CN103113566A - Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof - Google Patents
Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof Download PDFInfo
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- CN103113566A CN103113566A CN201310039857XA CN201310039857A CN103113566A CN 103113566 A CN103113566 A CN 103113566A CN 201310039857X A CN201310039857X A CN 201310039857XA CN 201310039857 A CN201310039857 A CN 201310039857A CN 103113566 A CN103113566 A CN 103113566A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 104
- 239000004645 polyester resin Substances 0.000 title claims abstract description 97
- 239000010703 silicon Substances 0.000 title claims abstract description 93
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 93
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 9
- 229920006150 hyperbranched polyester Polymers 0.000 title abstract description 5
- 239000003921 oil Substances 0.000 claims abstract description 84
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- -1 amido silicon Chemical compound 0.000 claims description 102
- 229920001225 polyester resin Polymers 0.000 claims description 92
- 238000000576 coating method Methods 0.000 claims description 70
- 239000011248 coating agent Substances 0.000 claims description 68
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- 229920001296 polysiloxane Polymers 0.000 claims description 53
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 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 24
- 238000010792 warming Methods 0.000 claims description 24
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000004821 distillation Methods 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
- 239000007822 coupling agent Substances 0.000 claims description 15
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229960001866 silicon dioxide Drugs 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 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 group [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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 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
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-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
- 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
- 239000002994 raw material Substances 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 59
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 229920005989 resin Polymers 0.000 abstract description 18
- 239000011347 resin Substances 0.000 abstract description 18
- 239000003973 paint 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
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 44
- 229910021529 ammonia Inorganic materials 0.000 description 22
- 238000000227 grinding Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000012752 auxiliary agent Substances 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 11
- 229920002545 silicone oil Polymers 0.000 description 11
- 238000002479 acid--base titration Methods 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 229920002050 silicone resin Polymers 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 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
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000011159 matrix material Substances 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
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 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
- 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
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000012496 blank sample Substances 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
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000019439 ethyl acetate Nutrition 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
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000011368 organic material Substances 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
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and a preparation method and application thereof. The method comprises the following steps: evenly mixing tribasic alcohol and m-phthalic acid, then heating to 70-90 DEG C, and adding amino-terminated silicon oil and dimethylbenzene; heating at 180-210 DEG C for 1-3 hours, then heating up to 220-240 DEG C, and heating for 1-3 hours; cooling to 90 DEG C, and adding organic solvent, organic silicon low polymer and 1-5% of crosslinking catalyst; heating to 110-120 DEG C, and heating for 2-3 hours; and cooling to 90 DEG C, and finally adding organic solvent until the solid content is regulated to 60-70%. According to the invention, in the synthesis process of polyester, the amino-terminated silicon oil is added to enhance the heat resistance and flexibility of the polyester; and the organic silicon low polymer and the polyester are subjected to crosslinking reaction, thus enhancing the heat resistance of the polyester. The resin prepared by 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 a kind of organic-silicon-modified superbrnaching end-hydroxy polyester resin and preparation method thereof and application, 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 (researchs of the superbrnaching end-hydroxy polyester resin of high functionality modification such as Yao Jiangliu, Shanghai coating, 2007,45 (7), 4～6) organic-silicon-modified polyol polyester resin 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.(the Ma Yiwen etc. such as Ma Yiwen, the preparation of silanol 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.(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 publication number is the made modified organic silicone resin of application for a patent for invention employing superbrnaching end-hydroxy polyester of CN102504271A, mechanical property, chemical resistance and the water resistance of silicone resin have been significantly improved, but snappiness is poor, can ftracture under high low temperature alternation condition, limit its application.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of resistance toheat and the good organic-silicon-modified superbrnaching end-hydroxy polyester resin of snappiness.
Second technical problem to be solved of the present invention is to provide the preparation method of organic-silicon-modified superbrnaching end-hydroxy polyester resin.
The 3rd problem to be solved by this invention is to provide the coating that contains this organic-silicon-modified superbrnaching end-hydroxy polyester resin.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of preparation method of organic-silicon-modified superbrnaching end-hydroxy polyester resin, the method is comprised of following steps:
The m-phthalic acid of 0.5～1.0 times of trivalent alcohol and trivalent alcohol mole number is mixed post-heating to 70～90 ℃, add the dimethylbenzene of 0.02～0.1 times of the end amido silicon oil of 0.05～0.1 times of trivalent alcohol weight and trivalent 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 trivalent alcohol weight, 1～5% crosslinking catalyst of the silicone oligomer that trivalent alcohol weight is 1.5～2.5 times and trivalent 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%.
Trivalent alcohol of the present invention is that trimethylolethane and TriMethylolPropane(TMP) are wherein a kind of or two kinds.
The weight-average molecular weight of described end amido silicon oil is 300～1000, and contains the amino of 0.1～2w%;
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 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.
Above-mentioned preparation method, described end amido silicon oil can be prepared by following methods:
Tetramethyl disiloxane with octamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane weight 0.01%, the tetramethyl ammonium hydroxide of octamethylcyclotetrasiloxane weight 0.02～0.08%, the amino silicane coupling agent of octamethylcyclotetrasiloxane weight 1～10% adds in reactor, be warming up to 120 ℃, react 2～3h under nitrogen protection; Low-boiling-point substance is removed in underpressure distillation, obtains holding amido silicon oil; Wherein said amino silicane coupling agent is aminopropyl triethoxysilane, aminopropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyldiethoxysilane is wherein a kind of or two or more.
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 end amido silicon oil preferably 300～800, and contain the amino of 0.5～1w%.
The organic-silicon-modified superbrnaching end-hydroxy polyester of method preparation of the present invention has the following advantages:
At first trivalent alcohol, m-phthalic acid and end amido silicon oil are reacted preparation superbrnaching end-hydroxy polyester resin, wherein the hydroxyl on trivalent alcohol and the carboxyl on m-phthalic acid carry out esterification, amino on carboxyl on m-phthalic acid and end amido silicon oil reacts 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 superbrnaching end-hydroxy polyester resin and the organic-silicon-modified superbrnaching end-hydroxy polyester resin of silicone oligomer reaction preparation, the hydroxyl 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.
Organic-silicon-modified superbrnaching end-hydroxy polyester 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.
Coating of the present invention, this coating contain the above-mentioned organic-silicon-modified superbrnaching end-hydroxy polyester of 60～80w%, the high temperature resistant filler of 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 CoatOSiI 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, is about to organic-silicon-modified superbrnaching end-hydroxy polyester, pigment, filler, organosilicon auxiliary agent and high boiling solvent and is mixed to get.
Because coating of the present invention adopts above-mentioned organic-silicon-modified superbrnaching end-hydroxy polyester preparation, 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 trivalent alcohol, m-phthalic acid and end amido silicon oil to preparation superbrnaching end-hydroxy polyester resin, wherein the hydroxyl on trivalent alcohol and the carboxyl on m-phthalic acid carry out esterification, amino on carboxyl on m-phthalic acid and end amido silicon oil reacts 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 superbrnaching end-hydroxy polyester resin and the organic-silicon-modified superbrnaching end-hydroxy polyester resin of silicone oligomer reaction preparation, the hydroxyl 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.Described organic-silicon-modified superbrnaching end-hydroxy polyester can be applied in the high temperature resistant low surface energy coatings of preparation, and this coating has good resistance toheat and snappiness.
Description of drawings
Fig. 1 is the infared spectrum of the embodiment 1 organic-silicon-modified superbrnaching end-hydroxy polyester resin of gained.
Embodiment
Embodiment 1:
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane 200g by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane 0.02g, tetramethyl ammonium hydroxide 0.04g, toluene 20g and amino silicane coupling agent N-6-aminoethyl-γ-aminopropyl methyldiethoxysilane 2g, nitrogen protection is warming up to 100 ℃, reaction 7h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 1002; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and its concrete steps are as follows: first accurately take the amido silicon oil of about 1.5g in Erlenmeyer flask, add 20mL tetrahydrofuran (THF) and toluene, stir it is dissolved fully; Add again 3～4 methyl orange indicators, the salt acidometric titration take concentration as 0.2mol/L, color is titration end point when becoming lightcoral by yellow.The ammonia value is calculated as follows
A＝(V-V
0)*c*1.5/m
A: the amino weight that the every gram amido silicon oil of ammonia value w% contains
V: amido silicon oil consumes the volume of hydrochloric acid standard solution, mL
V
0: blank sample consumes the volume of hydrochloric acid standard solution, mL
C: concentration of hydrochloric acid, mol/L;
M: the weight of amido silicon oil, g
The ammonia value of the amido silicon oil of above-mentioned preparation is 0.102w%.(this expression 1g amido silicon oil contains amino 0.102%g)
2) preparation of organic-silicon-modified superbrnaching end-hydroxy polyester resin
Trivalent alcohol TriMethylolPropane(TMP) 134g (1.0mol) and m-phthalic acid 107.9g (0.65mol) are mixed post-heating to 80 ℃, add end amido silicon oil 6.7g and dimethylbenzene 2.74g; 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 134g of 1.0 times of trivalent alcohol weight, the silicone oligomer 229g of the silicone resin KR150 of SHIN-ETSU HANTOTAI and crosslinking catalyst tetra-n-butyl titanate 2.5g; Be heated to 110 ℃, heating 2h; Be cooled to 90 ℃, add at last residue organic solvent 1-Methoxy-2-propyl acetate 176g, controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer reaction modifying to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.Show as accompanying drawing 1 middle infrared spectrum: 3100～3600cm
-1Place's broad peak be-OH and-NH-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, 1250cm
-1And 800cm
-1The place is Si-CH
3Absorption peak.Hydroxyl peak and ester group peak have proved the polyester construction of matrix resin, and silica peak and silicon methyl peak have proved that resin successfully passes through the modification of silicone oil.Infared spectrum and Fig. 1 about organic-silicon-modified superbrnaching end-hydroxy polyester resin in following embodiment are basic identical, do not provide one by one.
Organic-silicon-modified superbrnaching end-hydroxy polyester resin property detection case is as shown in table 1.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 390 ℃, snappiness 1mm.Organic-silicon-modified superbrnaching end-hydroxy polyester resin-phase can prove that in the lifting on resistance toheat the organosilicon segment has been incorporated on the Hyperbranched Polyester Resin matrix than vibrin.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 1
1
*Solvent resistance detection method: under 25 ℃, come with wiping 100 times with butanone.
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 preparation of the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin
With pigment carbon black 40g, filler titanium dioxide 20g, organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 arrive required particle diameter, both.After tested, the coating property of preparation is as shown in table 2.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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
1*: solvent resistance detection method: under 25 ℃, come with wiping 100 times with butanone.
2*: 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.
Embodiment 2:
1) preparation of end amido silicon oil:
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, amino silicane coupling agent and toluene, nitrogen protection is warming up to 90 ℃, reaction 9h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Wherein octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.04g, tetramethyl disiloxane 0.01g, amino silicane coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane 11g, toluene 10g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 310; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 0.12wt%.
2) preparation of organic-silicon-modified superbrnaching end-hydroxy polyester resin
TriMethylolPropane(TMP) 134g and m-phthalic acid 83g are mixed post-heating to 80 ℃, add end amido silicon oil 13.4g and the dimethylbenzene 13.4g of above-mentioned preparation; After heating 3h under 200 ℃, be warming up to 220 ℃, after heating 2h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate 141g, the silicone resin KR150100g of SHIN-ETSU HANTOTAI, the KR212101g of company of SHIN-ETSU HANTOTAI and tetra-n-butyl titanate 6.7g; Be heated to 115 ℃, heating 3h; Be cooled to 90 ℃, add at last butanols 34g.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer modified-reaction to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
The Performance Detection of organic-silicon-modified superbrnaching end-hydroxy polyester resin is listed in table 3.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 390 ℃, snappiness 1mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 3
3) coating
Form: the organic-silicon-modified superbrnaching end-hydroxy polyester resin 160g of above-mentioned preparation; Titanium dioxide 10g; Silicon-dioxide 8g; Carbon black 8g; Silicone oil
/ 350cst1g; Ethylene glycol ether acetate 10g.
Preparation technology: pigment, filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin, high boiling solvent, auxiliary agent are mixed, add grinding machine for grinding to arrive required particle diameter, both.Film performance is listed in table 4.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 57 times.
The performance index of table 4 coating
Embodiment 3:
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, toluene and amino silicane coupling agent, nitrogen protection is warming up to 95 ℃, reaction 8h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Material consumption situation wherein: octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.06g, tetramethyl disiloxane 0.015g, N-β-aminoethyl-γ-aminopropyl methyldiethoxysilane 3g, toluene 15g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 499; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 1.14w%.
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, 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 organic-silicon-modified superbrnaching end-hydroxy polyester resin
120g trimethylolethane and 166g m-phthalic acid are mixed post-heating to 85 ℃, add end amido silicon oil and the 8.7g dimethylbenzene of the above-mentioned preparation of 9.6g; After heating 2.5h under 210 ℃, be warming up to 235 ℃, after heating 3h; Be cooled to 90 ℃, add the 180g dipropylene glycol methyl ether acetate, the silicone oligomer of the above-mentioned preparation of 200g, 249 of 110g Dow Corning Corporation, 2.5g iso-butyl titanate and 3.5g tetrabutyl titanate crosslinking catalyst; Be heated to 120 ℃, heating 2.5h; Be cooled to 90 ℃, add at last 70g dipropylene glycol monobutyl ether acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer modified-reaction to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
Resin property detects lists in table 5.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 400 ℃, snappiness 2mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 5
4) coating
Form: the organic-silicon-modified superbrnaching end-hydroxy polyester resin of 100g step 3 preparation; 20g silicon-dioxide; 10g titanium dioxide; The 5g phthalocyanine blue; The 2g iron oxide red; 4g CoatOSiI7001; 6g silicone oil
/ 350cst; 5g Diethylene Glycol monobutyl ether acetate; The 5g N-BUTYL ACETATE.
Preparation technology: pigment, filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 60 times.
The performance index of table 6 coating
Embodiment 4:
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, toluene and amino silicane coupling agent, nitrogen protection is warming up to 90 ℃, reaction 9h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Material consumption situation wherein: octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.1g, tetramethyl disiloxane 0.02g, propyl-triethoxysilicane 4g, aminopropyl trimethoxysilane 6g, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane 3g, N-β-aminoethyl-γ-aminopropyl methyldiethoxysilane 7g, toluene 20g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 712; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 1.4w%.
2) preparation of organic-silicon-modified superbrnaching end-hydroxy polyester resin
With the 67g TriMethylolPropane(TMP), 60g trimethylolethane and 86g m-phthalic acid mix post-heating to 80 ℃, add end amido silicon oil and the 2.6g dimethylbenzene of the above-mentioned preparation of 6.4g; After heating 2.5h under 220 ℃, be warming up to 230 ℃, after heating 2.5h; Be cooled to 90 ℃, add the 27g 1-Methoxy-2-propyl acetate, the 100g butanols, 54g Dow Corning Corporation 3074,50g Dow Corning Corporation 3037, the KR9218 of company of 120g SHIN-ETSU HANTOTAI, KR217 and the 2.7g tetra-n-butyl titanate of company of 30g SHIN-ETSU HANTOTAI; Be heated to 110 ℃, heating 3h; Be cooled to 70 ℃, add at last 30g dipropylene glycol methyl ether acetate and 40g dipropylene glycol monobutyl ether acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer reaction modifying to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
Resin property detects lists in table 7.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 400 ℃, snappiness 1mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 7
3) coating
Form: the over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of 120g step 2 preparation; 10g silicon carbide; 10g silicon-dioxide; 5g titanium dioxide; 4g CoatOSiI3500; 4g silicone oil
β 50cst; 20g propionic acid-3-ether ethyl ester (EEP).
Preparation technology: over-all properties, organosilicon auxiliary agent, the high boiling solvent of filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin are mixed, add grinding machine for grinding to arrive required particle diameter, both.Film performance is listed in table 8.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 59 times.
The performance index of table 8 coating
Embodiment 5
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, toluene and amino silicane coupling agent, nitrogen protection is warming up to 90 ℃, reaction 9h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Material consumption situation wherein: octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.08g, tetramethyl disiloxane 0.02g, aminopropyl trimethoxysilane 6g, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane 4g, N-β-aminoethyl-γ-aminopropyl methyldiethoxysilane 6g toluene 20g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 507; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 0.94w%.
2) preparation of organic-silicon-modified superbrnaching end-hydroxy polyester resin
134g TriMethylolPropane(TMP) and 132.8g m-phthalic acid are mixed post-heating to 80 ℃, add epoxy-terminated silicone oil and the 8.0g dimethylbenzene of the above-mentioned preparation of 9.38g; After heating 3h under 190 ℃, be warming up to 220 ℃, after heating 2h; Be cooled to 90 ℃, add the 201g 1-Methoxy-2-propyl acetate, 28.0g 233 of Dow Corning Corporation, 249 of 70g Dow Corning Corporation, the Z-6108 of 40g Dow Corning Corporation, the IC836 of 50g Wa Ke company, the KR213 of company of 20g SHIN-ETSU HANTOTAI, the KR9218 of company of 30g SHIN-ETSU HANTOTAI, KR217 and the 4.3g tetra-n-butyl titanate of company of 55g SHIN-ETSU HANTOTAI; Be heated to 115 ℃, heating 3h; Be cooled to 90 ℃, add at last the 74g butanols.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer reaction modifying to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
Resin property detects lists in table 9.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 390 ℃, snappiness 1mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 9
3) coating
Form: the organic-silicon-modified superbrnaching end-hydroxy polyester resin of 140g step 2 preparation; 20g silicon-dioxide; 14g silicon-dioxide; 4g CoatOSiI3500; 2g CoatOSiI7650; 2g methyl isoamyl ketone (MIAK); The 4g isobutyl isobutyrate.
Preparation technology: filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.Film performance is listed in table 10.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 61 times.
The performance index of table 10 coating
Embodiment 6
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, toluene and amino silicane coupling agent, nitrogen protection is warming up to 90 ℃, reaction 9h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Material consumption situation wherein: octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.12g, tetramethyl disiloxane 0.02g, aminopropyl triethoxysilane 5g, toluene 20g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 845; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 0.23w%.
2) preparation of organic-silicon-modified superbrnaching end-hydroxy polyester resin
120g trimethylolethane and 99.6g m-phthalic acid are mixed post-heating to 70 ℃, add end amido silicon oil and 4. dimethylbenzene of 8.7g step 1 preparation; After heating 1h under 210 ℃, be warming up to 220 ℃, after heating 3h; Be cooled to 90 ℃, add the 190g 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, KR216 and the 3.6g tetra-n-butyl titanate of company of 60g SHIN-ETSU HANTOTAI; Be heated to 120 ℃, heating 3h; Add at last 50g dipropylene glycol methyl ether acetate and 40g dipropylene glycol monobutyl ether acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer reaction modifying to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
Table 11 is listed in the resin property test.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 400 ℃, snappiness 1mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 11
3) coating
Form: the organic-silicon-modified superbrnaching end-hydroxy polyester resin of 120g step 2 preparation; 15g silicon-dioxide; 15g titanium dioxide; 4g CoatOSiI3500; 2g CoatOSiI7510; 4g silicone oil
/ 350cst; 12g propionic acid-3-ether ethyl ester.
Preparation technology: filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.Film performance is listed in table 12.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 60 times.
The performance index of table 12 coating
Embodiment 7
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, toluene and amino silicane coupling agent, nitrogen protection is warming up to 90 ℃, reaction 9h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Material consumption situation wherein: octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.09g, tetramethyl disiloxane 0.02g, aminopropyl triethoxysilane 4g aminopropyl trimethoxysilane 4g, toluene 20g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 661; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 1.54w%.
2) preparation of organic-silicon-modified superbrnaching end-hydroxy polyester resin
134g TriMethylolPropane(TMP) and 116.2g m-phthalic acid are mixed post-heating to 75 ℃, add end amido silicon oil and the 12g dimethylbenzene of 10.6g step 1 preparation; After heating 1h under 180 ℃, be warming up to 240 ℃, after heating 1h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, the 168g silicone resin KR150 of SHIN-ETSU HANTOTAI, IC836 and the 5.2g tetra-n-butyl titanate of 100g Wa Ke company; Be heated to 110 ℃, heating 2h; Add at last the 55g butanols.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer reaction modifying to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
Table 13 is listed in the resin property test.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 400 ℃, snappiness 1mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 13
3) coating
Form: the organic-silicon-modified superbrnaching end-hydroxy polyester resin of 110g step 2 preparation; 5g silicon-dioxide; 25g silicon carbide; Isobutyl isobutyrate 60g.
Preparation technology: filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.Film performance is listed in table 14.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 58 times.
The performance index of table 14 coating
Embodiment 8
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, toluene and amino silicane coupling agent, nitrogen protection is warming up to 90 ℃, reaction 9h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Material consumption situation wherein: octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.11g, tetramethyl disiloxane 0.02g, aminopropyl triethoxysilane 12g, toluene 20g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 297; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 2.01w%.
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 organic-silicon-modified superbrnaching end-hydroxy polyester resin
134g TriMethylolPropane(TMP) and 107.9g m-phthalic acid are mixed post-heating to 90 ℃, add end amido silicon oil and the 6.7g dimethylbenzene of 6.5g step 1 preparation; After heating 1h under 180 ℃, be warming up to 240 ℃, after heating 1h; Be cooled to 90 ℃, add the 134g 1-Methoxy-2-propyl acetate, 228g step 2 preparation silicone oligomer and 3.1g tetra-n-butyl titanate; Be heated to 110 ℃, heating 2h; Add at last the 146g 1-Methoxy-2-propyl acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer reaction modifying to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
Resin property detects lists in table 15.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 400 ℃, snappiness 2mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 15
4) coating
Form: the organic-silicon-modified superbrnaching end-hydroxy polyester resin of 150g step 3 preparation; 15g silicon-dioxide; 5g titanium dioxide; 5g CoatOSiI3500; 5g silicone oil
/ 350cst; The 10g methyl isoamyl ketone
Preparation technology: filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.Film performance is listed in table 16.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 59 times.
The performance index of table 16 coating
Embodiment 9
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, toluene and amino silicane coupling agent, nitrogen protection is warming up to 90 ℃, reaction 9h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Material consumption situation wherein: octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.14g, tetramethyl disiloxane 0.02g, aminopropyl triethoxysilane 9g, N-β-aminoethyl-γ-aminopropyl methyldiethoxysilane 9g, toluene 20g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 985; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 0.17w%.
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 organic-silicon-modified superbrnaching end-hydroxy polyester resin
The pure and mild 116.2g m-phthalic acid of 134g TriMethylolPropane(TMP) is mixed post-heating to 80 ℃, add end amido silicon oil and the 7.2g dimethylbenzene of 9g step 1 preparation; After heating 1.5h under 190 ℃, be warming up to 230 ℃, after heating 2h; Be cooled to 90 ℃, add the 160g 1-Methoxy-2-propyl acetate, the 120g silicone resin KR150 of SHIN-ETSU HANTOTAI, the silicone oligomer of 41g step 2 preparation, IC836 and the 5.4g tetra-n-butyl titanate of 80g Wa Ke company; Be heated to 120 ℃, heating 2h; Cool to 90 ℃, add at last 70g propandiol butyl ether acetic ester.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer reaction modifying to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
Resin property detects lists in table 17.Can see: organic-silicon-modified superbrnaching end-hydroxy polyester resin all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 400 ℃, snappiness 1mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 17
4) coating
Form: the organic-silicon-modified superbrnaching end-hydroxy polyester resin of 150g step 3 preparation; 40g titanium dioxide; 8gCoatOSiI7510; The 2g isobutyl isobutyrate.
Preparation technology: filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.Film performance is listed in table 18.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 61 times.
The performance index of table 18 coating
Embodiment 10
1) preparation of end amido silicon oil
Add successively octamethylcyclotetrasiloxane by proportioning in the reactor that prolong, thermometer and agitator are housed, after tetramethyl disiloxane, tetramethyl ammonium hydroxide, toluene and amino silicane coupling agent, nitrogen protection is warming up to 90 ℃, reaction 9h; Low-boiling-point substance and solvent are removed in underpressure distillation, obtain holding amido silicon oil.Material consumption situation wherein: octamethylcyclotetrasiloxane 200g, tetramethyl ammonium hydroxide 0.1g, tetramethyl disiloxane 0.02g, N-β-aminoethyl-γ-aminopropyl methyldiethoxysilane 20g, toluene 20g.
The weight-average molecular weight of end amido silicon oil adopts gel permeation chromatography to detect, and result is 603; The ammonia value of end amido silicon oil adopts determination of acid-basetitration, and the ammonia value is 1.07w%.
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 organic-silicon-modified superbrnaching end-hydroxy polyester resin
134g TriMethylolPropane(TMP) and 149.4g m-phthalic acid are mixed post-heating to 90 ℃, add end amido silicon oil and the 13.2g dimethylbenzene of 11.8g step 1 preparation; After heating 3h under 190 ℃, be warming up to 230 ℃, after heating 3h; Be cooled to 90 ℃, add the 134g 1-Methoxy-2-propyl acetate, the KR212 of company of 110g SHIN-ETSU HANTOTAI, silicone oligomer and the 3.9g tetra-n-butyl titanate of the preparation of 120g step 2; Be heated to 115 ℃, heating 3h; Be cooled to 80 ℃, add at last the 146g 1-Methoxy-2-propyl acetate.Controlling solid content is 60%, has so just obtained organic-silicon-modified superbrnaching end-hydroxy polyester.With respect to superbrnaching end-hydroxy polyester, add end amido silicon oil and silicone oligomer reaction modifying to obtain containing the superbrnaching end-hydroxy polyester of organosilicon segment.
Organic-silicon-modified superbrnaching end-hydroxy polyester resin property is listed in table 19.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin preparation all has excellent performance in hardness, sticking power and snappiness, especially heat-resistingly can arrive 400 ℃, snappiness 2mm.
The over-all properties of the organic-silicon-modified superbrnaching end-hydroxy polyester resin of table 19
4) coating
Form: the organic-silicon-modified superbrnaching end-hydroxy polyester resin of 120g step 3 preparation; 40g titanium dioxide; 20g silicon-dioxide; The 5g iron oxide red; 2g CoatOSiI7510:18g isobutyl isobutyrate.
Preparation technology: pigment, filler, organic-silicon-modified superbrnaching end-hydroxy polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.Film performance is listed in table 20.Can see: the coating of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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 61 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 (CN102504271A) preparation.The performance test situation of contrast coating sees Table 21.In table, 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 the terminal hydroxy group Hyperbranched Polyester Resin, and this resin has good resistance toheat, and its heat resisting temperature reaches 350 ℃.But only adopt diprotic acid and the trimethylolethanes, 1 such as terephthalic acid, m-phthalic acid, hexanodioic acid and succinic acid in preparation superbrnaching end-hydroxy polyester process, 3,5-benzene three pure and mild 1,2, the reaction of the trivalent alcohols such as 4-benzene triol, 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 more than 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 an organic-silicon-modified superbrnaching end-hydroxy polyester resin, it is characterized in that: the m-phthalic acid of 0.5～1.0 times of trivalent alcohol and trivalent alcohol mole number is mixed post-heating to 70～90 ℃, add respectively end amido silicon oil and the dimethylbenzene of 0.05～0.1 times of trivalent 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 organic solvent, silicone oligomer and the crosslinking catalyst of 1.0～1.5 times of trivalent alcohol weight, 1.5～2.5 times and 1～5%; Be heated to 110～120 ℃, heating 2～3h; Be cooled to 80～90 ℃, adding at last organic solvent to adjust solid content is 60～70%;
Trivalent alcohol of the present invention is trimethylolethane and/or TriMethylolPropane(TMP);
The weight-average molecular weight of described end amido silicon oil is 300～1000, and in the end amido silicon oil, amino mass content is 0.1～2%;
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 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.
2. the preparation method of organic-silicon-modified superbrnaching end-hydroxy polyester resin according to claim 1, it is characterized in that, described end amido silicon oil prepares by the following method: be that 1: 0.005～0.01%: 0.02～0.08%: 1～10%: 5～10% octamethylcyclotetrasiloxane, tetramethyl disiloxane, tetramethyl ammonium hydroxide, amino silicane coupling agent and toluene add in reactor with mass ratio, be warming up to 90～100 ℃, react 7～9h under nitrogen protection; Low-boiling-point substance is removed in underpressure distillation, obtains holding amido silicon oil; Described amino silicane coupling agent is one or more in aminopropyl triethoxysilane, aminopropyl trimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane and N-β-aminoethyl-γ-aminopropyl methyldiethoxysilane.
3. the preparation method of organic-silicon-modified superbrnaching end-hydroxy polyester resin according to claim 1, is characterized in that, the weight-average molecular weight of described end amido silicon oil is 300～800, and in the end amido silicon oil, amino mass content is 0.5～1%.
4. the preparation method of organic-silicon-modified superbrnaching end-hydroxy polyester resin according to claim 1, it is characterized in that, described silicone oligomer is got by methltriethoxysilone, dimethyldiethoxysilane and one or more hydrolysis-condensation reactions of phenyl triethoxy.
5. the preparation method of organic-silicon-modified superbrnaching end-hydroxy polyester resin according to claim 1, it is characterized in that, described silicone oligomer is obtained by monomethyl Trimethoxy silane, dimethyldimethoxysil,ne and one or more condensation reactions that are hydrolyzed of a phenyl trimethoxy.
6. the preparation method of organic-silicon-modified superbrnaching end-hydroxy polyester resin 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. an organic-silicon-modified superbrnaching end-hydroxy polyester resin, 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 60～80% described organic-silicon-modified superbrnaching end-hydroxy polyester resins, 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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