CN102977350A - Preparation method of modified carboxyl-terminated hyperbranched polyester resin and coating containing resin - Google Patents
Preparation method of modified carboxyl-terminated hyperbranched polyester resin and coating containing resin Download PDFInfo
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Abstract
The invention relates to a preparation method of a modified carboxyl-terminated hyperbranched polyester resin. The method comprises the following steps of: mixing diol and triacid uniformly, then heating the mixture to 70-90 DEG C and adding silanol and dimethylbenzene; heating the materials at 180-210 DEG C for 1-3 hours, then continuously raising the temperature to 220-240 DEG C and carrying out heating for 1-3 hours; then reducing the temperature to 90 DEG C and adding organic solvents, organic silicon oligomers, epoxy resins and crosslinking catalysts; raising the temperature to 110-120 DEG C and carrying out heating for 2-3 hours; and finally reducing the temperature to 90 DEG C, adding other organic solvents and regulating the solid content to be 60-70%. The preparation method has the beneficial effects that as silanol is added when carboxyl-terminated hyperbranched polyester is synthesized, the heat resistance and flexibility of polyester are improved; as the organic silicon oligomers and polyester are subjected to crosslinking reaction, the heat resistance of polymer is improved; and the polyester resin prepared by the method can be used for preparing a coating with high temperature resistance and good flexibility.
Description
Technical field
The present invention relates to the organic high molecular compound field, relate to the macromolecular compound that esterification obtains, be specifically related to vibrin.
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 the low and poor shortcoming of weather resistance of water 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 that vibrin is carried out modification, can improve resistance toheat, water resistance and the chemical resistance of vibrin.Such as (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 as properties-correcting agent, 1,2-PD and hexanodioic acid are carried out polycondensation 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. (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.
Hyperbranched polymer has highly branched structure and a large amount of end group active groups, has high resolution, low viscosity and higher chemical reactivity, is widely used in paint field.Low viscosity can reduce system viscosity with the blend of line polymer coating so that hyperbranched polymer is fit to be applied to high solid component coating, and the improvement system is mobile; High solvability can reduce the consumption of solvent, reduces cost, reduces noxious gas emission; Highly branched structure is difficult for crystallization so that the entanglement of hyperbranched polymer molecule interchain is less, makes coating have good film forming properties; Numerous terminal functionality can prepare and be fit to multi-purpose coating so that Hyperbranched Polymer has very strong correctability ability.Such as (Yao Jiangliu etc. such as Yao Jiangliu, the research of the organic-silicon-modified end carboxyl super branched vibrin of high functionality, Shanghai coating, 2007,45(7), 4 ~ 6) organic-silicon-modified end carboxyl super branched vibrin has been synthesized in design, and this resin and polyurethane curing agent HDI biuret and HDI tripolymer are prepared two component coating.This coating has excellent weathering resistance, good sticking power and elasticity, but this modified poly ester must be used with polyurethane curing agent, exists to use efficiently shortcoming of inconvenience.Publication number is to adopt the prepared modified organic silicone resin of end carboxyl super branched polyester in the application for a patent for invention of CN 102504293A, mechanical property, chemical resistance and the water resistance of silicone resin have been significantly improved, but snappiness is poor, can ftracture under the high low temperature alternation condition, limit its application.
Summary of the invention
The technical problem that the present invention solves provides a kind of preparation method of end carboxyl super branched vibrin of modification, and the prepared modified polyester resin of the method is good heat resistance not only, and snappiness is also very good.
The scheme of the technical problem that the present invention is above-mentioned is:
A kind of preparation method of end carboxyl super branched vibrin of modification, the method is comprised of following steps:
Be that the triprotic acid of 1 ~ 1.5 times of dibasic alcohol mixes post-heating to 70 ~ 90 ℃ with dibasic alcohol and molar weight, the silanol and the weight that add weight and be 0.05 ~ 0.1 times of dibasic alcohol are the dimethylbenzene of 0.02 ~ 0.1 times of dibasic alcohol; Behind 180 ~ 210 ℃ of lower heating 1 ~ 3h, continue to be warming up to 220 ~ 240 ℃ of heating 1 ~ 3h; Then, be cooled to 90 ℃, organic solvent, the weight that adds weight and be 1.0 ~ 1.5 times of dibasic alcohol is that silicone oligomer, the weight of 1.5 ~ 2.0 times of dibasic alcohol is that Resins, epoxy and the weight of 0.1 ~ 0.5 times of dibasic alcohol is the crosslinking catalyst of dibasic alcohol 1 ~ 5%; Be warming up to 110 ~ 120 ℃, heating 2 ~ 3h; At last, be cooled to 90 ℃, other adds organic solvent adjustment solid content is 60 ~ 70%; Wherein,
Described dibasic alcohol is a kind of or two or more in neopentyl glycol, 2-methyl 1,3-PD and the Isosorbide-5-Nitrae-cyclohexanediol;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3, the 5-benzene tricarboxylic acid or two kinds;
Described silanol is a kind of or two or more in seven poly-(cyclopentyl) silsesquioxane three silanols, seven phenyl silsesquioxanes, three silanols, seven isobutyl-silsesquioxanes, three silanols and the hydroxy silicon oil;
The weight-average molecular weight of described hydroxy silicon oil is 300 ~ 1000, and contains the hydroxyl of 3 ~ 10w%;
The weight-average molecular weight of described silicone oligomer is 800 ~ 2000, and contains the hydroxyl of 3 ~ 20w% and the methoxy or ethoxy of 2.5 ~ 15w%;
Described crosslinking catalyst is a kind of or two or more in tetrabutyl titanate, tetrabutyl titanate, dioctyl tin oxide, diisooctyl stannic oxide, dioctyl zinc oxide and the diisooctyl zinc oxide;
Described Resins, epoxy is bicyclopentadiene dioxide, 3,4-epoxidation naphthenic acid 3 ', 4 '-epoxidation hexanaphthene methyl esters, two ((3, the 4-epoxycyclohexyl) methyl) a kind of or two or more in adipic acid ester, two (2,3-oxirane ring amyl group) ether, bisphenol-s epoxy resin, the TriMethylolPropane(TMP) glycidyl ether;
Described organic solvent is one or more in butanols, isopropylcarbinol, propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and the dipropylene glycol monobutyl ether acetate.
Above-mentioned preparation method, wherein said hydroxy silicon oil can be the KR220L of company of SHIN-ETSU HANTOTAI and the W-62m of Wa Ke company, can also be prepared by following methods:
With octamethylcyclotetrasiloxane, N; N '-dimethyl formamide and weight are that the tetramethyl ammonium hydroxide of octamethylcyclotetrasiloxane weight 0.01% adds in the reactor; under nitrogen protection, be warming up to 80 ~ 90 ℃; under agitation drip the distilled water that weight is octamethylcyclotetrasiloxane weight 0.2 ~ 6%; after dropwising, isothermal reaction 8 ~ 10h again, after be warming up to 150 ℃ of reaction 1h; low-boiling-point substance is removed in decompression, obtains product.
Above-mentioned preparation method, wherein said silicone oligomer can be obtained by the condensation reaction that is hydrolyzed of the siloxanes such as methltriethoxysilone, dimethyldiethoxysilane and a phenyl triethoxy, also can be obtained by the condensation reaction that is hydrolyzed of the siloxanes such as monomethyl Trimethoxy silane, dimethyldimethoxysil,ne and a phenyl trimethoxy.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,
Described crosslinking catalyst better is tetrabutyl titanate;
Described silanol is hydroxy silicon oil preferably, the weight-average molecular weight of this hydroxy silicon oil preferably 500 ~ 800, and contain the hydroxyl of 3 ~ 8w%.
The end carboxyl super branched vibrin of the modification of method preparation of the present invention has the following advantages:
Dibasic alcohol, triprotic acid and silanol are reacted the end carboxyl super branched vibrin of preparation, when wherein the hydroxyl on the dibasic alcohol and the carboxyl on the triprotic acid carry out esterification, the hydroxyl of dibasic alcohol and the silicon hydroxyl on the silanol react, flexible organosilicon segment is embedded in the hyper-branched polyester, both improve the resistance toheat of polyester and the cold-and-heat resistent variation performance of filming, improved again the snappiness of polyester.
On the other hand, end carboxyl super branched vibrin with end carboxyl super branched vibrin and silicone oligomer reaction preparation modification, hydroxyl and the carboxyl on the superbrnaching end-hydroxy polyester resin wherein, under the crosslinking catalyst effect can with silicone oligomer on alkoxyl group or silicon hydroxyl generation crosslinking reaction, also be conducive to improve the resistance toheat of vibrin.
The end carboxyl super branched vibrin of modification 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 high temperature resistant filler of end carboxyl super branched vibrin, 10 ~ 20w% and 5 ~ 20w% high boiling solvent of the obtained modification of 60 ~ 80w% aforesaid method, 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 the methyl isoamyl ketone;
Described filler is this area high temperature resistant filler commonly used, can be in titanium dioxide, silicon-dioxide and the silicon carbide one or more.
Also can add this area high-temperature resisting pigment commonly used in the above-mentioned coating, described high-temperature resisting pigment can be the inorganic high-temperature resistant pigment such as carbon black, iron oxide red, also can be the organic high temperature-resistant pigment such as phthalocyanine blue.
Can also add this area organosilicon auxiliary agent commonly used in the above-mentioned coating, as, play the effects such as levelling, froth breaking, pigment wetting, viscosity adjustment.Above-mentioned organosilicon auxiliary agent can also be silicone oil, organic silicon modified by polyether auxiliary agent, as, step the CoatOSil series organic silicon modified by polyether auxiliary agent of figure new high-tech material company limited.Those skilled in the art can be according to the kind and the consumption that require to determine organic silicon additive, and the consumption that the inventor recommends is 1 ~ 5w%.
The preparation method of above-mentioned coating is this area preparation method commonly used, and the end carboxyl super branched vibrin, pigment, filler, organosilicon auxiliary agent and the high boiling solvent that are about to modification are mixed to get.
Because coating of the present invention adopts the end carboxyl super branched vibrin preparation of above-mentioned modification, therefore has high heat resistance energy and good snappiness.
Embodiment
It below is the non-limiting example of technical scheme of the present invention.
Embodiment 1:
1) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: neopentyl glycol 104g(1mol);
Triprotic acid: 1,3,5-benzene tricarboxylic acid 210g(1mmol)
Silanol: the KR220L 5.2g of company of SHIN-ETSU HANTOTAI
Dimethylbenzene: 2.08g
Silicone oligomer: the silicone resin KR150 156g of SHIN-ETSU HANTOTAI
Resins, epoxy: bicyclopentadiene dioxide 10g;
Crosslinking catalyst: tetrabutyl titanate 1.04g;
Organic solvent: 1-Methoxy-2-propyl acetate 300g;
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 70 ℃, add silanol and dimethylbenzene; Behind 180 ℃ of lower heating 1h, be warming up to 240 ℃, behind the heating 1h; Be cooled to 90 ℃, add 1.0 times organic solvent of trivalent alcohol weight, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Be cooled to 90 ℃, add at last the residue organic solvent.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
1* solvent resistance: under 25 ℃, use back and forth wiping 100 times of butanone.
The 2* resistance toheat: 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 behind the 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.
2) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 100g of the modification of above-mentioned preparation;
Filler: titanium dioxide 40g;
Organosilicon auxiliary agent: silicone oil
/ 350cst 8g;
High boiling solvent: divalent ester mixture (DBE) 5g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 2:
1) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: neopentyl glycol 62.4g(0.6mol); The 2-methyl isophthalic acid, 3 propylene glycol 36g(0.4mol);
Triprotic acid: 1,2,4-benzene tricarboxylic acid 210g(1.0mol), 1,3,5-benzene tricarboxylic acid 105g(0.5mol) silanol: seven poly-(cyclopentyl) silsesquioxane three silanol 4.84g, seven isobutyl-silsesquioxanes, three silanol 5.0g dimethylbenzene: 9.84g
Silicone oligomer: the silicone resin KR150 100g of SHIN-ETSU HANTOTAI, the KR21247.6g of company of SHIN-ETSU HANTOTAI
Resins, epoxy: TriMethylolPropane(TMP) glycidyl ether 49.2g;
Crosslinking catalyst: tetrabutyl titanate 4.9g
Organic solvent: 1-Methoxy-2-propyl acetate 147g butanols 23g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 90 ℃, add silanol and dimethylbenzene; Behind 200 ℃ of lower heating 3h, be warming up to 220 ℃, behind the heating 2h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 115 ℃, heating 3h; Be cooled to 90 ℃, add at last butanols.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
2) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 160g of the modification of step 1 preparation;
Filler: titanium dioxide 20g, silicon-dioxide 8g
Organosilicon auxiliary agent: silicone oil
/ 350cst 1g.
High boiling solvent: divalent ester mixture (DBE) 5g; Ethylene glycol ether acetate (CAC): 5g.
B) preparation technology
End carboxyl super branched vibrin, high boiling solvent, the auxiliary agent of filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 3:
1) preparation of hydroxy silicon oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 7.4g
DMF：60g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the DMF, begin to stir and heat up, keep homo(io)thermism after being warmed up to 90 ℃, under agitation drip distilled water, after dropwising, behind the isothermal reaction 9.5h, be warming up to 150 ℃ of reaction 1h again, be cooled to 80 ℃, the beginning underpressure distillation, pressure-controlling boils off the small molecules that produces in the reaction process, cool to room temperature at 0.06MPa, adjusting solid content is 60%, obtains hydroxy silicon oil 157g.
C) performance
The weight-average molecular weight of hydroxy silicon oil adopts gel permeation chromatography to detect, and the result is 504; The hydroxy radical content of hydroxy silicon oil adopts diacetyl oxide method method to measure, and the result is 8.2w%.
2) preparation of silicone oligomer
A) form
Monomethyl Trimethoxy silane: 42.0g(0.28mol)
Dimethyldimethoxysil,ne: 18.7g(0.14mol)
One phenyltrimethoxysila,e: 123.0g(0.58mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 4.5mmol hydrochloric acid by proportioning, 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, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 60%, obtains silicone oligomer 290g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and the result is 802; The hydroxy radical content of silicone oligomer adopts the diacetyl oxide method to measure, and the result is 10.6w%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and the result is 7.4w%; R/Si=1.14; Ph/Me=1.04.
3) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: neopentyl glycol 52g(0.5mol); 2-methyl 1,3-PD 27g(0.3mol) and Isosorbide-5-Nitrae-cyclohexanediol 23.2(0.2mol)
Silanol: the hydroxy silicon oil 5g of step 1 preparation, seven phenyl silsesquioxanes, three silanol 3.2g
Triprotic acid: 1,2,4-benzene tricarboxylic acid 252g(1.2mmol)
Dimethylbenzene: 7.3g
Silicone oligomer: the silicone oligomer 120g of step 2 preparation, 249 87.4g of Dow Corning Corporation
Resins, epoxy: two ((3,4-epoxycyclohexyl) methyl) adipic acid ester 4g; Bisphenol-s epoxy resin 8g;
Crosslinking catalyst: tetrabutyl titanate 2.9g, tetrabutyl titanate 2.0g
Organic solvent: dipropylene glycol methyl ether acetate 158g, dipropylene glycol monobutyl ether acetate 90g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 85 ℃, add silanol and dimethylbenzene; Behind 210 ℃ of lower heating 2.5h, be warming up to 235 ℃, behind the heating 3h; Be cooled to 90 ℃, add dipropylene glycol methyl ether acetate, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 120 ℃, heating 2.5h; Be cooled to 90 ℃, add at last the dipropylene glycol monobutyl ether acetate.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
4) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 100g of the modification of step 3 preparation;
Filler: silicon-dioxide 20g; Titanium dioxide 10g, silicon carbide 10g
Organosilicon auxiliary agent: CoatOSil 7001 4g; Silicone oil
/ 350cst 6g;
High boiling solvent: Diethylene Glycol monobutyl ether acetate 5g; N-BUTYL ACETATE 5g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) be coated with performance
The performance index of coating
Embodiment 4:
1) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: 2-methyl 1,3-PD 63g(0.7mol), Isosorbide-5-Nitrae-cyclohexanediol 81.2g(0.3mol)
Silanol: seven poly-(cyclopentyl) silsesquioxane three silanol 10g
Triprotic acid: 1,2,4-benzene tricarboxylic acid 252g(1.2mmol)
Dimethylbenzene: 5.76g
Silicone oligomer: the 307450g of Dow Corning Corporation, the 303750g of Dow Corning Corporation, the KR921860g of company of SHIN-ETSU HANTOTAI, the KR21740g of company of SHIN-ETSU HANTOTAI
Resins, epoxy: two ((3,4-epoxycyclohexyl) methyl) adipic acid ester 9g; 3,4-epoxidation naphthenic acid, 3 ', 4 '-epoxidation hexanaphthene methyl esters 12g; Bicyclopentadiene dioxide 22g;
Crosslinking catalyst: tetrabutyl titanate 4.32g
Organic solvent: 1-Methoxy-2-propyl acetate 72.8g, butanols 100g, dipropylene glycol methyl ether acetate 30g, dipropylene glycol monobutyl ether acetate 20g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 80 ℃, add silanol and dimethylbenzene; Behind 220 ℃ of lower heating 2.5h, be warming up to 230 ℃, behind the heating 2.5h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, butanols, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 110 ℃, heating 3h; Be cooled to 70 ℃, add at last dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
2) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 120g of the modification of step 1 preparation;
Filler: silicon carbide 10g; Silica 1 0g;
Organosilicon auxiliary agent: CoatOSil 3500 4g; Silicone oil
/ 350cst 4g;
High boiling solvent: propionic acid-3-ether ethyl ester (EEP) 10g; Divalent ester mixture (DBE) 10g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 5
1) preparation of hydroxy silicon oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 3.6g
DMF：50g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the DMF, begin to stir and heat up, keep homo(io)thermism after being warmed up to 80 ℃, under agitation drip distilled water, after dropwising, again behind the isothermal reaction 8h, be warming up to 150 ℃ of reaction 1h, be cooled to 80 ℃, the beginning underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature obtains hydroxy silicon oil 176g.
C) performance
The weight-average molecular weight of hydroxy silicon oil adopts gel permeation chromatography to detect, and the result is 1103; The hydroxy radical content of hydroxy silicon oil adopts the diacetyl oxide method to measure, and the result is 2.9w%.
2) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: neopentyl glycol 83.2g(0.8mol); The 2-methyl isophthalic acid, 3 propylene glycol 18g(0.2mol)
Silanol: the hydroxy silicon oil 4g of step 1 preparation
Triprotic acid: 1,3,5-benzene tricarboxylic acid 231g(1.1mmol)
Dimethylbenzene: 7g
Silicone oligomer: 233 21.3g of Dow Corning Corporation, 249 20g of Dow Corning Corporation, the Z-610820g of Dow Corning Corporation, the KR9218 20g of the IC836 20g of Wa Ke company, the KR213 10g of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAI, the KR217 20g of company of SHIN-ETSU HANTOTAI
Resins, epoxy: two (2,3-oxirane ring amyl group) ether 14g; 3,4-epoxidation naphthenic acid, 3 ', 4 '-epoxidation hexanaphthene methyl esters 12g;
Crosslinking catalyst: tetrabutyl titanate 3.1g
Organic solvent: 1-Methoxy-2-propyl acetate 151g, butanols 34g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 80 ℃, add silanol and dimethylbenzene; Behind 190 ℃ of lower heating 3h, be warming up to 220 ℃, behind the heating 2h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 115 ℃, heating 3h; Be cooled to 90 ℃, add at last butanols.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
3) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 140g of the modification of step 2 preparation;
Filler: silicon-dioxide 25g; Titanium dioxide 10g;
Pigment: carbon black 10g;
Organosilicon auxiliary agent: CoatOSil 35004g; CoatOSil 76502g;
High boiling solvent: methyl isoamyl ketone (MIAK) 2g; Isobutyl isobutyrate 4g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of pigment, filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 6
1) preparation of hydroxy silicon oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 4g
DMF：60g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the DMF, begin to stir and heat up, keep homo(io)thermism after being warmed up to 85 ℃, under agitation drip distilled water, after dropwising, again behind the isothermal reaction 10h, be warming up to 150 ℃ of reaction 1h, be cooled to 80 ℃, the beginning underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature obtains hydroxy silicon oil 143g.
C) performance
The weight-average molecular weight of hydroxy silicon oil adopts gel permeation chromatography to detect, and the result is 997; The hydroxy radical content of hydroxy silicon oil adopts diacetyl oxide method method to measure, and the result is 3.02w%.
2) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: neopentyl glycol 104g(1.0mol);
Silanol: the hydroxy silicon oil 3.36g of step 1 preparation, the KR220L 6g of company of SHIN-ETSU HANTOTAI
Triprotic acid: 1,2,4-benzene tricarboxylic acid 252g(1.2mol)
Dimethylbenzene: 4.12g
Silicone oligomer: the silicone resin KR150 27g of SHIN-ETSU HANTOTAI, the KR211 30g of company of SHIN-ETSU HANTOTAI, the KR212 40g of company of SHIN-ETSU HANTOTAI, the KR214 60g of company of SHIN-ETSU HANTOTAI, the KR216 40g of company of SHIN-ETSU HANTOTAI
Resins, epoxy: bicyclopentadiene dioxide 32g;
Crosslinking catalyst: tetrabutyl titanate 2.8g
Organic solvent: 1-Methoxy-2-propyl acetate 135g, dipropylene glycol methyl ether acetate 20g, dipropylene glycol monobutyl ether acetate 10g
B) preparation technology
Dibasic alcohol and triprotic acid are mixed post-heating to 70 ℃, add silanol and dimethylbenzene; Behind 210 ℃ of lower heating 1h, be warming up to 220 ℃, behind the heating 3h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 120 ℃, heating 3h; Add at last dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
3) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 120g of the modification of step 2 preparation;
Filler: silicon-dioxide 25g; Titanium dioxide 5g;
Pigment: iron oxide red 5g;
Organosilicon auxiliary agent: CoatOSil 3500 4g; CoatOSil 7510 2g; Silicone oil
/ 350cst4g;
High boiling solvent: divalent ester mixture (DBE) 12g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of pigment, filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 7
1) preparation of hydroxy silicon oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 4.8g
DMF：60g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the DMF, begin to stir and heat up, keep homo(io)thermism after being warmed up to 80 ℃, under agitation drip distilled water, after dropwising, again behind the isothermal reaction 10h, be warming up to 150 ℃ of reaction 1h, be cooled to 80 ℃, the beginning underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature obtains hydroxy silicon oil 166g.
C) performance
The weight-average molecular weight of hydroxy silicon oil adopts gel permeation chromatography to detect, and the result is 806; The hydroxy radical content of hydroxy silicon oil adopts diacetyl oxide method method to measure, and the result is 4.6w%.
2) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: neopentyl glycol 104g(1.0mol);
Silanol: the hydroxy silicon oil 7.3g of step 1 preparation
Triprotic acid: 1,2,4-benzene tricarboxylic acid 294g(1.4mol)
Dimethylbenzene: 6.4g
Silicone oligomer: the silicone resin KR150 160g of SHIN-ETSU HANTOTAI, the IC836 100g of Wa Ke company
Resins, epoxy: TriMethylolPropane(TMP) glycidyl ether 11g; 3,4-epoxidation naphthenic acid, 3 ', 4 '-epoxidation hexanaphthene methyl esters 13g; Bisphenol-s epoxy resin 10g;
Crosslinking catalyst: tetrabutyl titanate 2.12g, dioctyl zinc oxide 1.0g
Organic solvent: 1-Methoxy-2-propyl acetate 156g butanols 25g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 75 ℃, add silanol and dimethylbenzene; Behind 180 ℃ of lower heating 1h, be warming up to 240 ℃, behind the heating 1h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Add at last butanols.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
3) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 110g of the modification of step 2 preparation;
Filler: silica 1 5g; Titanium dioxide 5g;
Pigment: phthalocyanine blue 8g;
High boiling solvent: divalent ester mixture (DBE) 40g; Isobutyl isobutyrate 20g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of pigment, filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 8
1) preparation of hydroxy silicon oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 5.8g
N, N '-dimethyl formamide (DMF): 60g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the DMF, begin to stir and heat up, keep homo(io)thermism after being warmed up to 85 ℃, under agitation drip distilled water, after dropwising, again behind the isothermal reaction 8h, be warming up to 150 ℃ of reaction 1h, be cooled to 80 ℃, the beginning underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature obtains hydroxy silicon oil.
C) performance
The weight-average molecular weight of hydroxy silicon oil adopts gel permeation chromatography to detect, and the result is 516; The hydroxy radical content of hydroxy silicon oil adopts diacetyl oxide method method to measure, and the result is 8.03w%.
2) preparation of silicone oligomer
A) form
Methltriethoxysilone: 44.5g(0.25mol)
Dimethyldiethoxysilane: 50.3g(0.34mol)
Phenyltriethoxysilane: 98.4g(0.41mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 7.0mmol hydrochloric acid by proportioning, 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, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 80%, obtains silicone oligomer 230g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and the result is 1986; The hydroxy radical content of silicone oligomer adopts the diacetyl oxide method to measure, and the result is 15w%; The oxyethyl group content of silicone oligomer adopts perchloric acid acetyl method to measure, and the result is 3w%; R/Si=1.34; Ph/Me=0.44.
3) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: neopentyl glycol 104g(1.0mol);
Silanol: the multi-hydroxy silicone oil 4.2g of step 1 preparation
Triprotic acid: 1,2,4-benzene tricarboxylic acid 210g(1mmol)
Dimethylbenzene: 3.64g
Silicone oligomer: step 2 preparation silicone oligomer 239
Resins, epoxy: bicyclopentadiene dioxide 10.4g;
Crosslinking catalyst: tetrabutyl titanate 1.5g dioctyl tin oxide 0.5g, tetra-n-butyl titanate 0.5g, dioctyl zinc oxide 0.5g, diisooctyl zinc oxide 0.5g;
Organic solvent: 1-Methoxy-2-propyl acetate 250g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 90 ℃, add silanol and dimethylbenzene; Behind 180 ℃ of lower heating 1h, be warming up to 240 ℃, behind the heating 1h; Be cooled to 90 ℃, add 1.0 times organic solvent of trivalent alcohol weight, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Add at last the residue organic solvent.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
4) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 150g of the modification of step 3 preparation;
Filler: silica 1 5g; Titanium dioxide 5g;
Organosilicon auxiliary agent: CoatOSil 3500 5g; Silicone oil
/ 350cst 5g;
High boiling solvent: divalent ester mixture (DBE) 10g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 9
1) silicone oligomer
A) form
Methltriethoxysilone: 69.1g(0.36mol)
Dimethyldiethoxysilane: 34.0g(0.21mol)
Phenyltriethoxysilane: 109.24g(0.43mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 5.5mmol hydrochloric acid by proportioning, 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, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 60%, obtains silicone oligomer 322g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and the result is 1808; The hydroxy radical content of silicone oligomer adopts the diacetyl oxide method to measure, and the result is 20w%; The oxyethyl group content of silicone oligomer adopts perchloric acid acetyl method to measure, and the result is 2.5w%; R/Si=1.21; Ph/Me=0.55.
2) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: neopentyl glycol 104g(1.0mol);
Silanol: seven poly-(cyclopentyl) silsesquioxane three silanol 4g, the KR220L 4.3g of company of SHIN-ETSU HANTOTAI
Triprotic acid: 1,2,4-benzene tricarboxylic acid 252g(1.2mmol)
Dimethylbenzene: 4.3g
Silicone oligomer: the silicone resin KR150 49g of SHIN-ETSU HANTOTAI, the Z-6108 100g of Dow Corning Corporation, the IC836 100g of Wa Ke company
Resins, epoxy: bicyclopentadiene dioxide 26g;
Crosslinking catalyst: tetrabutyl titanate 2.0g diisooctyl zinc oxide 1.2g, diisooctyl stannic oxide 1.4g
Organic solvent: 1-Methoxy-2-propyl acetate 156g, propandiol butyl ether acetic ester 20g, isopropylcarbinol 10g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 80 ℃, add silanol and dimethylbenzene; Behind 190 ℃ of lower heating 1.5h, be warming up to 230 ℃, behind the heating 2h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 120 ℃, heating 2h; Cool to 90 ℃, add at last propandiol butyl ether acetic ester and isopropylcarbinol.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
3) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 150g of the modification of step 2 preparation;
Filler: titanium dioxide 40g;
Organic additive: CoatOSil 7510 8g;
Height boils and reaches solvent: divalent ester mixture (DBE) 2g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 10
1) preparation of hydroxy silicon oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.02g
Water: 12g
DMF：60g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the DMF, begin to stir and heat up, keep homo(io)thermism after being warmed up to 90 ℃, under agitation drip distilled water, after dropwising, behind the isothermal reaction 9.5h, be warming up to 150 ℃ of reaction 1h again, be cooled to 80 ℃, the beginning underpressure distillation, pressure-controlling boils off the small molecules that produces in the reaction process, cool to room temperature at 0.06MPa, adjusting solid content is 60%, obtains hydroxy silicon oil 157g.
C) performance
The weight-average molecular weight of hydroxy silicon oil adopts gel permeation chromatography to detect, and the result is 301; The hydroxy radical content of hydroxy silicon oil adopts diacetyl oxide method method to measure, and the result is 10.1w%.
2) silicone oligomer
A) form
Monomethyl Trimethoxy silane: 42.0g(0.28mol)
Dimethyldimethoxysil,ne: 18.7g(0.14mol)
One phenyltrimethoxysila,e: 123.0g(0.58mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 4.5mmol hydrochloric acid by proportioning, 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, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 60%, obtains silicone oligomer 290g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and the result is 802; The hydroxy radical content of silicone oligomer adopts the diacetyl oxide method to measure, and the result is 10.6w%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and the result is 7.4w%; R/Si=1.14; Ph/Me=1.04.
3) preparation of the end carboxyl super branched vibrin of modification
A) form:
Dibasic alcohol: 2-methyl 1,3-PD 90g(1.0mol);
Silanol: the hydroxyl silanol 3.8g of step 1 preparation, the KR220L 1.5g of company of SHIN-ETSU HANTOTAI, seven phenyl silsesquioxanes, three silanol 1.0g
Triprotic acid: 1,2,4-benzene tricarboxylic acid 84g(0.4mol), 1,3,5-benzene tricarboxylic acid 126g(0.6mmol)
Dimethylbenzene: 3.2g
Silicone oligomer: the silicone intermediate 70g of KR212 110g step 2 preparation of company of SHIN-ETSU HANTOTAI
Resins, epoxy: TriMethylolPropane(TMP) glycidyl ether 14g; Two (2,3-oxirane ring amyl group) ether 21g;
Crosslinking catalyst: tetrabutyl titanate 1.6g dioctyl zinc oxide 2.0g
Organic solvent: 1-Methoxy-2-propyl acetate 128g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 90 ℃, add silanol and dimethylbenzene; Behind 190 ℃ of lower heating 3h, be warming up to 230 ℃, behind the heating 3h; Be cooled to 90 ℃, add 1.2 times 1-Methoxy-2-propyl acetate of trivalent alcohol weight, silicone oligomer, Resins, epoxy and crosslinking catalyst; Be heated to 115 ℃, heating 3h; Be cooled to 80 ℃, add at last the residue 1-Methoxy-2-propyl acetate.
C) the end carboxyl super branched vibrin performance of modification
The over-all properties of the end carboxyl super branched vibrin of modification
4) coating
A) form
The end carboxyl super branched vibrin of modification: the end carboxyl super branched vibrin 120g of the modification of step 3 preparation;
Filler: titanium dioxide 20g; Silicon-dioxide 40g;
Organosilicon auxiliary agent: CoatOSil 7510:2g;
High boiling solvent: divalent ester mixture (DBE): 18g.
B) preparation technology
End carboxyl super branched vibrin, organosilicon auxiliary agent, the high boiling solvent of filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
The comparative example
Contrast coating 1 reference (Ma Yiwen etc., the preparation of end amino-modified silicone vibrin is electroplated and covering with paint, 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 (CN 102504271A) preparation
Performance
The performance index of coating
Thermotolerance detects according to method 1*; Snappiness detects according to GB/T1731-1993; Alternating hot and cold detects according to method GB 9278.
Degradation temperature during a thermogravimetric analysis.
Polyester in the 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 that polyester is carried out modification, 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 the contrast coating 2 is to adopt silicone intermediate that the polyol polyester resin is carried out modification, 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, the water boiling resistance performance only be 2.4h, cold-hot alternation ability 19 times.
Resin in the contrast coating 3 is to adopt silicone intermediate that vibrin is carried out modification, and this resin has good resistance toheat, and its heat resisting temperature reaches 360 ℃.But only adopt dibasic alcohol and the benzene tricarboxylic acid reactions such as neopentyl glycol, 2-methyl 1,3-PD and 1,6-hexylene glycol in the preparation PET Process, do not add low molecular weight silicone oil, the snappiness that causes filming is relatively poor, only 6mm.
The standby coating resistance toheat of resin of the present invention reaches 510 ℃, 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 (4)
1. the preparation method of the end carboxyl super branched vibrin of a modification, the method is comprised of following steps:
Be that the triprotic acid of 1 ~ 1.5 times of dibasic alcohol mixes post-heating to 70 ~ 90 ℃ with dibasic alcohol and molar weight, the silanol and the weight that add weight and be 0.05 ~ 0.1 times of dibasic alcohol are the dimethylbenzene of 0.02 ~ 0.1 times of dibasic alcohol; Behind 180 ~ 210 ℃ of lower heating 1 ~ 3h, continue to be warming up to 220 ~ 240 ℃ of heating 1 ~ 3h; Then, be cooled to 90 ℃, organic solvent, the weight that adds weight and be 1.0 ~ 1.5 times of dibasic alcohol is that silicone oligomer, the weight of 1.5 ~ 2.0 times of dibasic alcohol is that Resins, epoxy and the weight of 0.1 ~ 0.5 times of dibasic alcohol is the crosslinking catalyst of dibasic alcohol 1 ~ 5%; Be warming up to 110 ~ 120 ℃, heating 2 ~ 3h; At last, be cooled to 90 ℃, other adds organic solvent adjustment solid content is 60 ~ 70%; Wherein,
Described dibasic alcohol is a kind of or two or more in neopentyl glycol, 2-methyl 1,3-PD and the Isosorbide-5-Nitrae-cyclohexanediol;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3, the 5-benzene tricarboxylic acid or two kinds;
Described silanol is a kind of or two or more in seven poly-(cyclopentyl) silsesquioxane three silanols, seven phenyl silsesquioxanes, three silanols, seven isobutyl-silsesquioxanes, three silanols and the hydroxy silicon oil; The weight-average molecular weight of wherein said hydroxy silicon oil is 300 ~ 1000, and contains the hydroxyl of 3 ~ 10w%;
The weight-average molecular weight of described silicone oligomer is 800 ~ 2000, and contains the hydroxyl of 3 ~ 20w% and the methoxy or ethoxy of 2.5 ~ 15w%;
Described crosslinking catalyst is a kind of or two or more in tetrabutyl titanate, tetrabutyl titanate, two octyloxy tin, two different octyloxy tin, dioctyl zinc oxide and the diisooctyl zinc oxide;
Described Resins, epoxy is bicyclopentadiene dioxide, 3,4-epoxidation naphthenic acid 3 ', 4 '-epoxidation hexanaphthene methyl esters, two ((3, the 4-epoxycyclohexyl) methyl) a kind of or two or more in adipic acid ester, two (2,3-oxirane ring amyl group) ether, bisphenol-s epoxy resin, the TriMethylolPropane(TMP) glycidyl ether;
Described organic solvent is one or more in butanols, isopropylcarbinol, propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and the dipropylene glycol monobutyl ether acetate.
2. the preparation method of end carboxyl super branched polyester modified organic silicon resin according to claim 1 is characterized in that, described silanol is hydroxy silicon oil.
3. the preparation method of end carboxyl super branched polyester modified organic silicon resin according to claim 2 is characterized in that, the weight-average molecular weight of described hydroxy silicon oil is 500 ~ 800, and contains the hydroxyl of 3 ~ 8w%.
4. coating, this coating contain the end carboxyl super branched vibrin of modification, the high temperature resistant filler of 10 ~ 20w% and 5 ~ 20w% high boiling solvent of 60 ~ 80w% claim 1,2 or 3 described methods preparations, 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 the methyl isoamyl ketone; Described high temperature resistant filler is one or more in titanium dioxide, silicon-dioxide and the silicon carbide.
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| CN102504293A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin |
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| CN102504293A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin |
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