CN104558577B - A kind of preparation method of nano aluminium oxide composite organic modified ultra-branching vibrin and the coating containing this resin - Google Patents
A kind of preparation method of nano aluminium oxide composite organic modified ultra-branching vibrin and the coating containing this resin Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of nano aluminium oxide composite organic modified ultra-branching vibrin and the coating containing this resin, method is as follows: first use nano aluminium oxide, ethanol, water and 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane to prepare organic modified nano aluminum oxide; By diprotic acid, trivalent alcohol, after being warming up to 170 ~ 210 DEG C of insulation 1 ~ 3h, being warming up to 225 DEG C and adding organic modified nano aluminum oxide insulation 1h, be then cooled to 85 DEG C, add silicone oligomer after crosslinking catalyst and dimethylbenzene mix; Be heated to 110 ~ 130 DEG C, insulation 1.5 ~ 2.5h; Be cooled to 85 DEG C, add organic solvent and make solid content be 51 ~ 60wt%.The method uses organic modified nano aluminum oxide, and diprotic acid and trivalent alcohol one react and prepare modified ultra-branching polyester, improves the hardness of polyester; Silicone oligomer and polyester are carried out crosslinking reaction, improves the resistance toheat of polyester.Vibrin prepared by present method can be used for preparing high temperature resistant low surface energy coatings.
Description
Technical field
The present invention relates to organic high molecular compound preparation field, particularly relate to the macromolecular compound that esterification obtains, be specifically related to Hyperbranched Polyester Resin.
Background technology
Vibrin is by the general name of the macromolecular compound of dibasic alcohol or diprotic acid or polyvalent alcohol and polyprotonic acid polycondensation, its good manufacturability, glue-line hardness after solidification is large, the transparency is good, luminance brightness is high, can room temperature pressurization fast setting, its thermotolerance, wearability, chemical proofing and mechanical property are better.Be mainly used in gluing glass reinforced plastic, rigid plastics, concrete, electrically potting etc., vibrin is also used widely in coating industry, but it also has obvious shortcoming, such as: vibrin molecular weight is large, poorly soluble, viscosity is high, and more difficult and other resins carry out chemical modification.
Hyperbranched Polyester Resin after hyperbranched has highly branched structure and a large amount of terminal reactive groups, has high resolution, low viscosity and higher chemical reactivity, compensate for its shortcoming to a certain extent.Our company Authorization Notice No. CN102504293B, the Chinese invention patent in authorized announcement date on August 14th, 2013 discloses a kind of preparation method of hyperbranched polyester modified organic silicon resin and the coating containing this resin, the method is: after the crosslinking catalyst of the silicone resin of end carboxyl super branched for 40-60wt% polyester, 1-10wt%3-glycidyl ether oxygen propyl trimethoxy silicane, 30-50wt% and end carboxyl super branched weight polyester 1-10% is heated 1-3 hour at 110-130 DEG C, be warming up to 150-180 DEG C, heating 1-3 hour; Finally be down to room temperature, adding organic solvent adjustment solid content is 60-70wt%.The advantages of end carboxyl super branched polyester and silicone resin is got up by the method, obtains excellent resistance toheat, good metal adhesion, low surface energy, excellent water boiling resistance performance and acid resistance.But hyperbranched polyester modified organic silicon resin prepared by this invention still leaves some room for improvement in thermotolerance and hardness.
Summary of the invention
Better resistance toheat and better hardness is had in order to make Hyperbranched Polyester Resin, the invention provides a kind of preparation method of nano aluminium oxide composite organic modified ultra-branching vibrin, present invention also offers a kind of coating of the nano aluminium oxide composite organic modified ultra-branching vibrin containing preparing by the inventive method.
Concrete technical scheme of the present invention is: a kind of preparation method of nano aluminium oxide composite organic modified ultra-branching vibrin, carries out as follows:
By nano aluminium oxide, ethanol, water and 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane mixes by weight 1:20 ~ 60:5 ~ 15:0.4 ~ 0.8, back flow reaction 8 ~ 24h in 55 DEG C of water-baths, reaction is down to room temperature after stopping, product, through centrifugation and washing, obtains organic modified nano aluminum oxide;
Be diprotic acid and the trivalent alcohol of 1:1 ~ 2 by mol ratio, and after the dimethylbenzene of weight to be the crosslinking catalyst of described diprotic acid 0.02 ~ 0.1 times and weight be diprotic acid 0.06 ~ 0.1 times mixes, be warming up to 170 ~ 210 DEG C, after insulation 1 ~ 3h, be warming up to 225 DEG C again, add the described organic modified nano aluminum oxide that weight is diprotic acid 0.5 ~ 1 times, insulation 1h, then, be cooled to 85 DEG C, add the silicone oligomer that organic solvent that weight is diprotic acid 1.5 ~ 2.0 times and weight are diprotic acid 1.0 ~ 1.5 times; Be warming up to 110 ~ 130 DEG C, heating 1.5 ~ 2.5h; Be cooled to 85 DEG C again, add organic solvent and make solid content be 51 ~ 60wt%, namely obtain nano aluminium oxide composite organic modified ultra-branching vibrin.
Wherein: described diprotic acid is one in m-phthalic acid and terephthalic acid or mixture.
Described trivalent alcohol is one in trimethylolethane and TriMethylolPropane(TMP) or mixture.
Described crosslinking catalyst is one in tetrabutyl titanate, tetrabutyl titanate, dioctyl zinc oxide and diisooctyl zinc oxide or two or more.
Described organic solvent is one or more in dipropylene glycol methyl ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, butanols, isopropylcarbinol, 1-Methoxy-2-propyl acetate and dipropylene acetic ester.
The weight-average molecular weight of described silicone oligomer is 700 ~ 2200, and containing the methoxy or ethoxy of 3 ~ 16wt% and the hydroxyl of 5 ~ 22wt%.
Alternatively, described 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 that the conventional siloxanes in this area is hydrolyzed condensation reaction, and its technique and reaction conditions are the routine techniquess that those skilled in the art should grasp.
Alternatively, described silicone oligomer also can the IC836 of Shi Wake company, 233 of Dow Corning Corporation, 249 of Dow Corning Corporation, the Z-6108 of Dow Corning Corporation, 3074 of Dow Corning Corporation, SHIN-ETSU HANTOTAI silicone resin KR150, the KR211 of company of SHIN-ETSU HANTOTAI, the KR212 of company of SHIN-ETSU HANTOTAI, the KR214 of company of SHIN-ETSU HANTOTAI, the KR216 of company of SHIN-ETSU HANTOTAI, the one in the KR213 of company of SHIN-ETSU HANTOTAI or two or more.
As preferably, the particle diameter of described organic modified nano aluminum oxide is 20 ~ 200nm, and epoxy group content is 10 ~ 20mmol/g.
Nano aluminium oxide composite organic modified ultra-branching vibrin prepared by method of the present invention, has the following advantages:
Diprotic acid, trivalent alcohol and organic modified nano aluminum oxide are carried out the nanometer alumina modified Hyperbranched Polyester Resin of reaction preparation, wherein diprotic acid and trivalent alcohol carry out esterification hyper-branched polyester are grafted to organic modified nano aluminum oxide, nano aluminium oxide is embedded in hyper-branched polyester, improves resistance toheat and the hardness of polyester; On the other hand, nanometer alumina modified Hyperbranched Polyester Resin and silicone oligomer are carried out crosslinking reaction and prepare nano aluminium oxide composite organic modified ultra-branching vibrin, improve resistance toheat and the hardness of vibrin further.
A kind of coating, this coating contains nano aluminium oxide composite organic modified ultra-branching vibrin that 55 ~ 75wt% prepared as stated above, 12.5 ~ 22.5wt% is high temperature resistant filler and 7.5 ~ 22.5wt% high boiling solvent.
Wherein: described high temperature resistant filler is one or more in titanium dioxide, silicon-dioxide and silicon carbide; Described high boiling solvent refers to one in ethylene glycol ether acetate, butyl acetic ester, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and methyl isoamyl ketone or two or more.
Also can add the high-temperature resisting pigment that this area is conventional in above-mentioned coating, described high-temperature resisting pigment can be the inorganic high-temperature resistant such as carbon black, iron oxide red pigment, also can be the organic high temperature-resistant pigment such as phthalocyanine blue.
The organosilicon auxiliary agent that this area is conventional can also be added in above-mentioned coating, 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, e.g., and the CoatOSil series polyether modified organic silicon auxiliary agent of Mai Tu new high-tech material company limited.Those skilled in the art can according to requiring kind and the consumption of determining organic silicon additive, and the consumption that the present inventor recommends is 1 ~ 5wt%.
The preparation method of above-mentioned coating is the preparation method that this area is commonly used, and is mixed to get by nano aluminium oxide composite organic modified ultra-branching vibrin, pigment, filler, organosilicon auxiliary agent and high boiling solvent.
The present invention carries out organically-modified to nano aluminium oxide, and carries out modification in conjunction with organosilicon to Hyperbranched Polyester Resin, has high heat resistance energy and good hardness by the modified coating prepared.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
1) preparation of organic modified nano aluminum oxide
A) fill a prescription
Nano aluminium oxide: 20g
3-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 0.8g
Ethanol: 400g
Water: 100g
B) preparation technology
Nano aluminium oxide, second alcohol and water is added in the reactor that prolong, thermometer and agitator are housed, 3-(2 is added after high speed dispersion is even, 3-epoxy third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 8h, reaction is cooled to room temperature after stopping, product, through centrifugation and washing, obtains organic modified nano aluminum oxide 18.9g.
C) performance
The particle diameter of organic modified nano aluminum oxide adopts DSL to detect, and result is 20nm;
The oxirane value of organic modified nano aluminum oxide adopts hydrochloric acid-acetone method to measure, and result is 12.6mmol/g.
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
Add siloxanes and 4.5mmol hydrochloric acid successively by proportioning in the reactor that prolong, thermometer, dropping funnel and agitator are housed after, start to stir and heat up, homo(io)thermism is kept after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, after dropwising, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules and water that produce in reaction process, cool to room temperature, is 60wt% with dipropylene glycol methyl ether acetate adjustment solid content, obtains silicone oligomer 290g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 802; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 10.6wt%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 7.4wt%; R/Si=1.14; Ph/Me=1.04.
3) preparation of nano aluminium oxide composite organic modified ultra-branching vibrin
A) form:
Diprotic acid: m-phthalic acid 8.3g (0.05mol); Terephthalic acid 8.3g (0.05mol);
Trivalent alcohol: trimethylolethane 6g (0.05mol); TriMethylolPropane(TMP) 6.7g (0.05mol);
Organic modified nano aluminum oxide: step 1) the preparation 16.6g of organic modified nano aluminum oxide for preparing
Crosslinking catalyst: tetrabutyl titanate 0.332g
Dimethylbenzene: 0.996g
Organic solvent: 1-Methoxy-2-propyl acetate 33.2g
Silicone oligomer: step 2) solid content prepared is 60wt% silicone oligomer 41.5g
B) synthesis step:
By diprotic acid, trivalent alcohol, after being incubated 3h, being warming up to 225 DEG C and adding organic modified nano aluminum oxide after crosslinking catalyst and dimethylbenzene mix at being warming up to 170 DEG C, and insulation 1h, is then cooled to 85 DEG C, adds silicone oligomer; Be heated to 110 DEG C, heating 1.5h; Be cooled to 85 DEG C, add organic solvent and make solid content be 51wt%.
C) modified ultra-branching vibrin performance
The over-all properties of modified ultra-branching vibrin
1* resistance toheat: by test piece after 180 DEG C of baking 2h, put into the Ovenized electric furnace that potentiometer is checked, by 5 DEG C/min raised temperature, start timing with furnace temperature to requirement of experiment temperature, sample, after continuous high temperature, takes out, be chilled to room temperature (25 DEG C), observe coatingsurface situation with magnifying glass, as without be full of cracks, obscission, namely illustrate that coating heat resistance can be good.
4) coating
A) form
Modified ultra-branching vibrin: the modified ultra-branching vibrin 100g of above-mentioned preparation;
Filler: titanium dioxide 30g;
Organosilicon auxiliary agent: silicone oil
8g;
High boiling solvent: ethylene glycol ether acetate 15g.
B) preparation technology
Filler, modified ultra-branching vibrin, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
Embodiment 2:
1) preparation of organic modified nano aluminum oxide
A) fill a prescription
Nano aluminium oxide: 20g
3-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 1.6g
Ethanol: 1200g
Water: 300g
B) preparation technology
Nano aluminium oxide, second alcohol and water is added in the reactor that prolong, thermometer and agitator are housed, 3-(2 is added after high speed dispersion is even, 3-epoxy third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 16h, reaction is cooled to room temperature after stopping, product, through centrifugation and washing, obtains organic modified nano aluminum oxide 19.8g.
C) performance
The particle diameter of organic modified nano aluminum oxide adopts DSL to detect, and result is 100nm;
The oxirane value of organic modified nano aluminum oxide adopts hydrochloric acid-acetone method to measure, and result is 14.5mmol/g.
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
Add siloxanes and 4.5mmol hydrochloric acid successively by proportioning in the reactor that prolong, thermometer, dropping funnel and agitator are housed after, start to stir and heat up, homo(io)thermism is kept after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, after dropwising, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules and water that produce in reaction process, cool to room temperature, is 60wt% with dipropylene glycol methyl ether acetate adjustment solid content, obtains silicone oligomer 280g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 914; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 13wt%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 7.3wt%.
3) preparation of nano aluminium oxide composite organic modified ultra-branching vibrin
A) form:
Diprotic acid: m-phthalic acid 6.64g (0.04mol); Terephthalic acid 9.96g (0.06mol);
Trivalent alcohol: trimethylolethane 16.8g (0.14mol); TriMethylolPropane(TMP) 7.8g (0.06mol);
Organic modified nano aluminum oxide: step 1) the preparation 12.45g of organic modified nano aluminum oxide for preparing
Crosslinking catalyst: dioctyl zinc oxide 1.66g
Dimethylbenzene: 1g
Organic solvent: dipropylene acetic ester 24.9g
Silicone oligomer: step 2) solid content prepared is 80wt% silicone oligomer 20.75g
B) synthesis step:
By diprotic acid, trivalent alcohol, after being incubated 3h, being warming up to 225 DEG C and adding organic modified nano aluminum oxide after crosslinking catalyst and dimethylbenzene mix at being warming up to 210 DEG C, and insulation 1h, is then cooled to 85 DEG C, adds silicone oligomer; Be heated to 130 DEG C, heating 2h; Be cooled to 85 DEG C, add organic solvent and make solid content be 60wt%.
C) modified ultra-branching vibrin performance
The over-all properties of modified ultra-branching vibrin
4) coating
A) form
Modified ultra-branching vibrin: the modified ultra-branching vibrin 115g of above-mentioned preparation;
Filler: silicon carbide 24g;
Organosilicon auxiliary agent: silicone oil
High boiling solvent: ethylene glycol ether acetate 14g.
B) preparation technology
Filler, modified ultra-branching vibrin, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
Embodiment 3:
1) preparation of organic modified nano aluminum oxide
A) fill a prescription
Nano aluminium oxide: 30g
3-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 1.5g
Ethanol: 600g
Water: 150g
B) preparation technology
Nano aluminium oxide, second alcohol and water is added in the reactor that prolong, thermometer and agitator are housed, 3-(2 is added after high speed dispersion is even, 3-epoxy third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 24h, reaction is cooled to room temperature after stopping, product, through centrifugation and washing, obtains organic modified nano aluminum oxide 28.6g.
C) performance
The particle diameter of organic modified nano aluminum oxide adopts DSL to detect, and result is 20nm;
The oxirane value of organic modified nano aluminum oxide adopts hydrochloric acid-acetone method to measure, and result is 16.2mmol/g.
2) preparation of silicone oligomer
A) form
Monomethyl Trimethoxy silane: 42.0g (0.28mol)
Dimethyldimethoxysil,ne: 22.7g (0.17mol)
One phenyltrimethoxysila,e: 123.0g (0.58mol),
B) preparation technology
Add siloxanes and 4.5mmol hydrochloric acid successively by proportioning in the reactor that prolong, thermometer, dropping funnel and agitator are housed after, start to stir and heat up, homo(io)thermism is kept after being warmed up to 60 DEG C, under agitation drip 28g distilled water, after dropwising, again after isothermal reaction 4h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules and water that produce in reaction process, cool to room temperature, is 60wt% with dipropylene glycol methyl ether acetate adjustment solid content, obtains silicone oligomer 252g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 1986; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 12wt%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 6.7wt%.
3) preparation of nano aluminium oxide composite organic modified ultra-branching vibrin
A) form:
Diprotic acid: m-phthalic acid 16.6g (0.1mol);
Trivalent alcohol: trimethylolethane 16.8g (0.14mol);
Organic modified nano aluminum oxide: step 1) the preparation 8.3g of organic modified nano aluminum oxide for preparing
Crosslinking catalyst: tetrabutyl titanate 0.83g
Dimethylbenzene: 1.66g
Organic solvent: dipropylene acetic ester 29.05g
Silicone oligomer: step 2) solid content prepared is 60wt% silicone oligomer 20.75g
B) synthesis step:
By diprotic acid, trivalent alcohol, after being incubated 3h, being warming up to 225 DEG C and adding organic modified nano aluminum oxide after crosslinking catalyst and dimethylbenzene mix at being warming up to 200 DEG C, and insulation 1h, is then cooled to 85 DEG C, adds silicone oligomer; Be heated to 125 DEG C, heating 2h; Be cooled to 85 DEG C, add organic solvent and make solid content be 55wt%.
C) modified ultra-branching vibrin performance
The over-all properties of modified ultra-branching vibrin
4) coating
A) form
Modified ultra-branching vibrin: the modified ultra-branching vibrin 100g of above-mentioned preparation;
Filler: titanium dioxide 28g;
Organosilicon auxiliary agent: CoatOSil70014g; Silicone oil
High boiling solvent: butyl acetic ester 7g; N-BUTYL ACETATE 7g.
B) preparation technology
Filler, modified ultra-branching vibrin, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
Embodiment 4:
1) preparation of organic modified nano aluminum oxide
A) fill a prescription
Nano aluminium oxide: 30g
3-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2.1g
Ethanol: 600g
Water: 150g
B) preparation technology
Nano aluminium oxide, second alcohol and water is added in the reactor that prolong, thermometer and agitator are housed, 3-(2 is added after high speed dispersion is even, 3-epoxy third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 24h, reaction is cooled to room temperature after stopping, product, through centrifugation and washing, obtains organic modified nano aluminum oxide 29.4g.
C) performance
The particle diameter of organic modified nano aluminum oxide adopts DSL to detect, and result is 200nm;
The oxirane value of organic modified nano aluminum oxide adopts hydrochloric acid-acetone method to measure, and result is 18.6mmol/g.
2) preparation of nano aluminium oxide composite organic modified ultra-branching vibrin
A) form:
Diprotic acid: terephthalic acid 16.6g (0.1mol);
Trivalent alcohol: TriMethylolPropane(TMP) 23.4g (0.18mol);
Organic modified nano aluminum oxide: step 1) the preparation 16.6g of organic modified nano aluminum oxide for preparing
Crosslinking catalyst: tetrabutyl titanate 0.83g
Dimethylbenzene: 1.33g
Organic solvent: 1-Methoxy-2-propyl acetate 8.2g, butanols 12g, dipropylene glycol methyl ether acetate 3g, dipropylene acetic ester 5g
Silicone oligomer: the 307433.2g of Dow Corning Corporation
B) synthesis step:
By diprotic acid, trivalent alcohol, after being incubated 3h, being warming up to 225 DEG C and adding organic modified nano aluminum oxide after crosslinking catalyst and dimethylbenzene mix at being warming up to 190 DEG C, and insulation 1h, is then cooled to 85 DEG C, adds silicone oligomer; Be heated to 130 DEG C, heating 2.5h; Be cooled to 85 DEG C, add organic solvent and make solid content be 58wt%.
C) modified ultra-branching vibrin performance
The over-all properties of modified ultra-branching vibrin
3) coating
A) form
Modified ultra-branching vibrin: the modified ultra-branching vibrin 90g of above-mentioned preparation;
Filler: silicon carbide 10g; Titanium dioxide 10g;
Organosilicon auxiliary agent: CoatOSil70014g; Silicone oil
High boiling solvent: propionic acid-3-ether ethyl ester (EEP) 10g; Methyl isoamyl ketone 10g.
B) preparation technology
Filler, modified ultra-branching vibrin, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
Embodiment 5:
1) preparation of organic modified nano aluminum oxide
A) fill a prescription
Nano aluminium oxide: 30g
3-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 1.95g
Ethanol: 600g
Water: 150g
B) preparation technology
Nano aluminium oxide, second alcohol and water is added in the reactor that prolong, thermometer and agitator are housed, 3-(2 is added after high speed dispersion is even, 3-epoxy third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 24h, reaction is cooled to room temperature after stopping, product, through centrifugation and washing, obtains organic modified nano aluminum oxide 28.7g.
C) performance
The particle diameter of organic modified nano aluminum oxide adopts DSL to detect, and result is 120nm;
The oxirane value of organic modified nano aluminum oxide adopts hydrochloric acid-acetone method to measure, and result is 16.9mmol/g.
2) preparation of nano aluminium oxide composite organic modified ultra-branching vibrin
A) form:
Diprotic acid: m-phthalic acid 16.6g (0.1mol);
Trivalent alcohol: TriMethylolPropane(TMP) 26.8g (0.2mol);
Organic modified nano aluminum oxide: step 1) the preparation 15.21g of organic modified nano aluminum oxide for preparing
Crosslinking catalyst: tetrabutyl titanate 0.95g
Dimethylbenzene: 1.5g
Organic solvent: 1-Methoxy-2-propyl acetate 5.9g, butanols 13g, isopropylcarbinol 6g
Silicone oligomer: the Z-61086g of the 2337g of Dow Corning Corporation, the 2497g of Dow Corning Corporation, Dow Corning Corporation, the IC8367g of Wa Ke company, the KR2136g of company of SHIN-ETSU HANTOTAI
B) synthesis step:
By diprotic acid, trivalent alcohol, after being incubated 2.5h, being warming up to 225 DEG C and adding organic modified nano aluminum oxide after crosslinking catalyst and dimethylbenzene mix at being warming up to 175 DEG C, and insulation 1h, is then cooled to 85 DEG C, adds silicone oligomer; Be heated to 115 DEG C, heating 2.5h; Be cooled to 85 DEG C, add organic solvent and make solid content be 59wt%.
C) modified ultra-branching vibrin performance
The over-all properties of modified ultra-branching vibrin
3) coating
A) form
Modified ultra-branching vibrin: the modified ultra-branching vibrin 120g of above-mentioned preparation;
Filler: silicon carbide 11g; Titanium dioxide 11g;
Pigment: carbon black 10g;
Organosilicon auxiliary agent: CoatOSil35004g; CoatOSil76502g;
High boiling solvent: methyl isoamyl ketone (MIAK) 6g; Isobutyl isobutyrate 8g.
B) preparation technology
Pigment, filler, modified ultra-branching vibrin, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent transformation, all still belong to the protection domain of technical solution of the present invention.
Comparative example 1
1) preparation of organic-silicon-modified Hyperbranched Polyester Resin
A) form:
Trivalent alcohol: TriMethylolPropane(TMP) 18.76g (0.14mol); Trimethylolethane 7.2g (0.06mol);
Diprotic acid: m-phthalic acid 8.3g (0.05mol); Terephthalic acid 8.3g (0.05mol);
Epoxy resin: epoxy resin E-125g
Silicone oligomer: silicone oligomer 25.7g
Crosslinking catalyst: tetrabutyl titanate 0.13g
Organic solvent: dipropylene glycol methyl ether acetate 55g, butanols 8g
B) synthesis step:
By diprotic acid, trivalent alcohol and crosslinking catalyst evenly after be warming up to 190 DEG C at heat 3h after, be cooled to 90 DEG C, add epoxy resin and silicone oligomer; Be heated to 130 DEG C, heating 2.5h; Be cooled to 90 DEG C, add organic solvent and make solid content be 60wt%.
C) modified polyester resin performance
The over-all properties of modified polyester resin
2) coating
A) form
Modified polyester resin: step 1) the modified polyester resin 160g for preparing;
Filler: titanium dioxide 20g, silicon carbide 8g
Organosilicon auxiliary agent: silicone oil
1g.
High boiling solvent: ethylene glycol ether acetate (CAC): 10g.
B) preparation technology
Filler, modified polyester resin, high boiling solvent, auxiliary agent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
Comparative example 2:
1) preparation of organic-silicon-modified Hyperbranched Polyester Resin
A) form:
Trivalent alcohol: TriMethylolPropane(TMP) 18.76g (0.14mol);
Diprotic acid: m-phthalic acid 16.6g (0.1mol);
Epoxy resin: epoxy resin E-514g
Silicone oligomer: silicone oligomer 41g
Crosslinking catalyst: tetrabutyl titanate 0.3g
Organic solvent: dipropylene glycol methyl ether acetate 50g, dipropylene acetic ester 10g
B) synthesis step:
By diprotic acid, trivalent alcohol and crosslinking catalyst evenly after be warming up to 210 DEG C at heat 2h after, be cooled to 90 DEG C, add epoxy resin and silicone oligomer; Be heated to 135 DEG C, heating 3h; Be cooled to 90 DEG C, add organic solvent and make solid content be 50wt%.
C) modified polyester resin performance
The over-all properties of modified polyester resin
2) coating
A) form
Modified polyester resin: step 1) the modified polyester resin 100g for preparing;
Filler: titanium dioxide 10g, silicon carbide 30g
Organosilicon auxiliary agent: CoatOSil70014g; Silicone oil
6g;
High boiling solvent: butyl acetic ester 5g; N-BUTYL ACETATE 5g.
B) preparation technology
Filler, modified polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
Comparative example 3
1) preparation of organic-silicon-modified Hyperbranched Polyester Resin
A) form:
Trivalent alcohol: trimethylolethane 21.8g (0.18mol);
Diprotic acid: m-phthalic acid 16.6g (0.1mol);
Epoxy resin: epoxy resin E-44 3g
Silicone oligomer: the 307455.5g of Dow Corning Corporation
Dipropylene glycol methyl ether acetate: 33.3g
Connection catalyzer: tetrabutyl titanate 0.64g
Organic solvent: 1-Methoxy-2-propyl acetate 41.3g, butanols 8g, dipropylene glycol methyl ether acetate 8g, dipropylene acetic ester 10g
B) synthesis step:
By diprotic acid, trivalent alcohol and crosslinking catalyst evenly after be warming up to 220 DEG C at heat 1h after, be cooled to 90 DEG C, add epoxy resin and silicone oligomer; Be heated to 140 DEG C, heating 2h; Be cooled to 90 DEG C, add organic solvent and make solid content be 55wt%.
C) organic-silicon-modified Hyperbranched Polyester Resin performance
The over-all properties of organic-silicon-modified Hyperbranched Polyester Resin
2) coating
A) form
Modified polyester resin: step 1) the organic-silicon-modified Hyperbranched Polyester Resin 120g for preparing;
Filler: silicon carbide 10g; Titanium dioxide 10g;
Organosilicon auxiliary agent: CoatOSil35004g; Silicone oil
4g;
High boiling solvent: propionic acid-3-ether ethyl ester (EEP) 10g; Methyl isoamyl ketone 10g.
B) preparation technology
Filler, modified polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
The performance index of coating
Comparative example 4
1) preparation of organic-silicon-modified Hyperbranched Polyester Resin
A) form:
Trivalent alcohol: TriMethylolPropane(TMP) 16.08g (0.12mol);
Diprotic acid: terephthalic acid 16.6g (0.1mol); ;
Epoxy terminated silicone oligomer: the Z-610810g of the 23320g of Dow Corning Corporation, the 24910g of Dow Corning Corporation, Dow Corning Corporation, the IC8366.6g of Wa Ke company
Crosslinking catalyst: tetrabutyl titanate 0.24g
Organic solvent: 1-Methoxy-2-propyl acetate 76g, butanols 6.5g
B) synthesis step:
By diprotic acid, trivalent alcohol and crosslinking catalyst evenly after be warming up to 200 DEG C at heat 3.5h after, be cooled to 90 DEG C, add epoxy resin and silicone oligomer; Be heated to 120 DEG C, heating 3h; Be cooled to 90 DEG C, add organic solvent and make solid content be 50wt%.
C) modified polyester resin performance
The over-all properties of modified polyester resin
2) coating
A) form
Modified polyester resin: step 1) the modified polyester resin 140g for preparing;
Filler: silicon-dioxide 25g; Titanium dioxide 10g;
Pigment: carbon black 10g;
Organosilicon auxiliary agent: CoatOSil35004g; CoatOSil76502g;
High boiling solvent: methyl isoamyl ketone (MIAK) 2g; Isobutyl isobutyrate 4g.
B) preparation technology
Pigment, filler, organic-silicon-modified Hyperbranched Polyester Resin, organosilicon auxiliary agent, high boiling solvent are mixed, adds grinding machine for grinding to required particle diameter, to obtain final product.
C) performance
The performance index of coating
Resin in contrast coating adopts silicone intermediate to carry out modification to vibrin, and this resin has good resistance toheat, and its heat resisting temperature reaches 380 DEG C.But do not add organic modified nano-alumina preparing in vibrin process, cause the hardness of film low, only 4H.
The standby coating resistance toheat of resin-made of the present invention reaches 410 ~ 440 DEG C, and hardness reaches 6 ~ 7H.Its resistance toheat and hardness are better than contrast coating far away.
Claims (3)
1. a preparation method for nano aluminium oxide composite organic modified ultra-branching vibrin, is characterized in that carrying out as follows:
By nano aluminium oxide, ethanol, water and 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane mixes by weight 1:20 ~ 60:5 ~ 15:0.4 ~ 0.8, back flow reaction 8 ~ 24h in 55 DEG C of water-baths, reaction is down to room temperature after stopping, product, through centrifugation and washing, obtains organic modified nano aluminum oxide;
Be diprotic acid and the trivalent alcohol of 1:1 ~ 2 by mol ratio, and after the dimethylbenzene of weight to be the crosslinking catalyst of described diprotic acid 0.02 ~ 0.1 times and weight be diprotic acid 0.06 ~ 0.1 times mixes, be warming up to 170 ~ 210 DEG C, after insulation 1 ~ 3h, be warming up to 225 DEG C again, add the described organic modified nano aluminum oxide that weight is diprotic acid 0.5 ~ 1 times, insulation 1h, then, be cooled to 85 DEG C, add the silicone oligomer that organic solvent that weight is diprotic acid 1.5 ~ 2.0 times and weight are diprotic acid 1.0 ~ 1.5 times; Be warming up to 110 ~ 130 DEG C, heating 1.5 ~ 2.5h; Be cooled to 85 DEG C again, add organic solvent and make solid content be 51 ~ 60wt%, namely obtain nano aluminium oxide composite organic modified ultra-branching vibrin; Wherein:
Described diprotic acid is one in m-phthalic acid and terephthalic acid or mixture;
Described trivalent alcohol is one in trimethylolethane and TriMethylolPropane(TMP) or mixture;
Described crosslinking catalyst is one in tetrabutyl titanate, tetrabutyl titanate or two kinds;
Described organic solvent is one or more in dipropylene glycol methyl ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, butanols, isopropylcarbinol, 1-Methoxy-2-propyl acetate and dipropylene acetic ester;
The weight-average molecular weight of described silicone oligomer is 700 ~ 2200, and containing the methoxy or ethoxy of 3 ~ 16wt% and the hydroxyl of 5 ~ 22wt%.
2. the preparation method of nano aluminium oxide composite organic modified ultra-branching vibrin according to claim 1, is characterized in that, the particle diameter of described organic modified nano aluminum oxide is 20 ~ 200nm, and epoxy group content is 10 ~ 20mmol/g.
3. a coating, this coating contains nano aluminium oxide composite organic modified ultra-branching vibrin that 55 ~ 75wt% prepared by method described in claim 1 or 2,12.5 ~ 22.5wt% is high temperature resistant filler and 7.5 ~ 22.5wt% high boiling solvent; Wherein:
Described high temperature resistant filler is one or more in titanium dioxide, silicon-dioxide and silicon carbide;
Described high boiling solvent refers to one in ethylene glycol ether acetate, butyl acetic ester, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and methyl isoamyl ketone or two or more.
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| CN114409883B (en) * | 2021-12-22 | 2023-11-14 | 长兴化学工业(中国)有限公司 | Aluminate glue modified polyester, preparation method thereof, paint and resin membrane |
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| CN102504271A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing hyperbranched polyester modified organic silicon resin |
| 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 |
| CN102977363A (en) * | 2012-11-27 | 2013-03-20 | 南方医科大学 | Preparation method of modified amino-terminated hyper-branched polyamide resin and coating comprising resin |
| CN103113566A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504271A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing hyperbranched polyester modified organic silicon resin |
| 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 |
| CN102977363A (en) * | 2012-11-27 | 2013-03-20 | 南方医科大学 | Preparation method of modified amino-terminated hyper-branched polyamide resin and coating comprising resin |
| CN103113566A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof |
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