CN103193986A - Epoxy-terminated silicone oil-modified hydroxyl-terminated hyperbranched polyester, and preparation method and application thereof - Google Patents
Epoxy-terminated silicone oil-modified hydroxyl-terminated hyperbranched polyester, and preparation method and application thereof Download PDFInfo
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- CN103193986A CN103193986A CN2013100420910A CN201310042091A CN103193986A CN 103193986 A CN103193986 A CN 103193986A CN 2013100420910 A CN2013100420910 A CN 2013100420910A CN 201310042091 A CN201310042091 A CN 201310042091A CN 103193986 A CN103193986 A CN 103193986A
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- epoxy
- terminated
- silicone oil
- hydroxyl
- hyperbranched polyester
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- 229920006150 hyperbranched polyester Polymers 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 24
- 229920002545 silicone oil Polymers 0.000 claims abstract description 195
- 238000010438 heat treatment Methods 0.000 claims abstract description 97
- 238000000576 coating method Methods 0.000 claims abstract description 76
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 36
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 123
- 229910052710 silicon Inorganic materials 0.000 claims description 103
- 239000010703 silicon Substances 0.000 claims description 103
- 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
- 239000002904 solvent Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 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
- 239000000945 filler Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 125000003700 epoxy group Chemical group 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 14
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 12
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 239000008096 xylene Substances 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
- 238000009835 boiling Methods 0.000 claims description 8
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 7
- 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
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-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
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 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 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- -1 ethoxyl Chemical group 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 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
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 26
- 239000000203 mixture Substances 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000004645 polyester resin Substances 0.000 description 82
- 229920001225 polyester resin Polymers 0.000 description 24
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000004593 Epoxy Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000011056 performance test Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000006872 improvement Effects 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920000587 hyperbranched polymer Polymers 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- NAHIZHJHSUSESF-UHFFFAOYSA-N perchloryl acetate Chemical compound CC(=O)OCl(=O)(=O)=O NAHIZHJHSUSESF-UHFFFAOYSA-N 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 238000002329 infrared spectrum Methods 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application 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
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 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
- 238000010998 test method Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging 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
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
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- 238000002411 thermogravimetry Methods 0.000 description 1
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Abstract
The invention discloses an epoxy-terminated silicone oil-modified hydroxyl-terminated hyperbranched polyester and a preparation method and application thereof. The method comprises the following steps: uniformly mixing trihydric alcohol and m-phthalic acid, heating an obtained mixture to a temperature of 70 to 90 DEG C and adding epoxy-terminated silicone oil and dimethylbenzene; carrying out heating at a temperature of 180 to 210 DEG C for 1 to 3 h, allowing temperature to rise to 220 to 240 DEG C and carrying out heating for 1 to 3 h; carrying out cooling to a temperature of 90 DEG C and adding an organic solvent, organosilicon oligomer and a cross-linking catalyst accounting for 1 to 5% of the weight of trihydric alcohol; carrying out heating to a temperature of 110 to 120 DEG C for 2 to 3 h; and carrying out cooling to a temperature of 90 DEG C and adding the organic solvent to adjust solid content to 60 to 70%. According to the method, epoxy-terminated silicone oil is added during synthesis of the polyester, so heat resistance and flexibility of the polyester are improved; and the organosilicon oligomer and the polyester undergo a cross-linking reaction, so heat resistance of the polyester is enhanced. The polyester prepared by using the method provided by the invention can be used for preparation of high-temperature resistant coating.
Description
Technical Field
The invention relates to hyperbranched polyester, in particular to hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil and a preparation method and application thereof, belonging to the field of organic high molecular compounds.
Background
The polyester resin has excellent metal adhesion, high hardness, high physical and mechanical performance, high chemical corrosion resistance and wide application in paint industry. However, polyester resin has the disadvantages of poor heat resistance, low water resistance and poor weather resistance, and the application of the polyester resin in high-temperature resistant coating is limited. In order to improve the high temperature resistance of polyester resins, other resins are often used to chemically modify the polyester resins. The organic silicon resin is an organic-inorganic hybrid material, and has excellent heat resistance, weather resistance, water resistance and lower surface tension. The organic silicon resin is used for modifying the polyester resin, so that the heat resistance, the water resistance and the chemical resistance of the polyester resin can be improved. For example, the Lidaming and the like (the Lidaming, the development of organosilicon modified polyester type durable coil finish, the coating industry, 2007, 37(12), 30-32) react hydroxyl-containing polyester and organosilicon resin to prepare organosilicon resin modified polyester, and the obtained modified polyester has good ageing resistance. The preparation method comprises the steps of designing and synthesizing organosilicon modified carboxyl-terminated polyester resin by using yaojiangliu and the like (research on high-functional organosilicon modified carboxyl-terminated polyester resin, Shanghai paint, 2007, 45(7), and 4-6), and preparing two-component paint by using the resin, polyurethane curing agents HDI biuret and HDI trimer. The coating has excellent weather resistance and good adhesive force and elasticity, but the modified polyester must be matched with a polyurethane curing agent for use, so that the coating has the defect of inconvenient and rapid use. Lihuagong and the like (Lihuagong and the like, synthesis of organic silicon modified hydroxyl-terminated polyester, synthetic resin and plastic, 2012, 29 (2): 20-23) adopt organic silicon prepolymer to modify the hydroxyl-terminated polyester, and improve the heat resistance and salt water resistance of the polyester.
The hyperbranched polymer has a highly branched structure and a large number of terminal active groups, has high solubility, low viscosity, higher chemical reaction activity and the like, and is widely applied to the field of coatings. The low viscosity makes the hyperbranched polymer suitable for being applied to high solid component coatings, and can be blended with linear polymer coatings to reduce the system viscosity and improve the system fluidity; the high solubility can reduce the dosage of the solvent, reduce the cost and reduce the emission of harmful gases; the hyperbranched structure ensures that the molecular chains of the hyperbranched polymer are less entangled and are not easy to crystallize, so that the coating has good film-forming property; the hyperbranched polymer coating has strong modification capacity due to a plurality of terminal functional groups, and can be used for preparing coatings suitable for various purposes. For example, chinese patent CN102504271A modifies hydroxyl-terminated hyperbranched polyester into silicone resin, so as to improve the mechanical properties, chemical resistance and water resistance of the silicone resin. However, the prepared hydroxyl-terminated hyperbranched polyester modified organic silicon resin has poor flexibility, can crack under high and low temperature alternating conditions, and limits the application of the resin.
Disclosure of Invention
The invention aims to solve the technical problem of providing the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil with good heat resistance and flexibility.
The second technical problem to be solved by the invention is to provide a preparation method of the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil.
The third technical problem to be solved by the invention is to provide a coating containing the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of organic silicon modified hydroxyl-terminated hyperbranched polyester comprises the following steps:
uniformly mixing trihydric alcohol and isophthalic acid with the molar weight 0.5-1.0 time of that of the trihydric alcohol, heating to 70-90 ℃, and adding epoxy-terminated silicone oil with the weight 0.05-0.1 time of that of the trihydric alcohol and xylene with the weight 0.02-0.1 time of that of the trihydric alcohol; heating at 180-210 ℃ for 1-3 h, heating to 220-240 ℃, and heating for 1-3 h; cooling to 90 ℃, adding an organic solvent which is 1.0-1.5 times of the weight of the trihydric alcohol, an organic silicon oligomer which is 1.5-2.5 times of the weight of the trihydric alcohol and a crosslinking catalyst which is 1-5% of the weight of the trihydric alcohol; heating to 110-120 ℃, and heating for 2-3 h; cooling to 90 ℃, and finally adding an organic solvent to adjust the solid content to 60-70%;
wherein,
the trihydric alcohol is one or two of trimethylolethane and trimethylolpropane.
The weight average molecular weight of the epoxy-terminated silicone oil is 300-1000, and each 100g of the epoxy-terminated silicone oil contains 8-100 mmol of epoxy groups;
the crosslinking catalyst is tetrabutyl titanate or tetraisobutyl titanate;
the organic solvent is one or more than two of butanol, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate and dipropylene glycol butyl ether acetate.
The weight average molecular weight of the organic silicon oligomer is 800-2000, and the organic silicon oligomer contains 2.5-15 w% of methoxyl or ethoxyl and 3-20 w% of hydroxyl.
The epoxy-terminated silicone oil can be prepared by the following method:
adding octamethylcyclotetrasiloxane, tetramethyldisiloxane accounting for 0.01-0.05% of the weight of octamethylcyclotetrasiloxane and concentrated sulfuric acid accounting for 2-6% of the weight of octamethylcyclotetrasiloxane into a reactor, and reacting for 7-10 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding hydrogen-terminated silicone oil, allyl glycidyl ether accounting for 1-10% of the weight of octamethylcyclotetrasiloxane, toluene accounting for 1-2% of the weight of octamethylcyclotetrasiloxane and chloroplatinic acid accounting for 0.01-0.05% of the weight of octamethylcyclotetrasiloxane into a reactor; heating to 70-90 ℃, reacting for 8-10 h under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The organosilicon oligomer can be obtained by one or more of siloxane such as monomethyltriethoxysilane, dimethyldiethoxysilane and monophenyltriethoxysilane through hydrolytic condensation reaction, or one or more of siloxane such as monomethyltrimethoxysilane, dimethyldimethoxysilane and monophenyltrimethoxy. Wherein the siloxane is hydrolyzed and condensed by the conventional siloxane in the field, and the process and reaction conditions are conventional techniques which should be understood by those skilled in the art.
The preparation method, wherein the organic silicon oligomer can also be one or more than two of KR211 of Xinyue company, KR212 of Xinyue company, KR214 of Xinyue company, KR216 of Xinyue company, IC836 of Wake company, KR213 of Xinyue company, KR9218 of Xinyue company, KR217 of Xinyue company, 233 of Dow Corning company, 249 of Dow Corning company, Z-6108 of Dow Corning company, 3074 of Dow Corning company and 3037 of Dow Corning company.
The above-mentioned production process, wherein,
wherein the crosslinking catalyst is tetrabutyl titanate.
The weight average molecular weight of the epoxy-terminated silicone oil is preferably 300 to 800, and each 100g of the epoxy-terminated silicone oil preferably contains 30 to 50mmol of epoxy groups.
The organic silicon modified hydroxyl-terminated hyperbranched polyester prepared by the method has the following advantages:
the preparation method comprises the following steps of firstly, reacting trihydric alcohol, isophthalic acid and epoxy-terminated silicone oil to prepare hydroxyl-terminated hyperbranched polyester resin, wherein hydroxyl on the trihydric alcohol and carboxyl on the isophthalic acid are subjected to esterification reaction, and meanwhile, hydroxyl on the trihydric alcohol and epoxy on the epoxy-terminated silicone oil are subjected to reaction, so that a flexible organic silicon chain segment is embedded into the hyperbranched polyester, and the heat resistance, flexibility and cold and heat change resistance of a coating film of the polyester are improved.
And then reacting the hydroxyl-terminated hyperbranched polyester resin with the organic silicon oligomer to prepare the organic silicon modified hydroxyl-terminated hyperbranched polyester resin, wherein hydroxyl on the hydroxyl-terminated hyperbranched polyester resin can be subjected to a crosslinking reaction with alkoxy or silicon hydroxyl on the organic silicon oligomer under the action of a crosslinking catalyst, so that the heat resistance of the polyester resin is improved.
The organic silicon modified hydroxyl-terminated hyperbranched polyester can be applied to preparing high-temperature-resistant low-surface-energy coatings, and the coatings have good heat resistance, flexibility and cold and heat change resistance.
The coating comprises 60-80 w% of the organic silicon modified hydroxyl-terminated hyperbranched polyester, 10-20 w% of high-temperature resistant filler and 5-20 w% of high-boiling point solvent, wherein,
the high boiling point solvent is one or more than two of dibasic acid ester mixture, ethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, isobutyl isobutyrate, 3-ethyl propionate and methyl isoamyl ketone;
the filler is a high-temperature resistant filler commonly used in the field and can be titanium dioxide, silicon dioxide or silicon carbide.
The coating can also be added with high-temperature resistant pigment commonly used in the field, and the high-temperature resistant pigment can be inorganic high-temperature resistant pigment such as carbon black, iron oxide red and the like, and can also be organic high-temperature resistant pigment such as phthalocyanine blue and the like.
The coating can also be added with organosilicon auxiliary agents commonly used in the field, for example, the functions of leveling, defoaming, pigment wetting, viscosity regulation and the like are realized. The organosilicon adjuvant can also be silicone oil or polyether modified organosilicon adjuvant, such as CoatOSil series polyether modified organosilicon adjuvant from Mitigo high-tech materials Co. The kind and amount of the organosilicon adjuvant can be determined by those skilled in the art according to the requirement, and the amount recommended by the inventor is 1-5 w%.
The preparation method of the coating is a preparation method commonly used in the field, namely, the coating is prepared by mixing the organic silicon modified polyester, the pigment, the filler, the organic silicon auxiliary agent and the high boiling point solvent.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the invention prepares the hydroxyl-terminated hyperbranched polyester resin by reacting trihydric alcohol, isophthalic acid and epoxy-terminated silicone oil, wherein hydroxyl on the trihydric alcohol and carboxyl on the isophthalic acid are subjected to esterification reaction, and meanwhile, hydroxyl on the trihydric alcohol and epoxy on the epoxy-terminated silicone oil are subjected to reaction, and a flexible organic silicon chain segment is embedded into the hyperbranched polyester, so that the heat resistance, the flexibility and the cold and heat change resistance of a coating film of the polyester are improved.
2) The hydroxyl-terminated hyperbranched polyester resin and the organic silicon oligomer are reacted to prepare the organic silicon modified hydroxyl-terminated hyperbranched polyester resin, wherein hydroxyl on the hydroxyl-terminated hyperbranched polyester resin can be subjected to a crosslinking reaction with alkoxy or silicon hydroxyl on the organic silicon oligomer under the action of a crosslinking catalyst, so that the heat resistance of the polyester resin is improved.
3) The paint is prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester, so that the paint has high heat resistance and good flexibility. The organic silicon modified hydroxyl-terminated hyperbranched polyester can be applied to preparing high-temperature-resistant low-surface-energy coatings, and the coatings have good heat resistance, flexibility and cold and heat change resistance.
Drawings
FIG. 1 is an infrared spectrum of the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil obtained in example 1.
Detailed Description
Example 1:
1) preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.04g of tetramethylammonium hydroxide and 6g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, the mixture is reacted for 7.5 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding 12g of the obtained terminal hydrogen silicone oil, 12g of allyl glycidyl ether, 350g of toluene and 0.05g of chloroplatinic acid into a reactor; heating to 75 ℃, reacting for 8.5h under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 708; the epoxy value content of the epoxy-terminated silicone oil was measured by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 52mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Uniformly mixing 134g (1.0mol) of trihydric alcohol trimethylolpropane and 107.9g (0.65mol) of isophthalic acid, heating to 80 ℃, and adding 6.7g of prepared epoxy terminated silicone oil and 2.68g of xylene; heating at 180 deg.C for 1h, heating to 240 deg.C, and heating for 1 h; cooling to 90 ℃, adding 134g of propylene glycol methyl ether acetate, 201g of silicone oligomer (201g of Xinyue silicone resin KR150) and 1.34g of crosslinking catalyst tetra-n-butyl titanate which are organic solvents and have the weight 1.0 time of that of the trihydric alcohol; heating to 110 ℃, and heating for 2 h; and cooling to 90 ℃ to obtain the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil. And finally, adding 50g of the residual organic solvent propylene glycol methyl ether acetate, and controlling the solid content to be 60%, so as to obtain the organic silicon modified hydroxyl-terminated hyperbranched polyester. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment. As shown in the infrared spectrum of figure 1: 3400cm-1The broad peak is-OH absorptionPeak at 2950cm-1Is represented by-CH3Absorption peak at 1730cm-1Absorption peak at-COO-, 1120cm-1Is treated as an Si-O-Si absorption peak of 980cm-1Has an epoxy absorption peak of 1250cm-1And 800cm-1Is of Si-CH3Absorption peak. The presence of-OH and-COO-indicates the polyester structure of the host, Si-O-Si and Si-CH3The existence of the (B) indicates that the polyester is modified by the silicone oil, which proves that the silicone oil modified hyperbranched polyester is successfully synthesized. In the following examples, the infrared spectra of the silicone-modified hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil are substantially the same as those in fig. 1, but not provided.
The performance test conditions of the organosilicon modified hydroxyl-terminated hyperbranched polyester resin are shown in table 1. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly heat resistance of 375 ℃ and flexibility of 1 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 1 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated silicone oils
1*The heat resistance method comprises the following steps: baking the test piece at 180 ℃ for 2h, putting the test piece into a constant temperature box type electric furnace checked by a potential difference meter, raising the temperature by 5 ℃/min, beginning timing along with the temperature of the furnace to the temperature required by the experiment, taking out the test piece after the test piece is continuously heated to room temperature (25 ℃), and observing the surface condition of the coating by using a magnifying glass, wherein if the test piece has no cracking or falling phenomena, the heat resistance of the coating is proved to be good.
3) Preparation of hydroxyl-terminated hyperbranched polyester coating modified by epoxy-terminated silicone oil
Filling material titanium dioxide 60g of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester 100g and silicone oil 2008g of organosilicon auxiliary agent per 350cst and 5g of divalent acid ester mixture (DBE) of high boiling point solvent, and adding the mixture into a grinder to grind to obtain the finished product with the required particle size. The properties of the coatings prepared by the tests are shown in table 2. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly heat resistance of 485 ℃, flexibility of 2mm and cold-heat alternation resistance of 68 times.
TABLE 2 Performance index of the coating
2*Solvent resistance test method: at 25 ℃, the wipe was rubbed back and forth 100 times with butanone.
Heat resistance test method is shown in Table 1, appendix 1*
Example 2:
1) preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.02g of tetramethylammonium hydroxide and 4g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, reacting for 7 hours under the protection of nitrogen; heating to 190 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained hydrogen-terminated silicone oil, 2g of allyl glycidyl ether, 200g of toluene and 0.02g of chloroplatinic acid into a reactor; heating to 70 ℃, reacting for 8.0h under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 1015; the epoxy value content of the epoxy-terminated silicone oil was measured by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 8.1mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Uniformly mixing 134g of trimethylolpropane and 83g of isophthalic acid, heating to 80 ℃, and adding 13.4g of the prepared epoxy terminated silicone oil and 13.4g of xylene; heating at 200 deg.C for 3 hr, heating to 220 deg.C, and heating for 2 hr; cooling to 90 ℃, and adding 141g of propylene glycol methyl ether acetate, KR150100g, KR212101g and 6.7g of tetra-n-butyl titanate from shin-Etsu silicone; heating to 115 deg.C for 3 h; the temperature is reduced to 90 ℃, and 34g of butanol is added finally. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the organosilicon modified hydroxyl-terminated hyperbranched polyester resin are shown in table 3. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly heat resistance of 375 ℃ and flexibility of 1 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 3 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated silicone oils
3) Coating material
Consists of the following components: 160g of the hydroxyl-terminated hyperbranched polyester modified by the epoxy-terminated silicone oil; 10g of titanium dioxide; 8g of silicon dioxide; 8g of carbon black; silicone oil
10g of ethylene glycol monoethyl ether acetate.
The preparation process comprises the following steps: the pigment, the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the high-boiling point solvent and the auxiliary agent are uniformly mixed and added into a grinding machine to be ground to the required particle size, and the pigment, the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the high-boiling point solvent and the auxiliary agent are obtained. The properties of the coatings prepared by the tests are shown in table 4. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly the heat resistance can reach 505 ℃, the flexibility is 2mm, and the cold-heat alternation resistance is 67 times.
TABLE 4 Performance index of the coating
Example 3:
1) preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.06g of tetramethylammonium hydroxide and 10g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, the reaction is carried out for 8 hours under the protection of nitrogen; heating to 185 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained terminal hydrogen silicone oil, 18g of allyl glycidyl ether, 350g of toluene and 0.07g of chloroplatinic acid into a reactor; heating to 80 ℃, reacting for 9h under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by gel permeation chromatography, and the result is 492; the epoxy value content of the epoxy-terminated silicone oil was measured by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 77mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Preparation of Silicone oligomers
42.0g of methyl trimethoxy silane, 18.7g of dimethyl dimethoxy silane, 132.0g of phenyl trimethoxy silane and 4.5mmol of hydrochloric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer according to the proportion, stirring and heating are started, the temperature is kept constant after the temperature is raised to 60 ℃, 31.7g of distilled water is dropwise added under stirring, after the dropwise addition is finished, constant-temperature reaction is carried out for 3 hours, reduced-pressure distillation is started, the pressure is controlled to be 0.06MPa, small molecules generated in the reaction process are evaporated, the reduced-pressure distillation is carried out, the reduced-pressure distillation is cooled to the room temperature, the solid content is adjusted to be 60%, and 290g of organic.
The weight average molecular weight of the organic silicon oligomer is detected by adopting gel permeation chromatography, and the result is 802; the hydroxyl content of the organic silicon oligomer is measured by an acetic anhydride method, and the result is 10.6 w%; the methoxy content of the organosilicon oligomer is determined by an acetyl perchlorate method, and the result is 7.4 w%; R/Si is 1.14; ph/Me 1.04.
3) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Uniformly mixing 120g of trimethylolethane and 166g of isophthalic acid, heating to 85 ℃, and adding 9.6g of the prepared epoxy-terminated silicone oil and 8.7g of xylene; heating at 210 deg.C for 2.5h, heating to 235 deg.C, and heating for 3 h; cooling to 90 deg.C, adding 180g dipropylene glycol methyl ether acetate, 200g of the above prepared silicone oligomer, 110g of 249 from Dow Corning, 2.5g of isobutyl titanate and 3.5g of n-butyl titanate crosslinking catalyst; heating to 120 deg.C for 2.5 h; the temperature was reduced to 90 ℃ and 70g dipropylene glycol butyl ether acetate was added. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the organosilicon modified hydroxyl-terminated hyperbranched polyester resin are shown in table 5. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly the heat resistance can reach 390 ℃, and the flexibility is 2 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 5 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated Silicone oils
4) Coating material
Consists of the following components: 100g of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil prepared in the step 3; 20g of silica; 10g of titanium dioxide; 5g phthalocyanine blue; 2g of iron oxide red; 4g CoatOSil 7001; 6g of silicone oil
5g diethylene glycol butyl ether acetate; 5g of butyl acetate.
The preparation process comprises the following steps: the pigment, the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the organic silicon assistant and the high-boiling-point solvent are uniformly mixed and added into a grinding machine to be ground to the required particle size, and the pigment, the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the organic silicon assistant and the high-boiling-point solvent are obtained. The properties of the coatings prepared by the tests are shown in table 6. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly heat resistance of 490 ℃, flexibility of 3mm and cold-heat alternation resistance of 66 times.
TABLE 6 Performance index of the coating
Example 4:
1) preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.04g of tetramethylammonium hydroxide and 4g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, the mixture is reacted for 7 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained hydrogen-terminated silicone oil, 8g of allyl glycidyl ether, 210g of toluene and 0.04g of chloroplatinic acid into a reactor; heating to 75 ℃, reacting for 8h under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 533; the epoxy value content of the epoxy-terminated silicone oil was measured by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 41mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Mixing 67g of trimethylolpropane, 60g of trimethylolethane and 86g of isophthalic acid uniformly, heating to 80 ℃, and adding 6.4g of the prepared epoxy-terminated silicone oil and 2.6g of xylene; heating at 220 deg.C for 2.5h, heating to 230 deg.C, and heating for 2.5 h; cooling to 90 deg.C, adding 27g propylene glycol methyl ether acetate, 100g butanol, 54g 3074 from Dow Corning Corp, 50g 3037 from Dow Corp, 120g KR9218 from Xinyue Corp, 30g KR217 from Xinyue Corp and 2.7g tetra-n-butyl titanate; heating to 110 deg.C for 3 h; the temperature was reduced to 70 ℃ and finally 30g dipropylene glycol methyl ether acetate and 40g dipropylene glycol butyl ether acetate were added. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the organosilicon modified hydroxyl-terminated hyperbranched polyester resin are shown in table 7. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly the heat resistance can reach 405 ℃ and the flexibility is 1 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 7 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated silicone oils
3) Coating material
Consists of the following components: 120g of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil prepared in the step 2; 10g of silicon carbide; 10g of silica; 5g of titanium dioxide; 4g CoatOSil 3500; 4g Silicone oil20g of propionic acid-3-Ethyl Ether (EEP).
The preparation process comprises the following steps: uniformly mixing the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the epoxy-terminated hyperbranched polyester/silicone oil. The properties of the coatings prepared by the tests are shown in Table 8. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly heat resistance of 500 ℃, flexibility of 2mm and cold-heat alternation resistance of 67 times.
TABLE 8 Performance index of the coating
Example 5
1) Preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.1g of tetramethylammonium hydroxide and 12g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, reacting for 9 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained terminal hydrogen silicone oil, 20g of allyl glycidyl ether, 400g of toluene and 0.1g of chloroplatinic acid into a reactor; heating to 90 ℃, reacting for 10 hours under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 303; the epoxy value content of the epoxy-terminated silicone oil was measured by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 86mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
134g of trimethylolpropane and 132.8g of isophthalic acid are uniformly mixed and heated to 80 ℃, and 9.38g of the epoxy-terminated silicone oil prepared above and 8.0g of xylene are added; heating at 190 deg.C for 3h, heating to 220 deg.C, and heating for 2 h; cooling to 90 ℃, adding 201g of propylene glycol methyl ether acetate, 28.0g of 233 g of Dow Corning company, 70g of 249 of Dow Corning company, 40g of Z-6108 of Dow Corning company, 50g of IC836 of Wake company, 20g of KR213 of Xinyue company, 30g of KR9218 of Xinyue company, 55g of KR217 of Xinyue company and 4.3g of tetra-n-butyl titanate; heating to 115 deg.C for 3 h; the temperature was reduced to 90 ℃ and 74g of butanol were added. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the organosilicon modified hydroxyl-terminated hyperbranched polyester resin are shown in table 9. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly the heat resistance can reach 390 ℃, and the flexibility is 1 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 9 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated Silicone oils
3) Coating material
Consists of the following components: 140g of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil prepared in the step 2; 20g of silica; 14g of silica; 4g CoatOSil 3500; 2g CoatOSil 7650; 2g methyl isoamyl ketone (MIAK); 4g of isobutyl isobutyrate.
The preparation process comprises the following steps: uniformly mixing the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the epoxy-terminated hyperbranched polyester/silicone oil. The properties of the coatings prepared by the tests are shown in Table 10. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly heat resistance of 500 ℃, flexibility of 2mm and cold-heat alternation resistance of 67 times.
TABLE 10 Performance indices of the coatings
Example 6
1) Preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.04g of tetramethylammonium hydroxide and 5g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, reacting for 9 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained terminal hydrogen silicone oil, 5g of allyl glycidyl ether, 240g of toluene and 0.04g of chloroplatinic acid into a reactor; heating to 90 ℃, reacting for 10 hours under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 833; the epoxy value content of the epoxy-terminated silicone oil was determined by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 32mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Uniformly mixing 120g of trimethylolethane and 99.6g of isophthalic acid, heating to 70 ℃, and adding 8.7g of epoxy-terminated silicone oil prepared in the step 1 and 4. dimethylbenzene; heating at 210 deg.C for 1h, heating to 220 deg.C, and heating for 3 h; cooling to 90 ℃, adding 190g of propylene glycol methyl ether acetate, 27g of Xinyue organic silicon resin KR150, 30g of Xinyue KR211, 40g of Xinyue KR212, 60g of Xinyue KR214, 60g of Xinyue KR216 and 3.6g of tetra-n-butyl titanate; heating to 120 deg.C for 3 h; finally 50g dipropylene glycol methyl ether acetate and 40g dipropylene glycol butyl ether acetate were added. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the silicone modified hydroxyl-terminated hyperbranched polyester resin are shown in table 11. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly the heat resistance can reach 405 ℃ and the flexibility is 1 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 11 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated Silicone oils
3) Coating material
Consists of the following components: 120g of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil prepared in the step 2; 15g of silica; 15g of titanium dioxide; 4g CoatOSil 3500; 2g CoatOSil 7510; 4g Silicone oil 200/350 cst; 12g of 3-diethylether propionate.
The preparation process comprises the following steps: uniformly mixing the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the epoxy-terminated hyperbranched polyester/silicone oil. The properties of the coatings prepared by the tests are shown in Table 12. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly heat resistance of 500 ℃, flexibility of 2mm and cold-heat alternation resistance of 66 times.
TABLE 12 Performance index of the coating
Example 7
1) Preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.07g of tetramethylammonium hydroxide and 7g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, the mixture is reacted for 8 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained hydrogen-terminated silicone oil, 16g of allyl glycidyl ether, 310g of toluene and 0.05g of chloroplatinic acid into a reactor; heating to 80 ℃, reacting for 8 hours under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 653; the epoxy value content of the epoxy-terminated silicone oil was measured by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 67mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Uniformly mixing 134g of trimethylolpropane and 116.2g of isophthalic acid, heating to 75 ℃, and adding 10.6g of epoxy-terminated silicone oil prepared in the step 1 and 12g of xylene; heating at 180 deg.C for 1h, heating to 240 deg.C, and heating for 1 h; cooling to 90 ℃, adding propylene glycol methyl ether acetate, 168g of Xinyue organic silicon resin KR150, 100g of IC836 from Wake company and 5.2g of tetra-n-butyl titanate; heating to 110 ℃, and heating for 2 h; finally 55g of butanol are added. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the silicone modified hydroxyl-terminated hyperbranched polyester resin are shown in table 13. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly the heat resistance can reach 395 ℃ and the flexibility is 1 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 13 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated Silicone oils
3) Coating material
Consists of the following components: 110g of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil prepared in the step 2; 5g of silica; 25g of silicon carbide; isobutyl isobutyrate 60 g.
The preparation process comprises the following steps: uniformly mixing the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the epoxy-terminated hyperbranched polyester. The properties of the coatings prepared by the tests are shown in Table 14. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly heat resistance of 500 ℃, flexibility of 3mm and cold-heat alternation resistance of 67 times.
TABLE 14 Performance indices of the coatings
Example 8
1) Preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.1g of tetramethylammonium hydroxide and 10g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, reacting for 9 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained terminal hydrogen silicone oil, 20g of allyl glycidyl ether, 360g of toluene and 0.08g of chloroplatinic acid into a reactor; heating to 90 ℃, reacting for 10 hours under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 313; the epoxy value content of the epoxy-terminated silicone oil was determined by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 98mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Preparation of Silicone oligomers
44.5g of methyltriethoxysilane, 50.3g of dimethyldiethoxysilane, 98.4g of monophenyltriethoxysilane and 7.0mmol of hydrochloric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer according to the proportion, stirring and heating are started, the temperature is kept constant after the temperature is raised to 70 ℃, 43.1g of distilled water is dropwise added under stirring, after the dropwise addition is finished, constant temperature reaction is carried out for 3 hours, reduced pressure distillation is started, the pressure is controlled to be 0.06MPa, small molecules generated in the reaction process are evaporated, the reduced pressure distillation is started, the temperature is cooled to room temperature, the solid content is adjusted to be 80%, and 230g of organic silicon oligomer is obtained.
The weight average molecular weight of the organic silicon oligomer is detected by adopting a gel permeation chromatography, and the result is 1986; the hydroxyl content of the organic silicon oligomer is determined by an acetic anhydride method, and the result is 15 w%; the ethoxy content of the organic silicon oligomer is determined by an acetyl perchlorate method, and the result is 3 w%; R/Si is 1.34; ph/Me 0.44.
3) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Uniformly mixing 134g of trimethylolpropane and 107.9g of isophthalic acid, heating to 90 ℃, and adding 6.5g of epoxy-terminated silicone oil prepared in the step 1 and 6.7g of xylene; heating at 180 deg.C for 1h, heating to 240 deg.C, and heating for 1 h; cooling to 90 ℃, adding 134g of propylene glycol methyl ether acetate, 228g of the organic silicon oligomer prepared in the step 2 and 3.1g of tetra-n-butyl titanate; heating to 110 ℃, and heating for 2 h; finally 146g of propylene glycol methyl ether acetate are added. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the silicone modified hydroxyl-terminated hyperbranched polyester resin are shown in table 15. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly the heat resistance can reach 395 ℃ and the flexibility is 2 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 15 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated Silicone oils
4) Coating material
Consists of the following components: 150g of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil prepared in the step 3; 15g of silica; 5g of titanium dioxide; 5g CoatOSil 3500; 5g Silicone oil10g methyl isoamyl ketone
The preparation process comprises the following steps: uniformly mixing the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the epoxy-terminated hyperbranched polyester/silicone oil. The properties of the coatings prepared by the tests are shown in Table 16. It can be seen that: the paint prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesion, cold-heat alternation and flexibility, particularly heat resistance of 495 ℃, flexibility of 3mm and cold-heat alternation resistance of 66 times.
TABLE 16 Performance indices of the coatings
Example 9
1) Preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.05g of tetramethylammonium hydroxide and 6g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, the reaction is carried out for 8 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained terminal hydrogen silicone oil, 11g of allyl glycidyl ether, 320g of toluene and 0.05g of chloroplatinic acid into a reactor; heating to 85 ℃, reacting for 8.5h under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 587; the epoxy value content of the epoxy-terminated silicone oil was measured by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 53mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Silicone oligomers
69.1g of methyltriethoxysilane, 34.0g of dimethyldiethoxysilane, 109.24g of monophenyltriethoxysilane and 5.5mmol of hydrochloric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer according to the proportion, stirring and heating are started, the temperature is kept constant after the temperature is raised to 70 ℃, 42.7g of distilled water is dropwise added under stirring, after the dropwise addition is finished, constant temperature reaction is carried out for 3 hours, reduced pressure distillation is started, the pressure is controlled to be 0.06MPa, small molecules generated in the reaction process are evaporated, the reduced pressure distillation is started, the solid content is cooled to room temperature, and 322g of organic silicon oligomer is obtained by adjusting the solid content to be 60%.
The weight average molecular weight of the silicone oligomer is detected by gel permeation chromatography, and the result is 1808; the hydroxyl content of the organic silicon oligomer is determined by an acetic anhydride method, and the result is 20 w%; the ethoxy content of the organic silicon oligomer is determined by an acetyl perchlorate method, and the result is 2.5 w%; R/Si is 1.21; ph/Me 0.55.
3) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Uniformly mixing 134g of trimethylolpropane alcohol and 116.2g of isophthalic acid, heating to 80 ℃, and adding 9g of epoxy-terminated silicone oil prepared in the step 1 and 7.2g of xylene; heating at 190 deg.C for 1.5h, heating to 230 deg.C, and heating for 2 h; cooling to 90 ℃, adding 160g of propylene glycol methyl ether acetate, 120g of silicone resin KR150, 41g of silicone oligomer prepared in step 2, 80g of IC836 from Wake's company and 5.4g of tetra-n-butyl titanate; heating to 120 ℃, and heating for 2 h; the temperature is reduced to 90 ℃, and 70g of propylene glycol butyl ether acetate is finally added. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the silicone modified hydroxyl-terminated hyperbranched polyester resin are shown in table 17. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly the heat resistance can reach 400 ℃, and the flexibility is 1 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 17 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated Silicone oils
4) Coating material
Consists of the following components: 150g of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil prepared in the step 3; 40g of titanium dioxide; 8g CoatOSil 7510; 2g of isobutyl isobutyrate.
The preparation process comprises the following steps: uniformly mixing the filler, the hydroxyl-terminated hyperbranched polyester ester modified by epoxy-terminated silicone oil, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the epoxy-terminated hyperbranched polyester ester. The properties of the coatings prepared by the tests are shown in Table 18. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly heat resistance of 500 ℃, flexibility of 2mm and cold-heat alternation resistance of 68 times.
TABLE 18 Performance indices of the coatings
Example 10
1) Preparation of epoxy-terminated silicone oil
After 200g of octamethylcyclotetrasiloxane, 0.03g of tetramethylammonium hydroxide and 3g of concentrated sulfuric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer, the reaction is carried out for 8 hours under the protection of nitrogen; heating to 180 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained terminal hydrogen silicone oil, 3g of allyl glycidyl ether, 2400g of toluene and 0.02g of chloroplatinic acid into a reactor; heating to 80 ℃, reacting for 10h under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
The weight average molecular weight of the epoxy-terminated silicone oil is detected by adopting gel permeation chromatography, and the result is 987; the epoxy value content of the epoxy-terminated silicone oil was measured by the hydrochloric acid-acetone method, and it was found that the epoxy-terminated silicone oil contained 13mmol of epoxy groups per 100g of the epoxy-terminated silicone oil.
2) Silicone oligomers
42.0g of methyl trimethoxy silane, 18.7g of dimethyl dimethoxy silane, 123.0g of phenyl trimethoxy silane and 4.5mmol of hydrochloric acid are sequentially added into a reactor provided with a condenser tube, a thermometer, a dropping funnel and a stirrer according to the proportion, stirring and heating are started, the temperature is kept constant after the temperature is raised to 60 ℃, 31.7g of distilled water is dropwise added under stirring, after the dropwise addition is finished, constant temperature reaction is carried out for 3 hours, reduced pressure distillation is started, the pressure is controlled to be 0.06MPa, small molecules generated in the reaction process are evaporated, the reduced pressure distillation is carried out, the temperature is cooled to room temperature, the solid content is adjusted to be 60 percent, and 290g of organic silicon oligomer is obtained.
The weight average molecular weight of the organic silicon oligomer is detected by adopting gel permeation chromatography, and the result is 802; the hydroxyl content of the organic silicon oligomer is measured by an acetic anhydride method, and the result is 10.6 w%; the methoxy content of the organosilicon oligomer is determined by an acetyl perchlorate method, and the result is 7.4 w%; R/Si is 1.14; ph/Me 1.04.
3) Preparation of epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester
Uniformly mixing 40.2g of trimethylolpropane, 84g of trimethylolethane and 149.4g of isophthalic acid, heating to 90 ℃, and adding 4.8g of epoxy-terminated silicone oil prepared in the step 1 and 8.7g of xylene; heating at 190 deg.C for 3h, heating to 230 deg.C, and heating for 3 h; cooling to 90 ℃, and adding 126.2g of propylene glycol methyl ether acetate, 120g of KR212 from shin-Etsu corporation, 120g of the organosilicon intermediate prepared in the step 2 and 3.9g of tetra-n-butyl titanate; heating to 115 deg.C for 3 h; the temperature was reduced to 80 ℃ and 154g propylene glycol methyl ether acetate was added. The solid content is controlled to be 60 percent, so that the organic silicon modified hydroxyl-terminated hyperbranched polyester is obtained. And adding amino-terminated silicone oil and organic silicon oligomer into the hydroxyl-terminated hyperbranched polyester to react and modify to obtain the hydroxyl-terminated hyperbranched polyester containing the organic silicon chain segment.
The performance test conditions of the silicone modified hydroxyl-terminated hyperbranched polyester resin are shown in table 19. It can be seen that: the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent properties in hardness, adhesive force and flexibility, particularly the heat resistance can reach 400 ℃, and the flexibility can reach 2 mm. Compared with polyester resin, the improvement of the heat resistance of the organic silicon modified hydroxyl-terminated hyperbranched polyester resin can prove that the organic silicon chain segment is introduced into the hyperbranched polyester resin matrix.
TABLE 19 comprehensive Properties of hydroxyl-terminated hyperbranched polyesters modified with epoxy-terminated Silicone oils
4) Coating material
Consists of the following components: 120g of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil prepared in the step 3; 40g of titanium dioxide; 20g of silica; 5g of iron oxide red; 2g CoatOSil 7510: 18g of isobutyl isobutyrate.
The preparation process comprises the following steps: uniformly mixing the pigment, the filler, the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil, the organic silicon assistant and the high-boiling-point solvent, and adding the mixture into a grinding machine to grind the mixture to the required particle size to obtain the pigment. The properties of the coatings prepared by the tests are shown in Table 20. It can be seen that: the coating prepared from the organic silicon modified hydroxyl-terminated hyperbranched polyester resin has excellent performances in hardness, adhesive force, cold-heat alternation and flexibility, particularly heat resistance of 510 ℃, flexibility of 3mm and cold-heat alternation resistance of 66 times.
TABLE 20 Performance indices of the coatings
Comparative examples
Comparative coating 1 reference (maozhou et al, preparation of amino-terminated silicone oil modified polyester resin, plating and finishing, 2011, stage 02) formulation in table 21; reference 2 of the comparative coating (Lihuagong et al, synthesis of silicone modified hydroxyl terminated polyester, synthetic resin and plastic, 2012, 29 (2): 20-23); comparative coating 3 reference (CN 102504271 a). The performance tests are shown in Table 21. Heat resistance in the tables according to method 1*Detecting; flexibility is detected according to GB/T1731-1993; cold Heat alternation Properties according to method 2*And (6) detecting. a degradation temperature in thermogravimetric analysis.
TABLE 21 Performance indices of the coatings
The polyester in the comparative coating 1 is prepared by reacting 1, 6-adipic acid, 1, 3-propanediol and hydroxyl silicone oil, the flexibility of the organic silicon modified polyester reaches 4mm, and the cold-hot alternation reaches 35 times, but only a small amount of silicone oil is used for modifying in the process of preparing resin, and an organic silicon intermediate is not used for modifying the polyester, so that the heat resistance of the prepared modified polyester is 280 ℃, and the heat resistance of the modified polyester is far inferior to that of the coating disclosed by the invention.
The resin in the comparative coating 2 is a polyhydroxy polyester resin modified by an organosilicon intermediate, and the resin has good heat resistance, and the heat resistance temperature of the resin reaches 350 ℃. However, the polyhydroxy polyester adopted is not modified by silanol, so that the flexibility is poor, and is only 6mm, and the cold-heat resistance is 19 times.
The resin in the comparative coating 3 is a polyester resin modified by an organosilicon intermediate, and the resin has good heat resistance, and the heat resistance temperature of the resin reaches 350 ℃. However, in the process of preparing polyester, only dibasic acid such as terephthalic acid, isophthalic acid, adipic acid and succinic acid is adopted to react with trihydric alcohol such as trimethylolethane, 1, 3, 5-benzenetriol and 1, 2, 4-benzenetriol, and no low molecular weight silicone oil is added, so that the flexibility of a coating film is poor, and is only 6 mm.
The coating prepared by the resin has the heat resistance of 500 ℃ and the flexibility of 3 mm. The heat resistance and flexibility of the paint are far better than those of a comparative paint 1, a comparative paint 2 and a comparative paint 3.
Claims (8)
1. A preparation method of hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil is characterized by comprising the following steps: uniformly mixing trihydric alcohol and isophthalic acid with the molar weight 0.5-1.0 time that of the trihydric alcohol, heating to 70-90 ℃, and respectively adding epoxy-terminated silicone oil and xylene with the weight 0.05-0.1 time and 0.02-0.1 time that of the trihydric alcohol; heating at 180-210 ℃ for 1-3 h, heating to 220-240 ℃, and heating for 1-3 h; cooling to 80-90 ℃, and respectively adding an organic solvent, an organic silicon oligomer and a crosslinking catalyst which are 1.0-1.5 times, 1.5-2.5 times and 1-5% of the weight of the trihydric alcohol; heating to 110-120 ℃, and heating for 2-3 h; cooling to 90 ℃, and adding an organic solvent to adjust the solid content to 60-70%;
the trihydric alcohol is trimethylolethane and/or trimethylolpropane;
the weight average molecular weight of the epoxy-terminated silicone oil is 300-1000, and each 100g of the epoxy-terminated silicone oil contains 8-100 mmol of epoxy groups;
the crosslinking catalyst is tetrabutyl titanate and/or tetraisobutyl titanate;
the organic solvent is one or more of butanol, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate and dipropylene glycol butyl ether acetate;
the weight average molecular weight of the organic silicon oligomer is 800-2000, and the organic silicon oligomer contains 2.5-15% of methoxyl or ethoxyl and 3-20% of hydroxyl in percentage by mass.
2. The method for preparing hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil according to claim 1, wherein the epoxy-terminated silicone oil is prepared by the following method: adding octamethylcyclotetrasiloxane, tetramethyldisiloxane and concentrated sulfuric acid into a reactor according to the mass ratio of 1: 0.01-0.05% to 2-6%, and reacting for 7-10 h under the protection of nitrogen; heating to 180-190 ℃, and distilling under reduced pressure to remove low-boiling-point substances to obtain hydrogen-terminated silicone oil; adding the obtained hydrogen-terminated silicone oil and allyl glycidyl ether, toluene and chloroplatinic acid which are 1-10%, 1-2 times and 0.01-0.05% of octamethylcyclotetrasiloxane in weight into a reactor; heating to 70-90 ℃, reacting for 8-10 h under the protection of nitrogen, and distilling under reduced pressure to remove the solvent to obtain the epoxy-terminated silicone oil.
3. The method for preparing hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil as claimed in claim 1, wherein the silicone oligomer is obtained by one or more hydrolytic condensation reactions of monomethyltriethoxysilane, dimethyldiethoxysilane and monophenyltriethoxysilane.
4. The method for preparing hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil as claimed in claim 1, wherein the silicone oligomer is obtained by hydrolysis condensation reaction of one or more of monomethyltrimethoxysilane, dimethyldimethoxysilane and monophenyltrimethoxy silane.
5. The method for preparing hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil as claimed in claim 1, wherein the silicone oligomer is one or more of KR211, KR212, KR214, KR216, IC836, KR213, KR9218, KR217, 233, 249, Z-6108, 3074 and 3037.
6. The method for preparing the hydroxyl-terminated hyperbranched polyester modified by epoxy-terminated silicone oil according to claim 1, wherein the weight average molecular weight of the epoxy-terminated silicone oil is 300-800, and each 100g of the epoxy-terminated silicone oil contains 30-50 mmol of epoxy groups.
7. An epoxy-terminated silicone oil modified hydroxyl-terminated hyperbranched polyester, characterized in that it is prepared by the process according to any one of claims 1 to 6.
8. A coating, characterized by: the raw materials of the coating comprise, by mass, 60-80 w% of the hydroxyl-terminated hyperbranched polyester modified by the epoxy-terminated silicone oil, 10-20% of high-temperature resistant filler and 5-20% of high-boiling point solvent; the high boiling point solvent is one or more than two of ethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, isobutyl isobutyrate, 3-ethyl propionate and methyl isoamyl ketone; the high temperature resistance is titanium dioxide, silicon dioxide or silicon carbide; the high-temperature resistant filler is one or more of titanium dioxide, silicon dioxide and silicon carbide.
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| CN104262599A (en) * | 2014-08-25 | 2015-01-07 | 华南理工大学 | Monoglycidyl ether-modified hyperbranched polyester, and preparing method and applications thereof |
| CN111234255A (en) * | 2020-03-10 | 2020-06-05 | 齐鲁工业大学 | Hyperbranched organic silicon wetting agent for waterborne polyurethane and preparation method thereof |
| CN115637098A (en) * | 2022-10-31 | 2023-01-24 | 江苏三木化工股份有限公司 | Preparation method of epoxy modified saturated polyester for coil back paint |
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| CN102504265A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing polyester modified organic silicon resin and coating containing the resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504265A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing polyester modified organic silicon resin and coating containing the resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262599A (en) * | 2014-08-25 | 2015-01-07 | 华南理工大学 | Monoglycidyl ether-modified hyperbranched polyester, and preparing method and applications thereof |
| CN104262599B (en) * | 2014-08-25 | 2016-03-02 | 华南理工大学 | A kind of monoglycidyl ether modified ultra-branching polyester and preparation method thereof and application |
| CN111234255A (en) * | 2020-03-10 | 2020-06-05 | 齐鲁工业大学 | Hyperbranched organic silicon wetting agent for waterborne polyurethane and preparation method thereof |
| CN115637098A (en) * | 2022-10-31 | 2023-01-24 | 江苏三木化工股份有限公司 | Preparation method of epoxy modified saturated polyester for coil back paint |
| CN115637098B (en) * | 2022-10-31 | 2023-11-03 | 江苏三木化工股份有限公司 | Preparation method of epoxy modified saturated polyester for coil back paint |
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Application publication date: 20130710 |