silicone oligomer
Prolong is being housed, thermometer, 44.5g methltriethoxysilone is added successively by proportioning in the reactor of dropping funnel and agitator, 50.3g dimethyldiethoxysilane, after 98.4g phenyltriethoxysilane and 7.0mmol hydrochloric acid, start to stir and heat up, homo(io)thermism is kept after being warmed up to 70 DEG C, under agitation drip 43.1g distilled water, after dropwising, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules produced in reaction process, cool to room temperature, adjustment solid content is 80%, obtain silicone oligomer 230g.
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 1986; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 15w%; The ethoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 3w%; R/Si=1.34; Ph/Me=0.44.
3) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 104g neopentyl glycol and 210g 1,2,4 ?benzene tricarboxylic acid mix post-heating to 90 DEG C, add epoxy-terminated silicone oil and the 3.64g dimethylbenzene of the preparation of 4.2g step 1; Heat 1h at 180 DEG C after, be warming up to 240 DEG C, after heating 1h; Be cooled to 90 DEG C, add 104g 1-Methoxy-2-propyl acetate, 239g step 2 prepares silicone oligomer, 10.4g bicyclopentadiene dioxide, 1.5g tetra-n-butyl titanate, 0.5g dioctyl tin oxide, 0.5g tetra-n-butyl titanate, 0.5g dioctyl zinc oxide and 0.5g diisooctyl zinc oxide; Be heated to 110 DEG C, heating 2h; Be cooled to 85 DEG C, finally add 146g 1-Methoxy-2-propyl acetate.Controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The silicon oil modified end carboxyl super branched polyester property detection case of end ring oxygen is as shown in Table 15.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 400 DEG C, snappiness 1mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 15 is organic-silicon-modified
4) coating
Coating forms: the end carboxyl super branched polyester that the end ring oxygen of the above-mentioned preparation of 150g is silicon oil modified; 15g silicon-dioxide, 5g titanium dioxide, 5g CoatOSil 3500,5g silicone oil
/ 350cst, 10g isobutyl isobutyrate.
Preparation technology: end carboxyl super branched polyester silicon oil modified to paint filler, end ring oxygen, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is shown in table 16: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 500 DEG C, snappiness 2mm, cold-hot alternation 54 times.
The performance index of table 16 coating
Embodiment 9
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.05g and vitriol oil 6g, nitrogen protection reaction 8h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 11g, toluene 320g and Platinic chloride 0.05g are added in reactor; Be warming up to 85 DEG C, nitrogen protection reaction 8.5h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 587; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 53mmol epoxy group(ing).
2) silicone oligomer
Prolong is being housed, thermometer, 69.1g methltriethoxysilone is added successively by proportioning in the reactor of dropping funnel and agitator, 34.0g dimethyldiethoxysilane, after 109.24g phenyltriethoxysilane and 5.5mmol hydrochloric acid, start to stir and heat up, homo(io)thermism is kept after being warmed up to 70 DEG C, under agitation drip 42.7g distilled water, after dropwising, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules produced in reaction process, cool to room temperature, adjustment solid content is 60%, obtain silicone oligomer 322g.
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 1808; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 20w%; The ethoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 2.5w%; R/Si=1.21; Ph/Me=0.55.
3) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 104g neopentyl glycol and 252g 1,2,4 ?benzene tricarboxylic acid mix post-heating to 80 DEG C, add epoxy-terminated silicone oil and the 4.3g dimethylbenzene of the preparation of 8.3g step 1; Heat 1.5h at 190 DEG C after, be warming up to 230 DEG C, after heating 2h; Be cooled to 90 DEG C, add 156g 1-Methoxy-2-propyl acetate, 49g SHIN-ETSU HANTOTAI silicone resin KR150, the IC836 of Z ?6108, the 100g Wa Ke company of 100g Dow Corning Corporation, 26g bicyclopentadiene dioxide, 2.0g tetra-n-butyl titanate, 1.2g diisooctyl zinc oxide and 4g diisooctyl stannic oxide; Be heated to 120 DEG C, heating 2h; Cool to 90 DEG C, finally add 30g propandiol butyl ether acetic ester.Controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The end carboxyl super branched polyester property detection case of end epoxy silicon oil and silicone oligomer modification is shown in table 17.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 400 DEG C, snappiness 1mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The end carboxyl super branched polyester property that table 17 end ring oxygen is silicon oil modified
4) coating
Composition: the end carboxyl super branched polyester that the end ring oxygen of the above-mentioned preparation of 150g is silicon oil modified; 40g titanium dioxide, 8g CoatOSil7510; 2g isobutyl isobutyrate
Preparation technology: end carboxyl super branched polyester silicon oil modified to filler, end ring oxygen, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is shown in table 18: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 510 DEG C, snappiness 2mm, cold-hot alternation 56 times.
The performance index of table 18 coating
Embodiment 10
1) preparation of epoxy-terminated silicone oil
Octamethylcyclotetrasiloxane 200g is added successively in the reactor that prolong, thermometer, dropping funnel and agitator are housed, after tetramethyl ammonium hydroxide 0.03g and vitriol oil 3g, nitrogen protection reaction 8h; Be warming up to 180 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and glycidyl allyl ether 3g, toluene 2400g and Platinic chloride 0.02g are added in reactor; Be warming up to 80 DEG C, nitrogen protection reaction 10h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil.
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and result is 987; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 13mmol epoxy group(ing).
2) silicone oligomer
Prolong is being housed, thermometer, 42.0g monomethyl Trimethoxy silane is added successively by proportioning in the reactor of dropping funnel and agitator, 18.7g dimethyldimethoxysil,ne, after 123.0g mono-phenyltrimethoxysila,e and 4.5mmol hydrochloric acid, start to stir and heat up, homo(io)thermism is kept after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, after dropwising, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules produced in reaction process, cool to room temperature, adjustment solid content is 60%, obtain silicone oligomer 290g.
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 802; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 10.6w%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 7.4w%; R/Si=1.14; Ph/Me=1.04.
3) preparation of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified
By 90g 2 ?methyl 1,3 ?propylene glycol, 84g 1,2,4 ?benzene tricarboxylic acid and 126g 1,3,5 ?benzene tricarboxylic acid mix post-heating to 90 DEG C, add epoxy-terminated silicone oil and the 3.2g dimethylbenzene of the preparation of 6.3g step 1; Heat 3h at 190 DEG C after, be warming up to 230 DEG C, after heating 3h; Be cooled to 90 DEG C, add 108g 1-Methoxy-2-propyl acetate, the KR212 of company of 110g SHIN-ETSU HANTOTAI, the silicone oligomer of 70g step 2 preparation, 14g TriMethylolPropane(TMP) glycidyl ether, 21g two (2,3-epoxycyclopentyl) ether, 1.6g tetra-n-butyl titanate and 2.0g dioctyl zinc oxide; Be heated to 115 DEG C, heating 3h; Be cooled to 80 DEG C, finally add 20g 1-Methoxy-2-propyl acetate.Controlling solid content is 60%, so just obtains organic-silicon-modified end carboxyl super branched polyester.Relative to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying and then obtain end carboxyl super branched polyester containing silicone segments.
The end carboxyl super branched polyester property detection case of end epoxy silicon oil and silicone oligomer modification is shown in table 19.Can see: organic-silicon-modified end carboxyl super branched vibrin all has excellent performance in hardness, sticking power and snappiness, especially heat-resisting can to 400 DEG C, snappiness 2mm.The lifting of vibrin in resistance toheat compared by organic-silicon-modified end carboxyl super branched vibrin can prove that silicone segments has been incorporated on Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 19 end ring oxygen is silicon oil modified
4) coating
Composition: the end carboxyl super branched polyester that the end ring oxygen of the above-mentioned preparation of 120g is silicon oil modified; 20g titanium dioxide 20g; 40g silicon-dioxide; 2g CoatOSil 7510; 18g isobutyl isobutyrate.
B) preparation technology: end carboxyl super branched polyester silicon oil modified to pigment, filler, end ring oxygen, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, both.
The coating property of preparation is shown in table 20: the coating of organic-silicon-modified end carboxyl super branched vibrin preparation all has excellent performance in hardness, sticking power, alternating hot and cold and snappiness, especially heat-resisting can to 510 DEG C, snappiness 3mm, cold-hot alternation 57 times.
The performance index of table 20 coating
Comparative example
Contrast coating 1 reference (Ma Yiwen etc., the preparation of the silicon oil modified vibrin of Amino End Group, plating and covering with paint, 2011,02 phase) preparation; Contrast coating 2 reference (Li Huagong etc., the synthesis of organic-silicon-modified hydroxyl telechelic polyester, synthetic resins and plastics, 2012,29 (2): 20 ~ 23) preparation; Contrast coating 3 reference (CN 102504293A) preparation.The performance test situation of contrast coating is in table 21.Thermotolerance foundation method 1* detects; Snappiness according to GB/T1731 ?1993 to detect; Alternating hot and cold foundation method 2* detects.
The performance index of table 21 coating
Polyester in contrast coating 1 is by 1,6 ?hexanodioic acid, 1,3 ?propylene glycol and hydroxy silicon oil reaction prepare, the snappiness of this organosilicon modified polyester reaches 4mm, alternating hot and cold reaches 35 times, but only adopts a small amount of silicone oil to carry out modification in preparation resin process, does not use silicone intermediate to carry out modification to polyester, cause the modified poly ester thermotolerance just 280 DEG C prepared, its resistance toheat is worse than coating of the present invention far away.
Resin in contrast coating 2 adopts silicone intermediate to carry out modification to polyol polyester resin, and this resin has good resistance toheat, and its heat resisting temperature reaches 350 DEG C.But do not use silanol-modified at the polyol polyester adopted, cause its snappiness poor, only 6mm, cold-hot alternation just 19 times.
Resin in contrast coating 3 adopts silicone intermediate to carry out modification to vibrin, and this resin has good resistance toheat, and its heat resisting temperature reaches 350 DEG C.But prepare in PET Process only adopt neopentyl glycol, 2 ?methyl 1,3 ?propylene glycol and 1,6 ?the dibasic alcohol such as hexylene glycol and benzene tricarboxylic acid react, do not add low molecular weight silicone oil, cause film snappiness poor, only 6mm.
The standby coating resistance toheat of resin-made of the present invention reaches 490 DEG C, and snappiness reaches 3mm.Its resistance toheat and snappiness are better than contrast coating 1 far away, contrast coating 2 and contrast coating 3.
Claims (7)
1. the preparation method of the end carboxyl super branched vibrin that an end ring oxygen is silicon oil modified, it is characterized in that: the triprotic acid of dibasic alcohol and dibasic alcohol mole number 1 ~ 1.5 times is mixed post-heating to 70 ~ 90 DEG C, add epoxy-terminated silicone oil and the dimethylbenzene of dibasic alcohol weight 0.05 ~ 0.1 times and 0.02 ~ 0.1 times respectively; Heat 1 ~ 3h at 180 ~ 210 DEG C after, be warming up to 220 ~ 240 DEG C, after heating 1 ~ 3h; Be cooled to 80 ~ 90 DEG C, add respectively dibasic alcohol weight 1.0 ~ 1.5 times, 1.5 ~ 2.0 times and 1 ~ 5% organic solvent, silicone oligomer and 1 ~ 5% crosslinking catalyst; Be heated to 110 ~ 120 DEG C, heating 2 ~ 3h; Be cooled to 80 ~ 90 DEG C, finally separately adding organic solvent adjustment solid content is 60 ~ 70%;
Described dibasic alcohol be neopentyl glycol, 2 ?methyl 1,3 ?propylene glycol and 1,4 ?one or more in cyclohexanediol;
Described triprotic acid is 1,2,4 ?benzene tricarboxylic acid and 1,3,5 ?one in benzene tricarboxylic acid or two kinds;
Described epoxy-terminated silicone oil is prepared by the following method: be that the octamethylcyclotetrasiloxane of 1:0.01 ~ 0.05%:2 ~ 6%, tetramethyl disiloxane and the vitriol oil add in reactor by mass ratio, nitrogen protection reaction 7 ~ 10h; Be warming up to 180 ~ 190 DEG C, underpressure distillation removing low-boiling-point substance, obtain end hydrogen silicone oil; Gained end hydrogen silicone oil and weight are respectively 1 ~ 10%, 1 ~ 2 times of octamethylcyclotetrasiloxane and 0.01 ~ 0.05% glycidyl allyl ether, toluene and Platinic chloride add in reactor; Be warming up to 70 ~ 90 DEG C, nitrogen protection reaction 8 ~ 10h, underpressure distillation, except desolventizing, obtains epoxy-terminated silicone oil; The weight-average molecular weight of described epoxy-terminated silicone oil is 300 ~ 1000, and every 100g epoxy-terminated silicone oil contains 8 ~ 100mmol epoxy group(ing);
The weight-average molecular weight of described silicone oligomer is 800 ~ 2000, and by percentage to the quality, in silicone oligomer, methoxy or ethoxy content is 2.5 ~ 15%, and hydroxy radical content is 3 ~ 20%;
Described crosslinking catalyst is one or more in tetrabutyl titanate, tetrabutyl titanate, two octyloxy tin, two different octyloxy tin, two octyloxy zinc and two different octyloxy zinc;
Described organic solvent is one or more in butanols, isopropylcarbinol, propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and dipropylene acetic ester.
2. the preparation method of the end carboxyl super branched polyester that end ring oxygen according to claim 1 is silicon oil modified, is characterized in that, epoxy-terminated silicone oil weight-average molecular weight is 300 ~ 800, and every 100g epoxy-terminated silicone oil contains 30 ~ 50mmol epoxy group(ing).
3. the preparation method of the end carboxyl super branched polyester that end ring oxygen according to claim 1 is silicon oil modified, it is characterized in that, described silicone oligomer is obtained by one or more hydrolysis-condensation reactions in methltriethoxysilone, dimethyldiethoxysilane and a phenyl triethoxy.
4. the preparation method of the end carboxyl super branched polyester that end ring oxygen according to claim 1 is silicon oil modified, it is characterized in that, described silicone oligomer is obtained by one or more condensation reactions that are hydrolyzed in monomethyl Trimethoxy silane, dimethyldimethoxysil,ne and a phenyl trimethoxy.
5. the preparation method of the end carboxyl super branched polyester that end ring oxygen according to claim 1 is silicon oil modified, it is characterized in that, described silicone oligomer be KR211, KR212, KR214, KR216, IC836, KR213, KR9218, KR217,233,249, Z ?one or more in 6108,3074 and 3037.
6. the end carboxyl super branched polyester that end ring oxygen is silicon oil modified, is characterized in that it is obtained by preparation method described in any one of claim 1 ?5.
7. the coating of the end carboxyl super branched polyester that end ring oxygen is silicon oil modified described in an application rights requirement 6, it is characterized in that: by percentage to the quality, containing end carboxyl super branched polyester, 10 ~ 20% high temperature resistant fillers and 5 ~ 20% high boiling solvents that end ring oxygen described in 60 ~ 80% is silicon oil modified in the raw material of this coating;
Described high boiling solvent is one or more in ethylene glycol ether acetate, butyl acetic ester, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and methyl isoamyl ketone;
Described high temperature resistant filler is one or more in titanium dioxide, silicon-dioxide and silicon carbide.
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| CN102504293A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin |
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| CN102504293A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin |
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