CN103113567A - 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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- CN103113567A CN103113567A CN2013100434881A CN201310043488A CN103113567A CN 103113567 A CN103113567 A CN 103113567A CN 2013100434881 A CN2013100434881 A CN 2013100434881A CN 201310043488 A CN201310043488 A CN 201310043488A CN 103113567 A CN103113567 A CN 103113567A
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- epoxy
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- silicon
- super branched
- carboxyl super
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- 238000002360 preparation method Methods 0.000 title claims abstract description 111
- 239000003921 oil Substances 0.000 title claims abstract description 77
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 71
- 239000010703 silicon Substances 0.000 title claims abstract description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229920006150 hyperbranched polyester Polymers 0.000 title abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 126
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 33
- 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
- 229920002545 silicone oil Polymers 0.000 claims description 123
- 238000000576 coating method Methods 0.000 claims description 79
- 239000011248 coating agent Substances 0.000 claims description 76
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 63
- 239000001301 oxygen Substances 0.000 claims description 63
- 229910052760 oxygen Inorganic materials 0.000 claims description 63
- 229920001296 polysiloxane Polymers 0.000 claims description 50
- 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
- 238000004821 distillation Methods 0.000 claims description 28
- 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
- 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
- -1 octyloxy tin Chemical compound 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
- 229910052799 carbon Inorganic materials 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
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-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
- JONNRYNDZVEZFH-UHFFFAOYSA-N 2-(2-butoxypropoxy)propyl acetate Chemical compound CCCCOC(C)COC(C)COC(C)=O JONNRYNDZVEZFH-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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 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
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims 1
- 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 12
- 239000011347 resin Substances 0.000 abstract description 12
- 239000003973 paint Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 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
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 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
- 238000001514 detection method Methods 0.000 description 12
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 229920002050 silicone resin Polymers 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture 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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 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
- 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 229920000647 polyepoxide Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 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
- 230000008901 benefit Effects 0.000 description 2
- 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 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
- 239000004922 lacquer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 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
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical class [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 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
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-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
- 239000004593 Epoxy Substances 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
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 239000011368 organic material Substances 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 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
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- 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 use, belong to the organic high molecular compound field.
Background technology
Vibrin has excellent metal adhesion, and the high good physical and mechanical properties of hardness and resistance to chemical corrosion preferably are used widely in coating industry.But vibrin exists resistance toheat poor, and water resistance hangs down and the poor shortcoming of weather resistance, limits its application in high-temperature resistant coating.In order to improve the resistance to elevated temperatures of vibrin, other resins commonly used carry out chemical modification to it.Silicone resin is a kind of hybrid inorganic-organic materials, has excellent thermotolerance, weathering resistance, water tolerance and lower surface tension.Use silicone resin to carry out modification to vibrin, can improve resistance toheat, water resistance and the chemical resistance of vibrin.Such as (Li Daming such as Li Daming, the development of the durable coiled material finishing paint of organosilicon modified polyester type, coatings industry, 2007,37 (12), 30-32) with hydroxyl polyester and silicone resin reaction preparation 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, and 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, electroplate and cover with paint, lacquer, colour wash, etc., 2011,02 phases) utilize saturated hydroxy silane for properties-correcting agent, carry out polycondensation with 1,2-PD and hexanodioic acid in, prepared acid modified alcoholic type vibrin, the adhesion 1 grade of this modified polyester resin, shock strength 4.5Mpa, hardness 2H; But there is stable on heating shortcoming.(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) organic-silicon-modified end carboxyl super branched polyester has been synthesized in design, with this resin and polyurethane curing agent HDI biuret and HDI tripolymer preparation two component coating.This coating has excellent weathering resistance, good sticking power and elasticity, but this modified poly ester must be used in conjunction with polyurethane curing agent, exists to use inconvenience shortcoming efficiently.(Li Huagong etc., organic-silicon-modified hydroxyl telechelic polyester synthetic, synthetic resins and plastics, 2012,29 (2): 20～23) adopt organosilicon performed polymer modification hydroxyl telechelic polyester, improved resistance toheat and the salt water resistance performance of polyester such as Li Huagong.
Hyperbranched polymer has highly branched structure and a large amount of end group active groups, has high resolution, low viscosity and higher chemical reactivity etc., is widely used in paint field.Low viscosity makes hyperbranched polymer be fit to be applied to high solid component coating, can reduce system viscosity with the blend of line polymer coating, improves the system mobility; High solvability can reduce the consumption of solvent, reduces costs, and reduces noxious gas emission; It is less that highly branched structure makes the hyperbranched polymer molecule interchain tangle, and is difficult for crystallization, makes coating have good film forming properties; Numerous terminal functionality makes Hyperbranched Polymer have very strong correctability ability, can prepare to be fit to multi-purpose coating.For example Chinese patent CN102504293A with organic-silicon-modified end carboxyl super branched polyester, improves mechanical property, chemical resistance and the water resistance of silicone resin.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, limits its application.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of resistance toheat and the good silicon oil modified end carboxyl super branched polyester of end ring oxygen of snappiness.
Second technical problem that will solve of the present invention is to provide the preparation method of the silicon oil modified end carboxyl super branched polyester of described end ring oxygen.
The 3rd technical problem that will solve of the present invention is to provide the coating that contains 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:
The preparation method of the end carboxyl super branched polyester that a kind of end ring oxygen is silicon oil modified, the method is comprised of following steps:
Dibasic alcohol and the molar weight triprotic acid that is 1～1.5 times of dibasic alcohol is mixed post-heating to 70～90 ℃, add the dimethylbenzene of 0.02～0.1 times of the epoxy-terminated silicone oil of 0.05～0.1 times of dibasic alcohol weight and dibasic alcohol weight; After heating 1～3h under 180～210 ℃, be warming up to 220～240 ℃, after heating 1～3h; Be cooled to 90 ℃, add the organic solvent of 1.0～1.5 times of dibasic alcohol weight, 1～5% crosslinking catalyst of the silicone oligomer that dibasic alcohol weight is 1.5～2.0 times and dibasic alcohol weight; Be heated to 110～120 ℃, heating 2～3h; Be cooled to 90 ℃, adding at last organic solvent to adjust solid content is 60～70%;
Described dibasic alcohol is a kind of or two or more in neopentyl glycol, 2-methyl 1,3-PD and Isosorbide-5-Nitrae-cyclohexanediol;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3,5-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 glycol monobutyl ether acetate.
The weight-average molecular weight of described silicone oligomer is 800～2000, and contains 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, the glycidyl allyl ether of octamethylcyclotetrasiloxane weight 1～10%, the Platinic chloride of the toluene of octamethylcyclotetrasiloxane weight 1～2 and octamethylcyclotetrasiloxane weight 0.01～0.05% adds in reactor; Be warming up to 70～90 ℃, nitrogen protection reaction 8～10h, the underpressure distillation 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 the condensation reaction that is hydrolyzed of this area siloxanes commonly used, 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 KR9218, the company of SHIN-ETSU HANTOTAI of KR213, the company of SHIN-ETSU HANTOTAI of IC836, the company of SHIN-ETSU HANTOTAI of KR216, the Wa Ke company of KR214, the company of SHIN-ETSU HANTOTAI of KR212, the company of SHIN-ETSU HANTOTAI of KR211, the company of SHIN-ETSU HANTOTAI of company of SHIN-ETSU HANTOTAI KR217, Dow Corning Corporation 233, Dow Corning Corporation 249, the Z-6108 of Dow Corning Corporation, Dow Corning Corporation 3074, Dow Corning Corporation 3037 in a kind of 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 better contains 30～50mmol epoxy group(ing).
The organic-silicon-modified end carboxyl super branched polyester of method preparation of the present invention has the following advantages:
At first dibasic alcohol, triprotic acid and epoxy-terminated silicone oil are reacted the end carboxyl super branched vibrin of preparation, wherein the hydroxyl on dibasic alcohol and the carboxyl on triprotic acid carry out esterification, the hydroxyl of dibasic alcohol and the epoxy group(ing) on epoxy-terminated silicone oil react simultaneously, flexible organosilicon segment is embedded in hyper-branched polyester, improve the resistance toheat of polyester, snappiness and the cold-and-heat resistent of filming change performance.
Then with end carboxyl super branched vibrin and the organic-silicon-modified end carboxyl super branched vibrin of silicone oligomer reaction preparation, hydroxyl and the carboxyl on the superbrnaching end-hydroxy polyester resin wherein, under the crosslinking catalyst effect can with silicone oligomer on alkoxyl group or silicon 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, and snappiness and cold-and-heat resistent change performance.
Coating of the present invention, this coating contain 60～80w% above-mentioned organic-silicon-modified high temperature resistant filler of superbrnaching end-hydroxy polyester resin, 10～20w% and 5～20w% high boiling solvent, wherein,
Described high boiling solvent is a kind of or two or more in divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and methyl isoamyl ketone;
Described filler is this area high temperature resistant filler commonly used, can be titanium dioxide, silicon-dioxide or silicon carbide.
Also can add this area high-temperature resisting pigment commonly used in above-mentioned coating, described high-temperature resisting pigment can be the inorganic high-temperature resistant pigment such as carbon black, iron oxide red, can be also the organic high temperature-resistant pigment such as phthalocyanine blue.
Can also add this area organosilicon auxiliary agent commonly used in above-mentioned coating, as, 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, as, step the CoatOSil series organic silicon modified by polyether auxiliary agent of figure new high-tech material company limited.Those skilled in the art can be according to the kind and the consumption that require to determine organic silicon additive, and the consumption that the inventor recommends is 1～5w%.
The preparation method of above-mentioned coating is this area preparation method commonly used, and the superbrnaching end-hydroxy polyester resin, pigment, filler, organosilicon auxiliary agent and the high boiling solvent that are about to modification are mixed to get.
Because coating of the present invention adopts the silicon oil modified end carboxyl super branched polyester of above-mentioned end ring oxygen standby, therefore have high heat resistance energy and good snappiness.
With respect to prior art, the present invention has following advantage and beneficial effect:
1) the present invention reacts dibasic alcohol, triprotic acid and epoxy-terminated silicone oil to the end carboxyl super branched vibrin of preparation, wherein the hydroxyl on dibasic alcohol and the carboxyl on triprotic acid carry out esterification, the hydroxyl of dibasic alcohol and the epoxy group(ing) on epoxy-terminated silicone oil react simultaneously, flexible organosilicon segment is embedded in hyper-branched polyester, improve the resistance toheat of polyester, snappiness and the cold-and-heat resistent of filming change performance.
2) the present invention is with end carboxyl super branched vibrin and the organic-silicon-modified end carboxyl super branched vibrin of silicone oligomer reaction preparation, hydroxyl and the carboxyl on the superbrnaching end-hydroxy polyester resin wherein, under the crosslinking catalyst effect can with silicone oligomer on alkoxyl group or silicon 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, and snappiness and cold-and-heat resistent change performance.
Description of drawings
Fig. 1 is the infared spectrum of the organic-silicon-modified end carboxyl super branched polyester of embodiment 1 gained.
Embodiment
Infared spectrum and Fig. 1 about organic-silicon-modified end carboxyl super branched polyester in following embodiment are basic identical, do not provide one by one.
Embodiment 1
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; With the end hydrogen silicone oil that makes, glycidyl allyl ether 2g, toluene 200g and Platinic chloride 0.02g add in reactor; Be warming up to 70 ℃, nitrogen protection reaction 8h, the underpressure distillation 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 the 8.1mmol epoxy group(ing).
2) preparation of organic-silicon-modified end carboxyl super branched polyester
With dibasic alcohol neopentyl glycol 104g (1mol) and triprotic acid 1,3,5-benzene tricarboxylic acid 210g (1mmol) mixes post-heating to 70 ℃, adds epoxy-terminated silicone oil 5.1g and dimethylbenzene 2.08g; After heating 1h under 180 ℃, be warming up to 240 ℃, after heating 1h; Be cooled to 90 ℃, add the organic solvent 1-Methoxy-2-propyl acetate 104g of 1.0 times of dibasic alcohol weight, the silicone oligomer 156g of the silicone resin KR150 of SHIN-ETSU HANTOTAI and crosslinking catalyst tetra-n-butyl titanate 1.04g; Be heated to 110 ℃, heating 2h; Be cooled to 90 ℃, add at last residue organic solvent 196g, controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.Show as accompanying drawing 1 middle infrared spectrum: 3500cm
-1Locating broad peak is-the OH absorption peak, 2950cm
-1The place is-CH
3Absorption peak, 1730cm
-1The place is the absorption peak of-COO-, 1120cm
-1The place is Si-O-Si absorption peak, 980cm
-1The place is epoxy absorption peak, 1250cm
-1And 800cm
-1The place is Si-CH
3Absorption peak.The existence of the absorption peak of-COO-shows the polyester construction of matrix resin, Si-O-Si and Si-CH
3The existence of absorption peak has proved that resin has passed through the modification of 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-resistingly can arrive 420 ℃, snappiness 1mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the 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: under 25 ℃, use butanone wiping 100 times back and forth.
2
*The resistance toheat detection method: with test piece in 180 ℃ the baking 2h after, put into the Ovenized electric furnace that potentiometer is checked, by 5 ℃/min rising temperature, begin timing with furnace temperature to the requirement of experiment temperature, sample takes out through after continuous high temperature, be chilled to room temperature (25 ℃), observe the coatingsurface situation with magnifying glass, as without be full of cracks, obscission, illustrate that namely coating heat resistance can be good.
3) contain the coating preparation of this organic-silicon-modified end carboxyl super branched polyester
With filler titanium dioxide 60g, silicon oil modified end carboxyl super branched polyester 100g, the silicone oil of end ring oxygen
Organosilicon auxiliary agent 8g, the high boiling solvent 5g of divalent ester mixture (DBE) mix, add grinding machine for grinding to arrive 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-resistingly can arrive 490 ℃, snappiness 2mm, cold-hot alternation 58 times.
The performance index of table 2 coating
Embodiment 2:
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 8.0h, the underpressure distillation 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 the 8.1mmol epoxy group(ing).
2) preparation of the silicon oil modified end carboxyl super branched polyester of end ring oxygen
With the 62.4g neopentyl glycol, 36g2-methyl isophthalic acid, 3 propylene glycol, 210g1,2,4-benzene tricarboxylic acid and 105g1,3,5-benzene tricarboxylic acid mix post-heating to 80 ℃, add epoxy-terminated silicone oil and the 9.84g dimethylbenzene of the above-mentioned preparation of 9.84g; After heating 3h under 200 ℃, be warming up to 220 ℃, after heating 2h; Be cooled to 80 ℃, add the 147g 1-Methoxy-2-propyl acetate, the 100g silicone resin KR150 of SHIN-ETSU HANTOTAI, 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 ℃, heating 3h; Be cooled to 80 ℃, add at last the 23g butanols, controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add the epoxy-terminated silicone oil reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
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-resistingly can arrive 420 ℃, snappiness 1mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the 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
Form: 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
The 10g ethylene glycol ether acetate.
Preparation technology: filler, silicon oil modified end carboxyl super branched polyester, high boiling solvent, the organosilicon auxiliary agent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 510 ℃, snappiness 2mm, cold-hot alternation 59 times.
The performance index of table 4 coating
Embodiment 3:
1) preparation of end ring oxygen silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 9h, the underpressure distillation 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 the 77mmol epoxy group(ing).
2) preparation of silicone oligomer
prolong is being housed, thermometer, add successively 42.0g monomethyl Trimethoxy silane by proportioning in the reactor of dropping funnel and agitator, 18.7g dimethyldimethoxysil,ne, 132.0g after a phenyltrimethoxysila,e and 4.5mmol hydrochloric acid, begin to stir and heat up, keep homo(io)thermism after being warmed up to 60 ℃, under agitation drip 31.7g distilled water, after dropwising, again after isothermal reaction 3h, the beginning underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in reaction process, cool to room temperature, adjusting 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 the 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 silicon oil modified end carboxyl super branched polyester of end ring oxygen
With the 52g neopentyl glycol, 27g2-methyl 1,3-PD, 23.2g1,4-cyclohexanediol and 252g1,2,4-benzene tricarboxylic acid mix post-heating to 85 ℃, add epoxy-terminated silicone oil and the 7.3g dimethylbenzene of the above-mentioned preparation of 8.2g; After heating 2.5h under 210 ℃, be warming up to 235 ℃, after heating 3h; Be cooled to 85 ℃, add the 158g dipropylene glycol methyl ether acetate, the silicone oligomer of 120g step 2 preparation, 87.4g 249 of Dow Corning Corporation, 4g two ((3, the 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 ℃, heating 2.5h; Be cooled to 85 ℃, add at last 90g dipropylene glycol monobutyl ether acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
The end carboxyl super branched polyester property detection case of end ring oxygen silicone 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-resistingly can arrive 410 ℃, snappiness 2mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the Hyperbranched Polyester Resin matrix.
The over-all properties of the end carboxyl super branched polyester that table 5 is organic-silicon-modified
4) coating
Form: 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 CoatOSil7001,6g silicone oil
5g Diethylene Glycol monobutyl ether acetate, the 5g N-BUTYL ACETATE.
Preparation technology: filler, silicon oil modified end carboxyl super branched polyester, organosilicon auxiliary agent, the high boiling solvent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 500 ℃, snappiness 3mm, cold-hot alternation 57 times.
The performance index of table 6 coating
Embodiment 4:
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 8h, the underpressure distillation 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 the 41mmol epoxy group(ing).
2) preparation of the silicon oil modified end carboxyl super branched polyester of end ring oxygen
With 63g2-methyl 1,3-PD, 81.2g1,4-cyclohexanediol and 252g1,2,4-benzene tricarboxylic acid mix post-heating to 80 ℃, add epoxy-terminated silicone oil and the 5.76g dimethylbenzene of 10g step 1 preparation; After heating 2.5h under 220 ℃, be warming up to 230 ℃, after heating 2.5h; Be cooled to 90 ℃, add the 72.8g 1-Methoxy-2-propyl acetate, 100g butanols, 3074 of 50g Dow Corning Corporation, 3037 of 50g Dow Corning Corporation, the KR9218 of company of 60g SHIN-ETSU HANTOTAI, the KR217 of company of 40g SHIN-ETSU HANTOTAI, epoxy resin: 9g two ((3, the 4-epoxycyclohexyl) methyl) adipic acid ester, 12g3,4-epoxidation naphthenic acid, 22g bicyclopentadiene dioxide and 4.32g tetra-n-butyl titanate; Be heated to 110 ℃, heating 3h; Be cooled to 70 ℃, add at last dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add the epoxy-terminated silicone oil reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
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-resistingly can arrive 410 ℃, snappiness 1mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the 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
Form: 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 CoatOSil3500,4g silicone oil
20g propionic acid-3-ether ethyl ester.
Preparation technology: filler, silicon oil modified end carboxyl super branched polyester, organosilicon auxiliary agent, the high boiling solvent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 500 ℃, snappiness 2mm, cold-hot alternation 57 times.
The performance index of table 8 coating
Embodiment 5
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 10h, the underpressure distillation 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 the 86mmol epoxy group(ing).
2) preparation of the silicon oil modified end carboxyl super branched polyester of end ring oxygen
With the 83.2g neopentyl glycol, 18g2-methyl isophthalic acid, 3 propylene glycol and 231g1,3,5-benzene tricarboxylic acid mix post-heating to 80 ℃, add epoxy-terminated silicone oil and the 7g dimethylbenzene of 4g step 1 preparation; After heating 3h under 190 ℃, be warming up to 220 ℃, after heating 2h; Be cooled to 90 ℃, add the 151g 1-Methoxy-2-propyl acetate, 21.3g Dow Corning Corporation 233,20g Dow Corning Corporation 249, the Z-6108 of 20g Dow Corning Corporation, the IC836 of 20g Wa Ke company, the KR213 of company of 10g SHIN-ETSU HANTOTAI, the KR9218 of company of 20g SHIN-ETSU HANTOTAI, the KR217 of company of 20g SHIN-ETSU HANTOTAI, two (2, the 3-oxirane ring amyl group) ethers of 14g, 12g3,4-epoxidation naphthenic acid 3 ', 4 '-epoxidation hexanaphthene methyl esters and 3.1g tetra-n-butyl titanate; Be heated to 115 ℃, heating 3h; Be cooled to 90 ℃, add at last the 34g butanols.Controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add the epoxy-terminated silicone oil reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
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-resistingly can arrive 400 ℃, snappiness 1mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the 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
Form: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 140g step 2 preparation, 25g silicon-dioxide, 10g titanium dioxide, the 10g carbon black, 4g CoatOSil3500,2g CoatOSil7650,2g methyl isoamyl ketone (MIAK), the 4g isobutyl isobutyrate.
Preparation technology: pigment, filler, silicon oil modified end carboxyl super branched polyester, organosilicon auxiliary agent, the high boiling solvent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 500 ℃, snappiness 2mm, cold-hot alternation 56 times.
The performance index of table 10 coating
Embodiment 6
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 10h, the underpressure distillation 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 the 32mmol epoxy group(ing).
2) preparation of the silicon oil modified end carboxyl super branched polyester of end ring oxygen
With 104g neopentyl glycol and 252g1,2,4-benzene tricarboxylic acid mixes post-heating to 70 ℃, adds epoxy-terminated silicone oil and the 4.12g dimethylbenzene of 9.36g step 1 preparation; After heating 1h under 210 ℃, be warming up to 220 ℃, after heating 3h; Be cooled to 85 ℃, add the 135g 1-Methoxy-2-propyl acetate, the 27g silicone resin KR150 of SHIN-ETSU HANTOTAI, the KR211 of company of 30g SHIN-ETSU HANTOTAI, the KR212 of company of 40g SHIN-ETSU HANTOTAI, the KR214 of company of 60g SHIN-ETSU HANTOTAI, KR21632g bicyclopentadiene dioxide and the 2.8g tetra-n-butyl titanate of company of 40g SHIN-ETSU HANTOTAI; Be heated to 120 ℃, heating 3h; Be cooled to 85 ℃, add at last 20g dipropylene glycol methyl ether acetate and 10g dipropylene glycol monobutyl ether acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add the epoxy-terminated silicone oil reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
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-resistingly can arrive 400 ℃, snappiness 2mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the 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
Form: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 120g step 2 preparation; 25g silicon-dioxide; 5g titanium dioxide; The 5g iron oxide red; 4g CoatOSil3500; 2g CoatOSil7510; 4g silicone oil
The 12g isobutyl isobutyrate
Preparation technology:
Pigment, filler, silicon oil modified end carboxyl super branched polyester, organosilicon auxiliary agent, the high boiling solvent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 510 ℃, snappiness 3mm, cold-hot alternation 57 times.
The performance index of table 12 coating
Embodiment 7
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 8h, the underpressure distillation 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 the 67mmol epoxy group(ing).
2) preparation of the silicon oil modified end carboxyl super branched polyester of end ring oxygen
With 104g neopentyl glycol and 294g1,2,4-benzene tricarboxylic acid mixes post-heating to 75 ℃, adds epoxy-terminated silicone oil and the 6.4g dimethylbenzene of 7.3g step 1 preparation; After heating 1h under 180 ℃, be warming up to 240 ℃, after heating 1h; Be cooled to 85 ℃, add the 156g 1-Methoxy-2-propyl acetate, the silicone resin KR150 of 160g SHIN-ETSU HANTOTAI, the IC836 of 100g Wa Ke company, 11g TriMethylolPropane(TMP) glycidyl ether, 13g3,4-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 ℃, heating 2h; Be cooled to 90 ℃, add at last the 25g butanols.Controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add the epoxy-terminated silicone oil reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
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-resistingly can arrive 410 ℃, snappiness 2mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the 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
Form: the silicon oil modified end carboxyl super branched polyester of end ring oxygen of 110g step 2 preparation; 15g silicon-dioxide; 5g titanium dioxide; The 8g phthalocyanine blue; Isobutyl isobutyrate 60g.
Preparation technology: pigment, filler, silicon oil modified end carboxyl super branched polyester, the high boiling solvent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 510 ℃, snappiness 3mm, cold-hot alternation 55 times.
The performance index of table 14 coating
Embodiment 8
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 10h, the underpressure distillation 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 the 98mmol epoxy group(ing).
2) preparation of silicone oligomer
prolong is being housed, thermometer, add successively the 44.5g methltriethoxysilone by proportioning in the reactor of dropping funnel and agitator, 50.3g dimethyldiethoxysilane, 98.4g after phenyltriethoxysilane and 7.0mmol hydrochloric acid, begin to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃, under agitation drip 43.1g distilled water, after dropwising, again after isothermal reaction 3h, the beginning underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in reaction process, cool to room temperature, adjusting 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 the diacetyl oxide method to measure, and result is 15w%; The oxyethyl group 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 silicon oil modified end carboxyl super branched polyester of end ring oxygen
With 104g neopentyl glycol and 210g1,2,4-benzene tricarboxylic acid mixes post-heating to 90 ℃, adds epoxy-terminated silicone oil and the 3.64g dimethylbenzene of 4.2g step 1 preparation; After heating 1h under 180 ℃, be warming up to 240 ℃, after heating 1h; Be cooled to 90 ℃, add the 104g 1-Methoxy-2-propyl acetate, 239g step 2 preparation 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 ℃, heating 2h; Be cooled to 85 ℃, add at last the 146g 1-Methoxy-2-propyl acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
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-resistingly can arrive 400 ℃, snappiness 1mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the 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 CoatOSil3500,5g silicone oil
The 10g isobutyl isobutyrate.
Preparation technology: paint filler, silicon oil modified end carboxyl super branched polyester, organosilicon auxiliary agent, the high boiling solvent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 500 ℃, snappiness 2mm, cold-hot alternation 54 times.
The performance index of table 16 coating
Embodiment 9
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 8.5h, the underpressure distillation 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 the 53mmol epoxy group(ing).
2) silicone oligomer
prolong is being housed, thermometer, add successively the 69.1g methltriethoxysilone by proportioning in the reactor of dropping funnel and agitator, 34.0g dimethyldiethoxysilane, 109.24g after phenyltriethoxysilane and 5.5mmol hydrochloric acid, begin to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃, under agitation drip 42.7g distilled water, after dropwising, again after isothermal reaction 3h, the beginning underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in reaction process, cool to room temperature, adjusting 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 the diacetyl oxide method to measure, and result is 20w%; The oxyethyl group 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 silicon oil modified end carboxyl super branched polyester of end ring oxygen
With 104g neopentyl glycol and 252g1,2,4-benzene tricarboxylic acid mixes post-heating to 80 ℃, adds epoxy-terminated silicone oil and the 4.3g dimethylbenzene of 8.3g step 1 preparation; After heating 1.5h under 190 ℃, be warming up to 230 ℃, after heating 2h; Be cooled to 90 ℃, add the 156g 1-Methoxy-2-propyl acetate, the 49g silicone resin KR150 of SHIN-ETSU HANTOTAI, the Z-6108 of 100g Dow Corning Corporation, the IC836 of 100g Wa Ke company, 26g bicyclopentadiene dioxide, 2.0g tetra-n-butyl titanate, 1.2g diisooctyl zinc oxide and 4g diisooctyl stannic oxide; Be heated to 120 ℃, heating 2h; Cool to 90 ℃, add at last 30g propandiol butyl ether acetic ester.Controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
The end carboxyl super branched polyester property detection case of end ring oxygen silicone 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-resistingly can arrive 400 ℃, snappiness 1mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the Hyperbranched Polyester Resin matrix.
The end carboxyl super branched polyester property that table 17 end ring oxygen is silicon oil modified
4) coating
Form: 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; The 2g isobutyl isobutyrate
Preparation technology: filler, silicon oil modified end carboxyl super branched polyester, organosilicon auxiliary agent, the high boiling solvent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 510 ℃, snappiness 2mm, cold-hot alternation 56 times.
The performance index of table 18 coating
Embodiment 10
1) preparation of epoxy-terminated silicone oil
Add successively octamethylcyclotetrasiloxane 200g 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 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding 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 ℃, nitrogen protection reaction 10h, the underpressure distillation 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 the 13mmol epoxy group(ing).
2) silicone oligomer
prolong is being housed, thermometer, add successively 42.0g monomethyl Trimethoxy silane by proportioning in the reactor of dropping funnel and agitator, 18.7g dimethyldimethoxysil,ne, 123.0g after a phenyltrimethoxysila,e and 4.5mmol hydrochloric acid, begin to stir and heat up, keep homo(io)thermism after being warmed up to 60 ℃, under agitation drip 31.7g distilled water, after dropwising, again after isothermal reaction 3h, the beginning underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in reaction process, cool to room temperature, adjusting 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 the 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 silicon oil modified end carboxyl super branched polyester of end ring oxygen
With 90g2-methyl 1,3-PD, 84g1,2,4-benzene tricarboxylic acid and 126g1,3,5-benzene tricarboxylic acid mix post-heating to 90 ℃, add epoxy-terminated silicone oil and the 3.2g dimethylbenzene of 6.3g step 1 preparation; After heating 3h under 190 ℃, be warming up to 230 ℃, after heating 3h; Be cooled to 90 ℃, add the 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-oxirane ring amyl group) ether, 1.6g tetra-n-butyl titanate and 2.0g dioctyl zinc oxide; Be heated to 115 ℃, heating 3h; Be cooled to 80 ℃, add at last the 20g 1-Methoxy-2-propyl acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified end carboxyl super branched polyester.With respect to end carboxyl super branched polyester, add epoxy-terminated silicone oil and silicone oligomer reaction modifying to obtain containing the end carboxyl super branched polyester of organosilicon segment.
The end carboxyl super branched polyester property detection case of end ring oxygen silicone 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-resistingly can arrive 400 ℃, snappiness 2mm.Organic-silicon-modified end carboxyl super branched vibrin is compared vibrin can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the 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
Form: 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 CoatOSil7510; The 18g isobutyl isobutyrate.
B) preparation technology: pigment, filler, silicon oil modified end carboxyl super branched polyester, organosilicon auxiliary agent, the high boiling solvent of end ring oxygen are mixed, add grinding machine for grinding to arrive 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-resistingly can arrive 510 ℃, snappiness 3mm, cold-hot alternation 57 times.
The performance index of table 20 coating
The comparative example
Contrast coating 1 reference (Ma Yiwen etc., the preparation of end amino-modified silicone vibrin are electroplated and covered with paint, lacquer, colour wash, etc. for 2011,02 phases) preparation; Contrast coating 2 reference (Li Huagong etc., organic-silicon-modified hydroxyl telechelic polyester synthetic, synthetic resins and plastics, 2012,29 (2): 20～23) preparation; Contrast coating 3 reference (CN102504293A) preparation.The performance test situation of contrast coating sees Table 21.Thermotolerance detects according to method 1*; Snappiness detects according to GB/T1731-1993; Alternating hot and cold detects according to method 2*.
The performance index of table 21 coating
Polyester in contrast coating 1 is by 1,6-hexanodioic acid, 1, ammediol 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 the preparation resin process, does not use silicone intermediate to carry out modification to polyester, cause just 280 ℃ of the modified poly ester thermotolerances that prepare, its resistance toheat is worse than coating of the present invention far away.
Resin in contrast coating 2 is to adopt silicone intermediate to carry out modification to the polyol polyester resin, and this resin has good resistance toheat, and its heat resisting temperature reaches 350 ℃.But do not use the silanol modification at the polyol polyester that adopts, cause its snappiness relatively poor, 6mm only, cold-hot alternation just 19 times.
Resin in contrast coating 3 is to adopt silicone intermediate to carry out modification to vibrin, and this resin has good resistance toheat, and its heat resisting temperature reaches 350 ℃.But only adopt dibasic alcohol and the benzene tricarboxylic acid reactions such as neopentyl glycol, 2-methyl 1,3-PD and 1,6-hexylene glycol in the preparation PET Process, do not add low molecular weight silicone oil, the snappiness that causes filming is relatively poor, only 6mm.
The standby coating resistance toheat of resin of the present invention reaches 490 ℃, 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 (8)
1. the preparation method of the silicon oil modified end carboxyl super branched vibrin of an end ring oxygen, it is characterized in that: the triprotic acid of 1～1.5 times of dibasic alcohol and dibasic alcohol mole number is mixed post-heating to 70～90 ℃, add respectively epoxy-terminated silicone oil and the dimethylbenzene of 0.05～0.1 times of dibasic alcohol weight and 0.02～0.1 times; After heating 1～3h under 180～210 ℃, be warming up to 220～240 ℃, after heating 1～3h; Be cooled to 80～90 ℃, add respectively the organic solvent of 1.0～1.5 times of dibasic alcohol weight, 1.5～2.0 times and 1～5%, silicone oligomer and 1～5% crosslinking catalyst; Be heated to 110～120 ℃, heating 2～3h; Be cooled to 80～90 ℃, separately adding at last organic solvent to adjust solid content is 60～70%;
Described dibasic alcohol is one or more in neopentyl glycol, 2-methyl 1,3-PD and Isosorbide-5-Nitrae-cyclohexanediol;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3,5-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);
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 glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate.
2. the preparation method of the silicon oil modified end carboxyl super branched polyester of end ring oxygen according to claim 1, it is characterized in that, described end amido silicon oil prepares by the following method: be that 1: 0.01～0.05%: 2～6% octamethylcyclotetrasiloxane, tetramethyl disiloxane and the vitriol oil add in reactor with mass ratio, and nitrogen protection reaction 7～10h; Be warming up to 180～190 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; With gained end hydrogen silicone oil and weight is respectively 1～10%, 1～2 times of octamethylcyclotetrasiloxane and 0.01～0.05% glycidyl allyl ether, toluene and Platinic chloride adds in reactor; Be warming up to 70～90 ℃, nitrogen protection reaction 8～10h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
3. the preparation method of the silicon oil modified end carboxyl super branched polyester of end ring oxygen according to claim 1, is characterized in that, the epoxy-terminated silicone oil weight-average molecular weight is 300～800, and every 100g epoxy-terminated silicone oil contains 30～50mmol epoxy group(ing).
4. the preparation method of the silicon oil modified end carboxyl super branched polyester of end ring oxygen according to claim 1, it is characterized in that, described silicone oligomer is got by one or more hydrolysis-condensation reactions in methltriethoxysilone, dimethyldiethoxysilane and a phenyl triethoxy.
5. the preparation method of the silicon oil modified end carboxyl super branched polyester of end ring oxygen according to claim 1, 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.
6. the preparation method of the silicon oil modified end carboxyl super branched polyester of end ring oxygen according to claim 1, it is characterized in that, described silicone oligomer is one or more in KR211, KR212, KR214, KR216, IC836, KR213, KR9218, KR217,233,249, Z-6108,3074 and 3037.
7. the end carboxyl super branched polyester that end ring oxygen is silicon oil modified, is characterized in that it is by the described method preparation of claim 1-6 any one.
8. a coating, is characterized in that: by percentage to the quality, contain the silicon oil modified end carboxyl super branched polyester of 60～80% described end ring oxygen, 10～20% high temperature resistant fillers and 5～20% high boiling solvents in the raw material of this coating;
Described high boiling solvent is one or more in ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, 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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| CN105482089A (en) * | 2015-12-26 | 2016-04-13 | 杭州吉华高分子材料股份有限公司 | Water-soluble organic silicone modified polyester resin as well as preparation method and application thereof |
| CN113461925A (en) * | 2021-07-01 | 2021-10-01 | 杭州鑫富科技有限公司 | Flame-retardant biodegradable polyester and preparation method thereof |
| CN113461925B (en) * | 2021-07-01 | 2022-12-13 | 杭州鑫富科技有限公司 | Flame-retardant biodegradable polyester and preparation method thereof |
| CN113801331A (en) * | 2021-09-06 | 2021-12-17 | 华南理工大学 | Waterborne hyperbranched polyester-based epoxy curing agent and preparation method thereof |
| CN113801331B (en) * | 2021-09-06 | 2022-06-14 | 华南理工大学 | Waterborne hyperbranched polyester-based epoxy curing agent and preparation method thereof |
| CN113845625A (en) * | 2021-10-25 | 2021-12-28 | 河北匠工新型建筑材料有限公司 | Environment-friendly modified white latex and preparation method thereof |
| CN113845625B (en) * | 2021-10-25 | 2023-08-22 | 河北匠工新型建筑材料有限公司 | Environment-friendly modified white latex and preparation method thereof |
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