CN104558571B - A kind of preparation method of nano zine oxide composite organic modified ultra-branching mylar and containing the coating of this resin - Google Patents
A kind of preparation method of nano zine oxide composite organic modified ultra-branching mylar and containing the coating of this resin Download PDFInfo
- Publication number
- CN104558571B CN104558571B CN201410766131.0A CN201410766131A CN104558571B CN 104558571 B CN104558571 B CN 104558571B CN 201410766131 A CN201410766131 A CN 201410766131A CN 104558571 B CN104558571 B CN 104558571B
- Authority
- CN
- China
- Prior art keywords
- mylar
- branching
- organic modified
- zinc oxide
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of nano zine oxide composite organic modified ultra-branching mylar and the coating containing this resin, method is as follows: first use nano zine oxide, ethanol, water and 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane to prepare organic modified nano zinc oxide; By dihydroxylic alcohols, ternary acid, is warming up to after crosslinking catalyst and dimethylbenzene mix after 170 ~ 210 DEG C of insulation 1 ~ 3h, is warming up to 225 DEG C and adds organic modified nano zinc oxide insulation 1h, is then cooled to 85 DEG C, adds silicone oligomer; Be heated to 110 ~ 130 DEG C, insulation 1.5 ~ 2.5h; Be cooled to 85 DEG C, adding organic solvent to make solid content is 51 ~ 60wt%. The method is used organic modified nano zinc oxide, and binary acid and trihydroxylic alcohol one react and prepare modified ultra-branching polyester, improves the hardness of polyester; Silicone oligomer and polyester are carried out to cross-linking reaction, improve the heat resistance of polyester. Mylar prepared by this 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, relate in particular to the macromolecular compound that esterification obtains, toolBody relates to Hyperbranched Polyester Resin.
Background technology
Mylar is the general name of the macromolecular compound that formed by dihydroxylic alcohols or binary acid or polyalcohol and polyacid polycondensation, itsGood manufacturability, the glue-line hardness after solidifying is large, the transparency is good, brightness is high, can room temperature pressurization rapid curing, its heat resistance,Mar proof, chemical proofing and mechanical property are better. Be mainly used in, gluing fiberglass, rigid plastics, concrete, electricityGas tank envelope etc., mylar is also used widely in coating industry, but it also has obvious shortcoming, such as: polyesterMolecular resin amount is large, poorly soluble, and 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 end group active groups, has Gao RongXie Xing, low viscosity and higher chemical reactivity, made up its shortcoming to a certain extent. The Granted publication CN of our company102504293B, it is ester modified organic that the Chinese invention patent in August 14 2013 Granted publication day discloses a kind of hyperbranched polyThe preparation method of silicones and the coating that contains this resin, the method is: by end carboxyl super branched 40-60wt% polyester,The organic siliconresin of 1-10wt%3-glycidyl ether oxygen propyl trimethoxy silicane, 30-50wt% and end carboxyl super branched polyester weightThe crosslinking catalyst of amount 1-10% heats after 1-3 hour at 110-130 DEG C, is warming up to 150-180 DEG C, heating 1-3 hour;Finally be down to room temperature, adding organic solvent to adjust solid content is 60-70wt%. The method is by end carboxyl super branched polyester and organosiliconThe advantages of resin is got up, and obtains excellent heat resistance, good metal adhesion, low-surface-energy, excellent water boiling resistancePerformance and acid resistance. But hyperbranched polyester modified organic silicon resin prepared by this invention is still having and is changing aspect heat resistance and hardnessThe leeway of entering.
Summary of the invention
In order to make Hyperbranched Polyester Resin have better heat resistance and better hardness, the invention provides a kind of nanometer oxygenThe preparation method who changes zinc composite organic modified ultra-branching mylar, the present invention also provides one to contain by the inventive method systemThe coating of standby nano zine oxide composite organic modified ultra-branching mylar.
Concrete technical scheme of the present invention is: a kind of preparation side of nano zine oxide composite organic modified ultra-branching mylarMethod, carry out as follows:
By nano zine oxide, ethanol, water and 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 1:20～60:5～15:0.4～0.8 by weightMix, back flow reaction 8～24h in 55 DEG C of water-baths, is down to room temperature after reaction stops, product process centrifugation and washing,Obtain organic modified nano zinc oxide;
The dihydroxylic alcohols that is 1:1～2 by mol ratio and ternary acid, and weight is the crosslinking catalyst of 0.02～0.1 times of described dihydroxylic alcohols and weighsAmount is, after the dimethylbenzene of 0.06～0.1 times of dihydroxylic alcohols mixes, to be warming up to 170～210 DEG C, after insulation 1～3h, then is warming up to225 DEG C, adding weight is the described organic modified nano zinc oxide of 0.5～1 times of dihydroxylic alcohols, and insulation 1h, then, is cooled to 85 DEG C,Adding weight is that organic solvent and the weight of 1.5～2.0 times of dihydroxylic alcohols is the silicone oligomer of 1.0～1.5 times of dihydroxylic alcohols; Be warming up to110～130 DEG C, heating 1.5～2.5h; Be cooled to 85 DEG C, adding organic solvent to make solid content is 51～60wt%, is received againRice zinc oxide composite organic modified ultra-branching mylar.
Wherein: described dihydroxylic alcohols is the one in neopentyl glycol, 2-methyl 1,3-PD and Isosorbide-5-Nitrae-cyclohexanediol or mixesCompound.
Described ternary acid is one or the mixture in 1,2,4-benzenetricarboxylic acid and 1,3,5-benzenetricarboxylic acid.
Described crosslinking catalyst is in butyl titanate, tetrabutyl titanate, dioctyl zinc oxide and diisooctyl zinc oxideA kind of or two or more.
Described organic solvent be dipropylene glycol methyl ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, butanols, isobutanol,One or more in 1-Methoxy-2-propyl acetate and DPG monobutyl ether acetate.
The weight average molecular weight of described silicone oligomer is 700～2200, and the methoxy or ethoxy that contains 3～16wt% andThe hydroxyl of 5～22wt%.
As one of selecting, described silicone oligomer can be by methltriethoxysilone, dimethyldiethoxysilaneThe condensation reaction that is hydrolyzed obtains with siloxanes such as phenyl triethoxies, also can be by monomethyl trimethoxy silane, dimethylThe condensation reaction that is hydrolyzed of the siloxanes such as dimethoxy silane and a phenyl trimethoxy obtains. Wherein, described siloxanes carries outHydrolysis-condensation reaction is the condensation reaction that is hydrolyzed of the conventional siloxanes in this area, and its technique and reaction condition are art technology peopleThe routine techniques that member should grasp.
As one of selecting, the IC836 that described silicone oligomer also can 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, the organic siliconresin KR150 of SHIN-ETSU HANTOTAI, letterThe more KR211 of company, the KR212 of company of SHIN-ETSU HANTOTAI, the KR214 of company of SHIN-ETSU HANTOTAI, the KR216 of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAIOne in KR213 or two or more.
As preferably, the particle diameter of described organic modified nano zinc oxide is 20～200nm, and epoxy group content is10～20mmol/g。
Nano zine oxide composite organic modified ultra-branching mylar prepared by method of the present invention, has following excellentPoint:
Dihydroxylic alcohols, ternary acid and organic modified nano zinc oxide are reacted to the nano zinc oxide modified Hyperbranched Polyester Resin of preparation, itsMiddle dihydroxylic alcohols and ternary acid carry out esterification hyper-branched polyester are grafted to organic modified nano zinc oxide, nano zine oxide embeddingEnter in hyper-branched polyester, improve heat resistance and the hardness of polyester; On the other hand, by nano zinc oxide modified hyper-branched polyester treeFat and silicone oligomer carry out cross-linking reaction and prepare nano zine oxide composite organic modified ultra-branching mylar, further carryThe heat resistance of superpolyester resin and hardness.
A kind of coating, this coating contains the nano zine oxide composite organic modification over-expense that 55～75wt% is prepared as stated aboveChange mylar, 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, silica and carborundum; DescribedHigh boiling solvent refers to ethylene glycol ether acetate, diethylene glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether secondOne in ester and methyl isoamyl ketone or two or more.
In above-mentioned coating, also can add the conventional high-temperature resisting pigment in this area, described high-temperature resisting pigment can be carbon black, iron oxide red etc.Inorganic high-temperature resistant pigment can be also the organic high temperature-resistant pigment such as phthalocyanine blue.
In above-mentioned coating, can also add the conventional organosilicon auxiliary agent in this area, as: play levelling, froth breaking, pigment wetting,The effects such as viscosity adjusting. Above-mentioned organosilicon auxiliary agent can also be silicone oil, organic silicon modified by polyether auxiliary agent, as, step figure new high-tech materialThe CoatOSil series organic silicon modified by polyether auxiliary agent of Co., Ltd. Those skilled in the art can be according to requiring to determine organosiliconThe kind of auxiliary agent and consumption, the consumption that the inventor recommends is 1～5wt%.
The preparation method of above-mentioned coating is the conventional preparation method in this area, super by the modification of nano zine oxide composite organicBranched polyester resin, pigment, filler, organosilicon auxiliary agent and high boiling solvent are mixed to get.
Of the present inventionly prepare by nano zine oxide composite organic modified ultra-branching mylar the coating obtaining and there is heightHeat resistance and good hardness.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
1) preparation of organic modified nano zinc oxide
A) formula
Nano zine oxide: 20g
3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane: 0.8g
Ethanol: 400g
Water: 100g
B) preparation technology
In the reactor that condenser pipe, thermometer and agitator are housed, add nano zine oxide, second alcohol and water, after high speed dispersion is even, addEnter 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 8h, after reaction stops, being cooled to room temperature,Product, through centrifugation and washing, obtains organic modified nano zinc oxide 18.6g.
C) performance
The particle diameter of organic modified nano zinc oxide adopts DSL to detect, and result is 50nm;
The epoxide number of organic modified nano zinc oxide adopts hydrochloric acid-acetone method to measure, and result is 11.4mmol/g.
2) preparation of silicone oligomer
A) composition
Monomethyl trimethoxy silane: 42.0g (0.28mol)
Dimethyldimethoxysil,ne: 18.7g (0.14mol)
One phenyltrimethoxysila,e: 123.0g (0.58mol),
B) preparation technology
In the reactor that condenser pipe, thermometer, dropping funel and agitator are housed, add successively siloxanes and 4.5mmol salt by proportioningAfter acid, start to stir and heat up, keep temperature constant after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, dripBi Hou, then after isothermal reaction 3h, start decompression distillation, pressure is controlled at 0.06MPa, boils off little point that in course of reaction, producesSon and water, cool to room temperature, adjusting solid content with dipropylene glycol methyl ether acetate is 60wt%, obtains silicone oligomer 287g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 802; The hydroxyl of silicone oligomer containsAmount adopts acetic anhydride method to measure, and result is 10.6wt%; The methoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure,Result is 7.6wt%; R/Si=1.16; Ph/Me=1.02.
3) preparation of nano zine oxide composite organic modified ultra-branching mylar
A) composition:
Dihydroxylic alcohols: neopentyl glycol 5.2g (0.05mol); 2-methyl 1,3-PD 4.5g (0.05mol);
Ternary acid: 1,2,4-benzenetricarboxylic acid 10.5g (0.05mol); 1,2,4-benzenetricarboxylic acid 10.5g (0.05mol);
Organic modified nano zinc oxide: step 1) the preparation 9.7g of the organic modified nano zinc oxide prepared
Crosslinking catalyst: butyl titanate 0.194g
Dimethylbenzene: 0.582g
Organic solvent: 1-Methoxy-2-propyl acetate 19.4g
Silicone oligomer: step 2) solid content prepared is 60wt% silicone oligomer 24.25g
B) synthesis step:
By dihydroxylic alcohols, ternary acid, is warming up at 170 DEG C and is incubated after 3h after crosslinking catalyst and dimethylbenzene mix, and is warming up to 225 DEG CAdd organic modified nano zinc oxide, 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, adding organic solvent to make solid content is 51wt%.
C) modified ultra-branching mylar performance
The combination property of modified ultra-branching mylar
1* heat resistance: test piece, after 180 DEG C of baking 2h, is put into the Ovenized electric furnace that potential difference meter is checked, by 5 DEG C/minRising temperature, starts timing with furnace temperature to requirement of experiment temperature, and sample, after continuous high temperature, takes out, and is chilled to room temperature (25 DEG C),Observe coating surface situation with magnifying glass, as without be full of cracks, obscission, illustrate that coating heat resistance can be good.
4) coating
A) composition
Modified ultra-branching mylar: the modified ultra-branching mylar 100g of above-mentioned preparation;
Filler: titanium dioxide 28g;
Organosilicon auxiliary agent: silicone oil/350cst8g；
High boiling solvent: ethylene glycol ether acetate 15g.
B) preparation technology
Filler, modified ultra-branching mylar, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to instituteNeed particle diameter, to obtain final product.
C) performance
The performance indications of coating
Embodiment 2:
1) preparation of organic modified nano zinc oxide
A) formula
Nano zine oxide: 20g
3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane: 1.6g
Ethanol: 1200g
Water: 300g
B) preparation technology
In the reactor that condenser pipe, thermometer and agitator are housed, add nano zine oxide, second alcohol and water, after high speed dispersion is even, addEnter 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 16h, after reaction stops, being cooled to room temperature,Product, through centrifugation and washing, obtains organic modified nano zinc oxide 18.9g.
C) performance
The particle diameter of organic modified nano zinc oxide adopts DSL to detect, and result is 90nm;
The epoxide number of organic modified nano zinc oxide adopts hydrochloric acid-acetone method to measure, and result is 18.3mmol/g.
2) preparation of silicone oligomer
A) composition
Monomethyl trimethoxy silane: 42.0g (0.28mol)
Dimethyldimethoxysil,ne: 18.7g (0.14mol)
One phenyltrimethoxysila,e: 123.0g (0.58mol),
B) preparation technology
In the reactor that condenser pipe, thermometer, dropping funel and agitator are housed, add successively siloxanes and 4.5mmol salt by proportioningAfter acid, start to stir and heat up, keep temperature constant after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, dripBi Hou, then after isothermal reaction 3h, start decompression distillation, pressure is controlled at 0.06MPa, boils off little point that in course of reaction, producesSon and water, cool to room temperature, adjusting solid content with dipropylene glycol methyl ether acetate is 60wt%, obtains silicone oligomer 280g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 919; The hydroxyl of silicone oligomer containsAmount adopts acetic anhydride method to measure, and result is 13wt%; The methoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure,Result is 7.3wt%.
3) preparation of nano zine oxide composite organic modified ultra-branching mylar
A) composition:
Dihydroxylic alcohols: Isosorbide-5-Nitrae-cyclohexanediol 4.64g (0.04mol); 2-methyl 1,3-PD 5.4g (0.06mol);
Ternary acid: 1,2,4-benzenetricarboxylic acid 29.4g (0.14mol); 1,3,5-benzenetricarboxylic acid 12.6g (0.06mol);
Organic modified nano zinc oxide: step 1) the preparation 7.53g of the organic modified nano zinc oxide prepared
Crosslinking catalyst: dioctyl zinc oxide 1.004g
Dimethylbenzene: 0.61g
Organic solvent: DPG monobutyl ether acetate 15.06g
Silicone oligomer: step 2) solid content prepared is 80wt% silicone oligomer 18.83g
B) synthesis step:
By dihydroxylic alcohols, ternary acid, is warming up at 210 DEG C and is incubated after 3h after crosslinking catalyst and dimethylbenzene mix, and is warming up to 225 DEG CAdd organic modified nano zinc oxide, 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, adding organic solvent to make solid content is 60wt%.
C) modified ultra-branching mylar performance
The combination property of modified ultra-branching mylar
4) coating
A) composition
Modified ultra-branching mylar: the modified ultra-branching mylar 115g of above-mentioned preparation;
Filler: carborundum 25g;
Organosilicon auxiliary agent: silicone oil/350cst1g；
High boiling solvent: ethylene glycol ether acetate 15g.
B) preparation technology
Filler, modified ultra-branching mylar, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to instituteNeed particle diameter, to obtain final product.
C) performance
The performance indications of coating
Embodiment 3:
1) preparation of organic modified nano zinc oxide
A) formula
Nano zine oxide: 30g
3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane: 1.5g
Ethanol: 600g
Water: 150g
B) preparation technology
In the reactor that condenser pipe, thermometer and agitator are housed, add nano zine oxide, second alcohol and water, after high speed dispersion is even, addEnter 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 24h, after reaction stops, being cooled to room temperature,Product, through centrifugation and washing, obtains organic modified nano zinc oxide 28.8g.
C) performance
The particle diameter of organic modified nano zinc oxide adopts DSL to detect, and result is 30nm;
The epoxide number of organic modified nano zinc oxide adopts hydrochloric acid-acetone method to measure, and result is 17.3mmol/g.
2) preparation of silicone oligomer
A) composition
Monomethyl trimethoxy silane: 42.0g (0.28mol)
Dimethyldimethoxysil,ne: 22.7g (0.17mol)
One phenyltrimethoxysila,e: 123.0g (0.58mol),
B) preparation technology
In the reactor that condenser pipe, thermometer, dropping funel and agitator are housed, add successively siloxanes and 4.5mmol salt by proportioningAfter acid, start to stir and heat up, keep temperature constant after being warmed up to 60 DEG C, under agitation drip 28g distilled water, dropwiseAfter, then after isothermal reaction 4h, starting decompression distillation, pressure is controlled at 0.06MPa, boils off the little molecule producing in course of reactionAnd water, cool to room temperature, adjusting solid content with dipropylene glycol methyl ether acetate is 60wt%, obtains silicone oligomer 254g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 1989; The hydroxyl of silicone oligomer containsAmount adopts acetic anhydride method to measure, and result is 13wt%; The methoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure,Result is 6.9wt%.
3) preparation of nano zine oxide composite organic modified ultra-branching mylar
A) composition:
Dihydroxylic alcohols: neopentyl glycol 10.4g (0.1mol);
Ternary acid: 1,2,4-benzenetricarboxylic acid 29.4g (0.14mol);
Organic modified nano zinc oxide: step 1) the preparation 10.4g of the organic modified nano zinc oxide prepared
Crosslinking catalyst: butyl titanate 0.52g
Dimethylbenzene: 0.73g
Organic solvent: DPG monobutyl ether acetate 20.8g
Silicone oligomer: step 2) solid content prepared is 60wt% silicone oligomer 22.17g
B) synthesis step:
By dihydroxylic alcohols, ternary acid, is warming up at 200 DEG C and is incubated after 3h after crosslinking catalyst and dimethylbenzene mix, and is warming up to 225 DEG CAdd organic modified nano zinc oxide, 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, adding organic solvent to make solid content is 55wt%.
C) modified ultra-branching mylar performance
The combination property of modified ultra-branching mylar
4) coating
A) composition
Modified ultra-branching mylar: the modified ultra-branching mylar 100g of above-mentioned preparation;
Filler: titanium dioxide 28g;
Organosilicon auxiliary agent: CoatOSil70014g; Silicone oil/350cst6g；
High boiling solvent: diethylene glycol monobutyl ether acetate 7g; Butyl acetate 7g.
B) preparation technology
Filler, modified ultra-branching mylar, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to instituteNeed particle diameter, to obtain final product.
C) performance
The performance indications of coating
Embodiment 4:
1) preparation of organic modified nano zinc oxide
A) formula
Nano zine oxide: 30g
3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane: 2.1g
Ethanol: 600g
Water: 150g
B) preparation technology
In the reactor that condenser pipe, thermometer and agitator are housed, add nano zine oxide, second alcohol and water, after high speed dispersion is even, addEnter 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 24h, after reaction stops, being cooled to room temperature,Product, through centrifugation and washing, obtains organic modified nano zinc oxide 29.1g.
C) performance
The particle diameter of organic modified nano zinc oxide adopts DSL to detect, and result is 200nm;
The epoxide number of organic modified nano zinc oxide adopts hydrochloric acid-acetone method to measure, and result is 18.1mmol/g.
2) preparation of nano zine oxide composite organic modified ultra-branching mylar
A) composition:
Dihydroxylic alcohols: neopentyl glycol 10.4g (0.1mol);
Ternary acid: 1,3,5-benzenetricarboxylic acid 37.8g (0.18mol);
Organic modified nano zinc oxide: step 1) the preparation 5.2g of the organic modified nano zinc oxide prepared
Crosslinking catalyst: butyl titanate 0.208g
Dimethylbenzene: 0.83g
Organic solvent: 1-Methoxy-2-propyl acetate 5.6g, butanols 2g, dipropylene glycol methyl ether acetate 3g, DPG butyl ether acetic acidEster 5g
Silicone oligomer: the 307414.85g of Dow Corning Corporation
B) synthesis step:
By dihydroxylic alcohols, ternary acid, is warming up at 190 DEG C and is incubated after 3h after crosslinking catalyst and dimethylbenzene mix, and is warming up to 225 DEG CAdd organic modified nano zinc oxide, 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, adding organic solvent to make solid content is 58wt%.
C) modified ultra-branching mylar performance
The combination property of modified ultra-branching mylar
3) coating
A) composition
Modified ultra-branching mylar: the modified ultra-branching mylar 90g of above-mentioned preparation;
Filler: carborundum 10g; Titanium dioxide 10g;
Organosilicon auxiliary agent: CoatOSil70014g; Silicone oil/350cst4g；
High boiling solvent: propionic acid-3-ether ethyl ester (EEP) 10g; Methyl isoamyl ketone 10g.
B) preparation technology
Filler, modified ultra-branching mylar, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to instituteNeed particle diameter, to obtain final product.
C) performance
The performance indications of coating
Embodiment 5:
1) preparation of organic modified nano zinc oxide
A) formula
Nano zine oxide: 30g
3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane: 1.95g
Ethanol: 600g
Water: 150g
B) preparation technology
In the reactor that condenser pipe, thermometer and agitator are housed, add nano zine oxide, second alcohol and water, after high speed dispersion is even, addEnter 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, at 55 DEG C of water-bath back flow reaction 24h, after reaction stops, being cooled to room temperature,Product, through centrifugation and washing, obtains organic modified nano zinc oxide 28.5g.
C) performance
The particle diameter of organic modified nano zinc oxide adopts DSL to detect, and result is 130nm;
The epoxide number of organic modified nano zinc oxide adopts hydrochloric acid-acetone method to measure, and result is 12.9mmol/g.
2) preparation of nano zine oxide composite organic modified ultra-branching mylar
A) composition:
Dihydroxylic alcohols: Isosorbide-5-Nitrae-cyclohexanediol 11.6g (0.1mol);
Ternary acid: 1,2,4-benzenetricarboxylic acid 42g (0.2mol);
Organic modified nano zinc oxide: step 1) the preparation 8.7g of the organic modified nano zinc oxide prepared
Crosslinking catalyst: butyl titanate 0.95g
Dimethylbenzene: 1.16g
Organic solvent: 1-Methoxy-2-propyl acetate 9g, butanols 2.3g, isobutanol 9g
Silicone oligomer: the Z-61085g of the 2335g of Dow Corning Corporation, the 2495g of Dow Corning Corporation, Dow Corning Corporation, Wa KeThe IC8365g of company, the KR2134g of company of SHIN-ETSU HANTOTAI
B) synthesis step:
By dihydroxylic alcohols, ternary acid, is warming up at 175 DEG C and is incubated after 2.5h after crosslinking catalyst and dimethylbenzene mix, and is warming up to 225 DEG CAdd organic modified nano zinc oxide, 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, adding organic solvent to make solid content is 59wt%.
C) modified ultra-branching mylar performance
The combination property of modified ultra-branching mylar
3) coating
A) composition
Modified ultra-branching mylar: the modified ultra-branching mylar 120g of above-mentioned preparation;
Filler: carborundum 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 mylar, organosilicon auxiliary agent, high boiling solvent are mixed, add in grinder and grindBe ground to required particle diameter, obtain final product.
C) performance
The performance indications of coating
The above, be only preferred embodiment of the present invention, not the present invention imposed any restrictions, every according to the technology of the present invention essenceAny simple modification, change and equivalent transformation that above embodiment is done, all still belong to the protection model of technical solution of the present inventionEnclose.
Comparative example 1
1) preparation of organic-silicon-modified Hyperbranched Polyester Resin
A) composition:
Trihydroxylic alcohol: trimethylolpropane 18.76g (0.14mol); Trimethylolethane 7.2g (0.06mol);
Binary acid: M-phthalic acid 8.3g (0.05mol); Terephthalic acid (TPA) 8.3g (0.05mol);
Epoxy resin: epoxy resin E-125g
Silicone oligomer: silicone oligomer 25.7g
Crosslinking catalyst: butyl titanate 0.13g
Organic solvent: dipropylene glycol methyl ether acetate 55g, butanols 8g
B) synthesis step:
By binary acid, after trihydroxylic alcohol and crosslinking catalyst are even, are warming up at 190 DEG C and heat after 3h, be cooled to 90 DEG C, add epoxy treeFat and silicone oligomer; Be heated to 130 DEG C, heating 2.5h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 60wt%.
C) modified polyester resin performance
The combination property of modified polyester resin
2) coating
A) composition
Modified polyester resin: step 1) the modified polyester resin 160g for preparing;
Filler: titanium dioxide 20g, carborundum 8g
Organosilicon auxiliary agent: silicone oil/350cst1g。
High boiling solvent: ethylene glycol ether acetate (CAC): 10g.
B) preparation technology
Filler, modified polyester resin, high boiling solvent, auxiliary agent are mixed, add grinding machine for grinding to arrive required particle diameter,.
C) performance
The performance indications of coating
Comparative example 2:
1) preparation of organic-silicon-modified Hyperbranched Polyester Resin
A) composition:
Trihydroxylic alcohol: trimethylolpropane 18.76g (0.14mol);
Binary acid: M-phthalic acid 16.6g (0.1mol);
Epoxy resin: epoxy resin E-514g
Silicone oligomer: silicone oligomer 41g
Crosslinking catalyst: butyl titanate 0.3g
Organic solvent: dipropylene glycol methyl ether acetate 50g, DPG monobutyl ether acetate 10g
B) synthesis step:
By binary acid, after trihydroxylic alcohol and crosslinking catalyst are even, are warming up at 210 DEG C and heat after 2h, be cooled to 90 DEG C, add epoxy treeFat and silicone oligomer; Be heated to 135 DEG C, heating 3h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) modified polyester resin performance
The combination property of modified polyester resin
2) coating
A) composition
Modified polyester resin: step 1) the modified polyester resin 100g for preparing;
Filler: titanium dioxide 10g, carborundum 30g
Organosilicon auxiliary agent: CoatOSil70014g; Silicone oil/350cst6g；
High boiling solvent: diethylene glycol monobutyl ether acetate 5g; Butyl acetate 5g.
B) preparation technology
Filler, modified polyester resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required grainFootpath, to obtain final product.
C) performance
The performance indications of coating
Comparative example 3
1) preparation of organic-silicon-modified Hyperbranched Polyester Resin
A) composition:
Trihydroxylic alcohol: trimethylolethane 21.8g (0.18mol);
Binary 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 catalyst: butyl titanate 0.64g
Organic solvent: 1-Methoxy-2-propyl acetate 41.3g, butanols 8g, dipropylene glycol methyl ether acetate 8g, DPG butyl ether acetic acidEster 10g
B) synthesis step:
By binary acid, after trihydroxylic alcohol and crosslinking catalyst are even, are warming up at 220 DEG C and heat after 1h, be cooled to 90 DEG C, add epoxy treeFat and silicone oligomer; Be heated to 140 DEG C, heating 2h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 55wt%.
C) organic-silicon-modified Hyperbranched Polyester Resin performance
The combination property of organic-silicon-modified Hyperbranched Polyester Resin
2) coating
A) composition
Modified polyester resin: step 1) the organic-silicon-modified Hyperbranched Polyester Resin 120g for preparing;
Filler: carborundum 10g; Titanium dioxide 10g;
Organosilicon auxiliary agent: CoatOSil35004g; Silicone oil/350cst4g；
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, add grinding machine for grinding to arrive required grainFootpath, to obtain final product.
C) performance
The performance indications of coating
The performance indications of coating
Comparative example 4
1) preparation of organic-silicon-modified Hyperbranched Polyester Resin
A) composition:
Trihydroxylic alcohol: trimethylolpropane 16.08g (0.12mol);
Binary acid: terephthalic acid (TPA) 16.6g (0.1mol); ;
Epoxy terminated silicone oligomer: the Z-6108 of the 23320g of Dow Corning Corporation, the 24910g of Dow Corning Corporation, Dow Corning Corporation10g, the IC8366.6g of Wa Ke company
Crosslinking catalyst: butyl titanate 0.24g
Organic solvent: 1-Methoxy-2-propyl acetate 76g, butanols 6.5g
B) synthesis step:
By binary acid, after trihydroxylic alcohol and crosslinking catalyst are even, are warming up at 200 DEG C and heat after 3.5h, be cooled to 90 DEG C, add epoxyResin and silicone oligomer; Be heated to 120 DEG C, heating 3h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) modified polyester resin performance
The combination property of modified polyester resin
2) coating
A) composition
Modified polyester resin: step 1) the modified polyester resin 140g for preparing;
Filler: silica 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, add grindingIn machine, be ground to required particle diameter, obtain final product.
C) performance
The performance indications of coating
Resin in contrast coating is to adopt silicone intermediate to carry out modification to mylar, and this resin has good heat resistance,Its heat resisting temperature reaches 380 DEG C. But do not add organic modified nano zinc oxide preparing in mylar process, cause filmHardness low, only 4H.
The standby coating heat resistance of resin of the present invention reaches 410～440 DEG C, and hardness reaches 6～7H. Its heat resistanceBe better than contrast coating far away with hardness.
Claims (3)
1. a preparation method for nano zine oxide composite organic modified ultra-branching mylar, is characterized in that carrying out as follows:
By nano zine oxide, ethanol, water and 3-(2,3-epoxy the 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, after stopping, reaction is down to room temperature, product, through centrifugation and washing, obtains organic modified nano zinc oxide;
The dihydroxylic alcohols that is 1:1 ~ 2 by mol ratio and ternary acid, and weight is that the crosslinking catalyst of 0.02 ~ 0.1 times of described dihydroxylic alcohols and weight are after the dimethylbenzene of 0.06 ~ 0.1 times of dihydroxylic alcohols mixes, be warming up to 170 ~ 210 DEG C, after insulation 1 ~ 3h, be warming up to again 225 DEG C, adding weight is the described organic modified nano zinc oxide of 0.5 ~ 1 times of dihydroxylic alcohols, insulation 1h, then, be cooled to 85 DEG C, adding weight is that organic solvent and the weight of 1.5 ~ 2.0 times of dihydroxylic alcohols is the silicone oligomer of 1.0 ~ 1.5 times of dihydroxylic alcohols; Be warming up to 110 ~ 130 DEG C, heating 1.5 ~ 2.5h; Be cooled to 85 DEG C, adding organic solvent to make solid content is 51 ~ 60wt%, obtains nano zine oxide composite organic modified ultra-branching mylar again; Wherein:
Described dihydroxylic alcohols is one or the mixture in neopentyl glycol, 2-methyl 1,3-PD and Isosorbide-5-Nitrae-cyclohexanediol;
Described ternary acid is one or the mixture in 1,2,4-benzenetricarboxylic acid and 1,3,5-benzenetricarboxylic acid;
Described crosslinking catalyst is a kind of in butyl 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, isobutanol, 1-Methoxy-2-propyl acetate and DPG monobutyl ether acetate;
The weight average molecular weight of described silicone oligomer is 700 ~ 2200, and the hydroxyl of the methoxy or ethoxy that contains 3 ~ 16wt% and 5 ~ 22wt%.
2. the preparation method of nano zine oxide composite organic modified ultra-branching mylar claimed in claim 1, is characterized in that, the particle diameter of described organic modified nano zinc oxide is 20 ~ 200nm, and epoxy group content is 10 ~ 20mmol/g.
3. a coating, this coating contains nano zine oxide composite organic modified ultra-branching mylar 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, silica and carborundum; Described high boiling solvent refers to a kind of or two or more in ethylene glycol ether acetate, diethylene glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and methyl isoamyl ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410766131.0A CN104558571B (en) | 2014-12-12 | 2014-12-12 | A kind of preparation method of nano zine oxide composite organic modified ultra-branching mylar and containing the coating of this resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410766131.0A CN104558571B (en) | 2014-12-12 | 2014-12-12 | A kind of preparation method of nano zine oxide composite organic modified ultra-branching mylar and containing the coating of this resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558571A CN104558571A (en) | 2015-04-29 |
| CN104558571B true CN104558571B (en) | 2016-05-04 |
Family
ID=53075706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410766131.0A Active CN104558571B (en) | 2014-12-12 | 2014-12-12 | A kind of preparation method of nano zine oxide composite organic modified ultra-branching mylar and containing the coating of this resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558571B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100274B (en) * | 2019-12-31 | 2021-11-23 | 杭州吉华高分子材料股份有限公司 | Preparation method of antibacterial nano-silver resin and non-stick coating containing resin |
| CN113621261B (en) * | 2020-05-07 | 2022-04-12 | 成都虹润制漆有限公司 | Organic-inorganic mixed flame-retardant mildew-proof coating and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205317B (en) * | 2007-11-30 | 2011-06-15 | 北京化工大学 | Preparation of high-damping rubber containing hindered phenol terminated hyper branched polymer |
| CN102504271B (en) * | 2011-11-03 | 2013-04-03 | 杭州吉华高分子材料有限公司 | Method for preparing hyperbranched polyester modified organic silicon resin |
| CN102977350B (en) * | 2012-11-27 | 2014-08-27 | 杭州吉华高分子材料有限公司 | Preparation method of modified carboxyl-terminated hyperbranched polyester resin and coating containing resin |
| CN103113566B (en) * | 2013-01-31 | 2014-12-03 | 华南理工大学 | Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof |
-
2014
- 2014-12-12 CN CN201410766131.0A patent/CN104558571B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558571A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102504265B (en) | Method for preparing polyester modified organic silicon resin and coating containing the resin | |
| CN103881104B (en) | A kind of preparation method of modified polyester resin and application | |
| CN102504293B (en) | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin | |
| CN105482089B (en) | A kind of water-soluble organic silicon modified polyester resin and the preparation method and application thereof | |
| CN103113566B (en) | Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof | |
| CN102504271B (en) | Method for preparing hyperbranched polyester modified organic silicon resin | |
| CN102964592B (en) | Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin | |
| CN103113578B (en) | Modified carboxyl-terminated hyperbranched polyamide resin, as well as preparation method and application thereof | |
| CN104558578B (en) | A kind of preparation method of nano silicon composite organic modified ultra-branching vibrin and the coating containing this resin | |
| CN104151925B (en) | High temperature resistant ink and preparation method thereof and OGS contact panels | |
| CN103589336B (en) | A kind of self-vulcanizing vinylformic acid heteropolysiloxane nano ceramics protective coating and preparation method thereof | |
| CN102977350B (en) | Preparation method of modified carboxyl-terminated hyperbranched polyester resin and coating containing resin | |
| CN103113570B (en) | Amino-terminated silicon oil modified carboxyl-terminated hyperbranched polyester resin, and preparation method and application thereof | |
| CN102977363B (en) | Preparation method of modified amino-terminated hyper-branched polyamide resin and coating comprising resin | |
| CN102746449A (en) | Fluorine-silicon modified hydroxy acrylic resin and preparation method thereof | |
| CN102977352B (en) | Preparation method of modified polyester resin and coating containing polyester resin obtained by same | |
| CN104558571B (en) | A kind of preparation method of nano zine oxide composite organic modified ultra-branching mylar and containing the coating of this resin | |
| CN102358822A (en) | Preparation method for composite transparent hard coating | |
| CN103992474B (en) | A kind of preparation method of ultrabranching polyamide modified organic silicone resin and the standby coating of this resin-made | |
| CN104558577B (en) | A kind of preparation method of nano aluminium oxide composite organic modified ultra-branching vibrin and the coating containing this resin | |
| CN102977351B (en) | Preparation method of modified polyester resin and coating containing polyester resin | |
| CN103113567B (en) | Epoxy-terminated silicon oil modified carboxyl-terminated hyperbranched polyester, and preparation method and application thereof | |
| CN104004197B (en) | The preparation method of a kind of polyamide modified organic siliconresin and the standby coating of this resin-made | |
| CN103193986A (en) | Epoxy-terminated silicone oil-modified hydroxyl-terminated hyperbranched polyester, and preparation method and application thereof | |
| CN103881105B (en) | A kind of preparation method of modified epoxy and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |