CN104004198B - The preparation method of the polyamide modified organic siliconresin of a kind of high rigidity and the coating containing this resin - Google Patents
The preparation method of the polyamide modified organic siliconresin of a kind of high rigidity and the coating containing this resin Download PDFInfo
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Abstract
The preparation method that the present invention relates to the polyamide modified organic siliconresin of a kind of high rigidity, the method is made up of following steps: will heat 1～4h after diamine, the ternary acid of diamine molal quantity 1～2.0 times, the amination ultra-fine alumina of diamine weight 1～2 times, the crosslinking catalyst of 1～5% of diamine weight and the dimethylbenzene mix homogeneously of diamine weight 3～8 times under 180～220 DEG C of conditions；Then it is cooled to 90 DEG C, adds the epoxy terminated silicone oligomer of diamine weight 1.5～2.0 times, under 120～140 DEG C of conditions, heat 2～3h；Finally it is cooled to 90 DEG C, adds organic solvent and make solid content be 40～50wt%.Resin prepared by the method for the invention may be used for preparing high temperature resistant low surface energy coatings.The method uses amination ultra-fine alumina, and diamine and ternary acid one react and prepare modified ultra-branching polyamide, improves heat resistance and the hardness of polyamide；Carry out cross-linking reaction by modified ultra-branching polyamide with containing epoxy silicones oligomer, improve heat resistance and the hardness of polyamide.
Description
Technical field
The present invention relates to field of organic polymer compound, relate to the macromolecular compound that amidation process obtains, be specifically related to polyamide.
Background technology
Polyamide has excellent thermostability, mar proof, chemical proofing and good mechanical property and processing characteristics, and coefficient of friction is low, has certain anti-flammability, it is easy to processing, is widely used as engineering plastics.Polyamide is good with the compatibility of various kinds of resin, is used widely in coating industry.But polyamide molecular weight is big, poorly soluble, viscosity is high, it is more difficult to carry out chemical modification with other resins.Ultrabranching polyamide resin has highly branched structure and substantial amounts of terminal reactive group, has highly dissoluble, low viscosity and higher chemical reactivity, and these make ultrabranching polyamide resin demonstrate tempting application prospect in many aspects.
Organic siliconresin has-Si-O-Si-structure, it is shown that the performance such as excellent weatherability, thermostability, anti-stain characteristic and chemically stable.But pure organic siliconresin needs hot setting and length construction inconvenience hardening time, simultaneously with the poor adhesive force of metal material, poor solvent resistance, mechanical strength is not high, expensive, so its use is somewhat limited, therefore it is modified by other resins conventional.Publication number is by ultrabranching polyamide modified organic silicone resin disclosed in the patent application of CN103113578A, improves the mechanical performance of organic siliconresin and the scheme of chemical resistance.
Ultra-fine alumina is nonpoisonous and tasteless Inorganic Non-metallic Materials, is widely used in coating, rubber, plastics etc. as filler, it is possible to improve the mechanical property of polymeric material, thermal property and electric property.Ultra-fine alumina has higher polarity, and Surface binding energy is strong, it is easy to reunites, is difficult to infiltrate and disperse in organic media.When ultra-fine alumina joins in non-polar polymer material, the two polarity spectrum is relatively big, causes that ultra-fine alumina is assembled, and interface binding power is poor, it is difficult to play the potentiation to polymeric material.(the Fu Jifang such as Fu Jifang, Xiao Yinglin, Chen Yi, Shi Liyi, Chen Liya, Zhong Qingdong, insulant 2011,44 (2), 4) the modified impregnating varnish of hyper-branched polyester functionalization ultra-fine alumina is adopted, it has been found that the Al2O3 of hyper-branched polyester graft modification can be effectively improved the heat conductivity of insulating impregnating varnish, mechanical property and specific insulation.The ultrabranching polyamide modified nano-alumina such as Yu Jinhong, it has been found that this modified aluminas can improve the thermodynamic property of epoxy resin.(JinhongYu,XingyiHuang,LichunWang,PengPeng,ChaoWu,XinfengWuandPingkaiJiang,Preparationofhyperbranchedaromaticpolyamidegraftednanoparticlesforthermalpropertiesreinforcementofepoxycomposites,PolymerChemistry,2011,2,1380-1388.)
But, the hardness of the organic siliconresin that above-mentioned prior art is obtained is still not ideal enough.
Summary of the invention
The preparation method that the technical problem to be solved is to provide the polyamide modified organic siliconresin of a kind of high rigidity, polyamide modified organic siliconresin prepared by the method has heat resistance and the good advantage of hardness.
This invention address that the scheme of above-mentioned technical problem is:
A kind of preparation method of the polyamide modified organic siliconresin of high rigidity, the method is made up of following steps:
1～4h will be heated under 180～220 DEG C of conditions after diamine, the ternary acid of diamine molal quantity 1～2.0 times, the amination ultra-fine alumina of diamine weight 1～2 times, the crosslinking catalyst of 1～5% of diamine weight and the dimethylbenzene mix homogeneously of diamine weight 3～8 times；Then it is cooled to 90 DEG C, adds the epoxy terminated silicone oligomer of diamine weight 1.5～2.0 times, under 120～140 DEG C of conditions, heat 2～3h；Finally it is cooled to 90 DEG C, adds organic solvent and make solid content be 40～50wt%；
Described diamine is the one in isophorone diamine, 4,4 '-MDA, 4,4 '-DADPS and 1,6-diamidogen or two or more；
Described ternary acid is the one in 1,2,4 benzenetricarboxylic acid and 1,3,5-benzenetricarboxylic acid or two kinds；
The particle diameter of described amination ultra-fine alumina is 30～150nm, and amino content is 1.2～2mmol/g；
The weight average molecular weight of described epoxy terminated silicone oligomer is 1000～4000, and every epoxy terminated silicone oligomer of 100g contains 20～200mmol epoxy radicals；
Described crosslinking catalyst is butyl titanate；
Described organic solvent is one or more in butanol, isobutanol, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate and dipropylene acetate.
In above-mentioned preparation method, described epoxy terminated silicone oligomer can by the γ of silicone oligomer and silicone oligomer weight 1～10%-(2,3-epoxy the third oxygen) propyl trimethoxy silicane or γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane hydrolysis-condensation reaction obtains, the molecular weight of wherein said silicone oligomer is for for 800～2000, and the hydroxyl of methoxy or ethoxy containing 2.5～15wt% and 3～20wt%；Wherein, described hydrolysis-condensation reaction is hydrolysis-condensation reaction commonly used in the art, and its technique and reaction condition are the routine techniquess that those skilled in the art should grasp.
Above-mentioned preparation method, wherein said silicone oligomer can be obtained by the siloxanes such as methltriethoxysilone, dimethyldiethoxysilane and the phenyl triethoxy condensation reaction that is hydrolyzed, it is also possible to is obtained by the siloxanes such as monomethyl trimethoxy silane, dimethyldimethoxysil,ne and the phenyl trimethoxy condensation reaction that is hydrolyzed.Wherein, the described siloxanes siloxanes that condensation reaction is commonly used in the art that is hydrolyzed is hydrolyzed condensation reaction, and its technique and reaction condition are the routine techniquess that those skilled in the art should grasp.
Above-mentioned preparation method, wherein said silicone oligomer can also is that the 233 of Dow Corning Corporation, the 249 of Dow Corning Corporation, the Z-6108 of Dow Corning Corporation, the IC836 of Wa Ke company, the 3074 of Dow Corning Corporation, SHIN-ETSU HANTOTAI organic siliconresin 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, one in the KR213 of company of SHIN-ETSU HANTOTAI or two or more.
Above-mentioned preparation method, wherein said amination ultra-fine alumina is prepared by following methods, is added in dry toluene by the gamma-aminopropyl-triethoxy-silane of ultra-fine alumina and ultra-fine alumina weight 0.4～0.8 times, is heated to reflux 3～5h；Product at reduced pressure sucking filtration, vacuum drying obtains amination ultra-fine alumina.
In the method for the invention, the weight average molecular weight of described epoxy terminated silicone oligomer preferably 2000～3000, and every epoxy terminated silicone oligomer of 100g contains 60～120mmol epoxy radicals.
In the method for the invention, the particle diameter of described amination ultra-fine alumina is 50～100nm, and amino content is 1.4～1.8mmol/g.
Polyamide modified organic siliconresin prepared by method of the present invention, has the advantage that
Diamine, ternary acid and amination ultra-fine alumina are reacted and prepares alumina modified ultrabranching polyamide resin, wherein diamine and ternary acid carry out ultrabranching polyamide prepared by amidation process and are grafted to the surface of amination ultra-fine alumina, ultra-fine alumina is embedded in ultrabranching polyamide, improve heat resistance and the hardness of polyamide.
On the other hand, alumina modified ultrabranching polyamide resin and epoxy terminated silicone oligomer are carried out cross-linking reaction and prepares polyamide modified organic silicone resin, improve heat resistance and the hardness of polyamide modified organic siliconresin.
A kind of coating, this coating contains the above-mentioned polyamide modified organic siliconresin of weight portion 60～80wt%, 10～20wt% is high temperature resistant filler and 5～20wt% high boiling solvent, wherein,
Described high boiling solvent is the one in ethylene glycol ether acetate, butyl acetate, isobutyl isobutyrate, propanoic acid-3-ether ethyl ester and methyl isoamyl ketone or two or more；
Described filler is high temperature resistant filler commonly used in the art, it is possible to be titanium dioxide or carborundum.
Also can adding high-temperature resisting pigment commonly used in the art in above-mentioned coating, described high-temperature resisting pigment can be the inorganic high-temperature resistant pigment such as carbon black, iron oxide red, it is also possible to be the organic high temperature-resistant pigment such as phthalocyanine blue.
Above-mentioned coating can also add organosilicon auxiliary agent commonly used in the art, e.g., play the effects such as levelling, froth breaking, pigment wetting, viscosity adjustment.Above-mentioned organosilicon auxiliary agent can also is that 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 to determine kind and the consumption of organosilicon auxiliary agent, and the consumption that the present inventor recommends is 1～5wt%.
The preparation method of above-mentioned coating is preparation method commonly used in the art, is mixed to get by polyamide modified organic siliconresin, pigment, filler, organosilicon auxiliary agent and high boiling solvent.
Owing to coating of the present invention adopts above-mentioned polyamide modified organic siliconresin to prepare, therefore having high-fire resistance can with good hardness.
Detailed description of the invention
The following is the non-limiting example of technical scheme of the present invention.
Embodiment 1:
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
Gamma-aminopropyl-triethoxy-silane: 12g
Toluene: 500g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 3h；Decompression filters, and dries and obtains amination ultra-fine alumina 39g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 100nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and it specifically comprises the following steps that the amination ultra-fine alumina first accurately weighing about 1.5g is in conical flask, adds 20mL oxolane and toluene, and stirring makes it be uniformly dispersed；Adding 3～4 methyl orange indicators, the HCI being 0.2mol/L with concentration, color from yellow is titration end-point when becoming lightcoral.Ammonia value is calculated as follows
A=(V-V0) * c/m
A: ammonia value is the molal quantity of amino in every gram of amination superfine silicon dioxide, and its unit is mmol/g
V: amination ultra-fine alumina consumes the volume of hydrochloric acid standard solution, mL
V0: blank sample consumes the volume of hydrochloric acid standard solution, mL
C: concentration of hydrochloric acid, mol/L；
M: the weight of amination ultra-fine alumina, g
The ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.2mmol/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
After reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into siloxanes and 4.5mmol hydrochloric acid by proportioning, start stirring and heat up, keeping temperature constant after being warmed up to 60 DEG C, under agitation dropping 31.7g distilled water, after dropwising, again after isothermal reaction 3h, starting decompression distillation, Stress control is at 0.06MPa, boil off the little molecule and water that produce in course of reaction, being cooled to room temperature, adding dimethylbenzene adjustment solid content is 60wt%, obtains silicone oligomer 280g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography detection, and result is 914；The hydroxy radical content of silicone oligomer adopts acetic anhydride method to measure, and result is 12wt%；The methoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 7.1wt%.
3) preparation of epoxy terminated silicone oligomer
Silicone oligomer: the silicone oligomer 100g of step 2 preparation
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 3.5g
γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane 1.5g
B) preparation technology
Equipped with condensing tube, thermometer, the reactor of Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.05g tetramethyl ammonium hydroxide and 30g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane and γ-(2, 3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane, again after isothermal reaction 3h, start decompression distillation, Stress control is at 0.06MPa, boil off the little molecule produced in course of reaction, it is cooled to room temperature, adjustment solid content is 60wt%, obtain epoxy terminated silicone oligomer 86g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 2588；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 110mmol/100g.
4) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,3,5-benzenetricarboxylic acid 31.5g (0.15mol)；
Diamine: 4,4 '-DADPS 2.88g (0.012mol)；Isophorone diamine 6.8g (0.04mol)；4,4 '-MDA 7.54g (0.038mol)；1,6-is diamidogen 1.16g (0.01mol)；
Amination ultra-fine alumina: the amination ultra-fine alumina 28.6g of step 1 preparation
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 48g that solid content is 60wt% of step 3 preparation
Dimethylbenzene: 95g
Crosslinking catalyst: butyl titanate 0.17g
Organic solvent: propylene glycol methyl ether acetate 15g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 180 DEG C after dimethylbenzene mix homogeneously to heat 4h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 130 DEG C, heats 3.5h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 50wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
1* heat resistance: after test piece is toasted 2h in 180 DEG C, put in the Ovenized electric furnace of potential difference meter verification, temperature is raised by 5 DEG C/min, starting timing with furnace temperature to requirement of experiment temperature, sample, after continuous high temperature, takes out, it is cooled to room temperature (25 DEG C), coating surface situation is observed, as without be full of cracks, obscission, namely illustrated that coating heat resistance can be good with magnifier.
5) coating
A) composition
Modified end polyamide: the polyamide modified organic siliconresin 100g of above-mentioned preparation；
Filler: titanium dioxide 60g；
Organosilicon auxiliary agent: silicone oil/350cst8g；
High boiling solvent: ethylene glycol ether acetate 5g.
B) preparation technology
By filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 2:
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 40g
γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane: 32g
Toluene: 600g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane afterwards, is heated to reflux 5h；Decompression filters, and dries and obtains amination ultra-fine alumina 68g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 150nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 2mmol/g.
2) preparation of epoxy terminated silicone oligomer
I) 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
After reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into siloxanes and 4.5mmol hydrochloric acid by proportioning, start stirring and heat up, keeping temperature constant after being warmed up to 60 DEG C, under agitation dropping 31.7g distilled water, after dropwising, again after isothermal reaction 3h, starting decompression distillation, Stress control is at 0.06MPa, boil off the little molecule and water that produce in course of reaction, being cooled to room temperature, adjusting solid content with dimethylbenzene is 60wt%, obtains silicone oligomer 290g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography detection, and result is 802；The hydroxy radical content of silicone oligomer adopts acetic anhydride method to measure, and result is 10.6wt%；The methoxyl 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 epoxy terminated silicone oligomer
Silicone oligomer: I) the 70% silicone oligomer 100g for preparing
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 1.0g
γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane 0.5g
B) preparation technology
Equipped with condensing tube, thermometer, the reactor of Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.03g tetramethyl ammonium hydroxide and 10g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane and γ-(2, 3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane, again after isothermal reaction 4h, start decompression distillation, Stress control is at 0.06MPa, boil off the little molecule produced in course of reaction, it is cooled to room temperature, adjustment solid content is 80wt%, obtain epoxy terminated silicone oligomer 105g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 2457；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 87mmol/100g.
4) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,2,4 benzenetricarboxylic acid 29.4g (0.14mol)；
Diamine: 1,6-is diamidogen 8.12g (0.05mol)；4,4 '-DADPS 7.44g (0.03mol)
Amination ultra-fine alumina: the amination ultra-fine alumina 22.5g of step 1 preparation
Dimethylbenzene: 120g
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 41g of step 2 preparation
Crosslinking catalyst: butyl titanate 0.3g
Organic solvent: dipropylene glycol methyl ether acetate 10g, dipropylene acetate 10g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 210 DEG C after dimethylbenzene mix homogeneously to heat 2h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 135 DEG C, heats 3h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 40wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
5) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 160g of step 4 preparation；
Filler: titanium dioxide 20g, carborundum 8g
Organosilicon auxiliary agent: silicone oil/350cst1g。
High boiling solvent: ethylene glycol ether acetate (CAC): 10g.
B) preparation technology
By filler, polyamide modified organic siliconresin, high boiling solvent, auxiliary agent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 3:
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 40g
Gamma-aminopropyl-triethoxy-silane: 20g
Toluene: 400g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 3h；Decompression filters, and dries and obtains amination ultra-fine alumina 57g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 30nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.48mmol/g.
2) preparation of silicone oligomer
A) composition
Monomethyl trimethoxy silane: 42.0g (0.28mol)
Dimethyldimethoxysil,ne: 22.7g (0.17mol)
One phenyltrimethoxysila,e: 116.0g (0.55mol),
B) preparation technology
After reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into siloxanes and 4.5mmol sulphuric acid by proportioning, start stirring and heat up, keeping temperature constant after being warmed up to 60 DEG C, under agitation dropping 28g distilled water, after dropwising, again after isothermal reaction 4h, starting decompression distillation, Stress control is at 0.06MPa, boil off the little molecule produced in course of reaction, being cooled to room temperature, adding dimethylbenzene adjustment solid content is 60wt%, obtains silicone oligomer 252g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography detection, and result is 1986；The hydroxy radical content of silicone oligomer adopts acetic anhydride method to measure, and result is 12wt%；The methoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 6.7wt%.
3) preparation of epoxy terminated silicone oligomer
A) composition
Silicone oligomer: the solid content of step 2 preparation is 60wt% silicone oligomer 100g
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 6g
B) preparation technology
Reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.2g tetramethyl ammonium hydroxide and 30g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start decompression distillation, Stress control, at 0.06MPa, boils off the little molecule produced in course of reaction, is cooled to room temperature, adjustment solid content is 60wt%, obtains epoxy terminated silicone oligomer 90g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 2635；Epoxide number content adopts hydrochloric acid-acetone method to measure, and result is 197mmol/100g.
4) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,2,4 benzenetricarboxylic acid 23.1g (0.11mol)；
Diamine: 4,4 '-DADPS 14.9g (0.05mol)；Isophorone diamine 8.5g (0.05mol)
Amination ultra-fine alumina: the amination ultra-fine alumina 37.4g of step 1 preparation
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 62.4g that solid content is 60wt% of step 2 preparation
Dimethylbenzene: 94g
Crosslinking catalyst: butyl titanate 0.33g
Organic solvent: propylene glycol methyl ether acetate 28g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 190 DEG C after dimethylbenzene mix homogeneously to heat 3h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 135 DEG C, heats 2h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 45wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
5) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 100g of step 4 preparation；
Filler: titanium dioxide 10g, carborundum 30g
Organosilicon auxiliary agent: CoatOSil70014g；Silicone oil/350cst6g；
High boiling solvent: butyl acetate 5g；Butyl acetate 5g.
B) preparation technology
By filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 4:
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
Gamma-aminopropyl-triethoxy-silane: 21g
Toluene: 350g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 3.5h；Decompression filters, and dries and obtains amination ultra-fine alumina 48.6g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 60nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.87mmol/g.
2) preparation of epoxy terminated silicone oligomer
Silicone oligomer: the 3074100g of Dow Corning Corporation
γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane 3g
B) preparation technology
Reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.03g tetramethyl ammonium hydroxide and 20g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane, again after isothermal reaction 3.5h, start decompression distillation, Stress control, at 0.06MPa, boils off the little molecule produced in course of reaction, is cooled to room temperature, adjustment solid content is 60wt%, obtains epoxy terminated silicone oligomer 114g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 1958；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 108mmol/100g.
3) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,3,5-benzenetricarboxylic acid 37.8g (0.18mol)；
Diamine: isophorone diamine 3.4g (0.02mol)；1,6-is diamidogen 5.81g (0.05mol)；4,4 '-DADPS 7.44g (0.03mol)
Amination ultra-fine alumina: the amination ultra-fine alumina 21.6g of step 1 preparation
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 55.5g of step 2 preparation
Dimethylbenzene: 50g
Crosslinking catalyst: butyl titanate 0.64g
Organic solvent: propylene glycol methyl ether acetate 7g, butanol 10g, dipropylene glycol methyl ether acetate 10g, dipropylene acetate 10g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 220 DEG C after dimethylbenzene mix homogeneously to heat 1h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 140 DEG C, heats 2h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 50wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
4) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 120g of step 3 preparation；
Filler: carborundum 20g；
Organosilicon auxiliary agent: CoatOSil35004g；Silicone oil/350cst4g；
High boiling solvent: propanoic acid-3-ether ethyl ester (EEP) 10g；Methyl isoamyl ketone 10g.
B) preparation technology
By filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 5
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
Gamma-aminopropyl-triethoxy-silane: 19.5g
Toluene: 310g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 4.5h；Decompression filters, and dries and obtains amination ultra-fine alumina 47.6g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 70nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.75mmol/g.
2) preparation of epoxy terminated silicone oligomer
Silicone oligomer: the 23330g of Dow Corning Corporation, the 24920g of Dow Corning Corporation, the IC83620g of Z-610820g, Wa Ke company of Dow Corning Corporation, company of SHIN-ETSU HANTOTAI KR21310g
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 4g
B) preparation technology
Reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.03g tetramethyl ammonium hydroxide and 20g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start decompression distillation, Stress control, at 0.06MPa, boils off the little molecule produced in course of reaction, is cooled to room temperature, adjustment solid content is 60wt%, obtains epoxy terminated silicone oligomer 97g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 1555；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 145mmol/100g.
3) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,2,4 benzenetricarboxylic acid 25.2g (0.12mol)；
Diamine: 1,6-is diamidogen 6.38g (0.055mol)；4,4 '-DADPS 11.16g (0.045mol)；
Amination ultra-fine alumina: the amination ultra-fine alumina 24.4g of step 1 preparation
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 46.6g that solid content is 60wt% of step 2 preparation
Dimethylbenzene: 70g
Crosslinking catalyst: butyl titanate 0.24g
Organic solvent: propylene glycol methyl ether acetate 3g, isobutanol 3g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 200 DEG C after dimethylbenzene mix homogeneously to heat 3.5h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 120 DEG C, heats 3h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 50wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
4) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 120g of step 3 preparation；
Filler: carborundum 25g；Titanium dioxide 5g；
Pigment: iron oxide red 5g；
Organosilicon auxiliary agent: CoatOSil35004g；CoatOSil75102g；Silicone oil/350cst4g；
High boiling solvent: methyl isoamyl ketone 12g.
B) preparation technology
By pigment, filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 6
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
Gamma-aminopropyl-triethoxy-silane: 18g
Toluene: 440g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 3.5h；Decompression filters, and dries and obtains amination ultra-fine alumina 45g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 90nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.67mmol/g.
2) preparation of epoxy terminated silicone oligomer
Silicone oligomer: SHIN-ETSU HANTOTAI organic siliconresin KR15015g, the KR2115g of company of SHIN-ETSU HANTOTAI, the KR21220g of company of SHIN-ETSU HANTOTAI, the KR21415g of company of SHIN-ETSU HANTOTAI, the KR21645g of company of SHIN-ETSU HANTOTAI
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 2g
γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane 3g
B) preparation technology
Equipped with condensing tube, thermometer, the reactor of Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.03g tetramethyl ammonium hydroxide and 20g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2, 3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start decompression distillation, Stress control is at 0.06MPa, boil off the little molecule produced in course of reaction, it is cooled to room temperature, adjustment solid content is 70wt%, obtain epoxy terminated silicone oligomer 81g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 2865；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 162mmol/100g.
3) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,3,5-benzenetricarboxylic acid 29.4g (0.14mol)；1,2,4 benzenetricarboxylic acid 12.6g (0.06mol)；
Diamine: 1,6-hexamethylene diamine 4.64g (0.04mol)；Isophorone diamine 6.8g (0.04mol)；4,4 '-MDA 3.96g (0.02mol)；
Amination ultra-fine alumina: the amination ultra-fine alumina 27g of step 1 preparation
Dimethylbenzene: 62g
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 25.7g that solid content is 80wt% of step 3 preparation
Crosslinking catalyst: butyl titanate 0.13g
Organic solvent: dipropylene glycol methyl ether acetate 10g, propylene glycol monomethyl ether 10g, butanol 8g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 190 DEG C after dimethylbenzene mix homogeneously to heat 3h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 130 DEG C, heats 2.5h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 45wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
4) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 110g of step 3 preparation；
Filler: carborundum 15g；Titanium dioxide 5g；
Pigment: phthalocyanine blue 8g；
High boiling solvent: methyl isoamyl ketone 40g；Isobutyl isobutyrate 20g.
B) preparation technology
By pigment/filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 7
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
Gamma-aminopropyl-triethoxy-silane: 13.5g
Toluene: 330g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 5h；Decompression filters, and dries and obtains amination ultra-fine alumina 39g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 110nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.4mmol/g.
2) preparation of epoxy terminated silicone oligomer
Silicone oligomer: the IC83650g of organic siliconresin KR15050g, Wa Ke company of SHIN-ETSU HANTOTAI
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 0.6g
B) preparation technology
Reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.01g tetramethyl ammonium hydroxide and 20g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start decompression distillation, Stress control, at 0.06MPa, boils off the little molecule produced in course of reaction, is cooled to room temperature, adjustment solid content is 70wt%, obtains epoxy terminated silicone oligomer 76g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 997；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 19mmol/100g.
3) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,3,5-benzenetricarboxylic acid 21g (0.10mol)；
Diamine: 4,4 '-DADPS 9.19g (0.037mol)；1,6-hexamethylene diamine 5.8g (0.05mol)
Amination ultra-fine alumina: the amination ultra-fine alumina 26.8g of step 1 preparation
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 38.5g that solid content is 70wt% of step 2 preparation
Dimethylbenzene: 60g
Crosslinking catalyst: butyl titanate 0.44g
Organic solvent: propylene glycol methyl ether acetate 7g butanol 11g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 190 DEG C after dimethylbenzene mix homogeneously to heat 3h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 135 DEG C, heats 2h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 50wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
4) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 140g of step 3 preparation；
Filler: carborundum 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
By pigment, filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 8
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
Gamma-aminopropyl-triethoxy-silane: 16.5g
Toluene: 420g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 4.5h；Decompression filters, and dries and obtains amination ultra-fine alumina 43g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 100nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.6mmol/g.
2) preparation of silicone oligomer
A) composition
Methltriethoxysilone: 44.5g (0.25mol)
Dimethyldiethoxysilane: 50.3g (0.34mol)
Phenyltriethoxysilane: 98.4g (0.41mol),
B) preparation technology
After reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into siloxanes and 7.0mmol hydrochloric acid by proportioning, start stirring and heat up, keeping temperature constant after being warmed up to 70 DEG C, under agitation dropping 43.1g distilled water, after dropwising, again after isothermal reaction 3h, starting decompression distillation, Stress control is at 0.06MPa, boil off the little molecule produced in course of reaction, being cooled to room temperature, adding dimethylbenzene adjustment solid content is 60wt%, obtains silicone oligomer 220g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography detection, and result is 1986；The hydroxy radical content of silicone oligomer adopts acetic anhydride method to measure, and result is 15wt%；The ethoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 3wt%；R/Si=1.34；Ph/Me=0.44.
3) preparation of epoxy terminated silicone oligomer
Silicone oligomer: the solid content of step 2 preparation is 60wt% silicone oligomer 100g
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 0.8g
B) preparation technology
Reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.02g tetramethyl ammonium hydroxide and 20g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start decompression distillation, Stress control, at 0.06MPa, boils off the little molecule produced in course of reaction, is cooled to room temperature, adjustment solid content is 80wt%, obtains epoxy terminated silicone oligomer 98g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 3445；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 34mmol/100g.
4) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,2,4 benzenetricarboxylic acid 4.2g (0.02mol)；1,3,5-benzenetricarboxylic acid 21g (0.1mol)
Diamine: 4,4 '-DADPS 14.9g (0.6mol)；1,6-hexamethylene diamine 4.64g (0.04mol)
Amination ultra-fine alumina: the amination ultra-fine alumina 33.9g of step 1 preparation
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 37.2g that solid content is 80wt% of step 2 preparation
Dimethylbenzene: 140g
Crosslinking catalyst: butyl titanate 0.26g
Organic solvent: propylene glycol methyl ether acetate 5g, dipropylene glycol methyl ether 5g, dipropylene 5g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 190 DEG C after dimethylbenzene mix homogeneously to heat 3h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 135 DEG C, heats 2h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 40wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
5) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 150g of step 4 preparation；
Filler: carborundum 20g；
Organosilicon auxiliary agent: CoatOSil35005g；Silicone oil/350cst5g；
High boiling solvent: methyl isoamyl ketone 10g.
B) preparation technology
By paint filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 9
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
Gamma-aminopropyl-triethoxy-silane: 15g
Toluene: 400g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 5h；Decompression filters, and dries and obtains amination ultra-fine alumina 41g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 75nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.48mmol/g.
2) preparation of silicone oligomer
A) composition
Methltriethoxysilone: 44.5g (0.25mol)
Dimethyldiethoxysilane: 50.3g (0.34mol)
Phenyltriethoxysilane: 98.4g (0.41mol),
B) preparation technology
After reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into siloxanes and 7.0mmol hydrochloric acid by proportioning, start stirring and heat up, keeping temperature constant after being warmed up to 70 DEG C, under agitation dropping 43.1g distilled water, after dropwising, again after isothermal reaction 3h, starting decompression distillation, Stress control is at 0.06MPa, boil off the little molecule produced in course of reaction, being cooled to room temperature, adding dimethylbenzene adjustment solid content is 60wt%, obtains silicone oligomer 220g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography detection, and result is 1986；The hydroxy radical content of silicone oligomer adopts acetic anhydride method to measure, and result is 15wt%；The ethoxyl content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 3wt%；R/Si=1.34；Ph/Me=0.44.
3) preparation of epoxy terminated silicone oligomer
Silicone oligomer: the solid content of step 2 preparation is 60wt% silicone oligomer 100g
γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane 1.4g
B) preparation technology
Reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.02g tetramethyl ammonium hydroxide and 20g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane, again after isothermal reaction 3h, start decompression distillation, Stress control, at 0.06MPa, boils off the little molecule produced in course of reaction, is cooled to room temperature, adjustment solid content is 80wt%, obtains epoxy terminated silicone oligomer 98g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 3985；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 44mmol/100g.
4) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,2,4 benzenetricarboxylic acid 4.2g (0.02mol)；1,3,5-benzenetricarboxylic acid 21g (0.1mol)
Diamine: 4,4 '-DADPS 14.9g (0.6mol)；1,6-hexamethylene diamine 4.64g (0.04mol)
Amination ultra-fine alumina: the amination ultra-fine alumina 19.54g of step 1 preparation
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 36.6g that solid content is 80wt% of step 2 preparation
Dimethylbenzene: 58.6g
Crosslinking catalyst: butyl titanate 0.26g
Organic solvent: propylene glycol methyl ether acetate 26g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 190 DEG C after dimethylbenzene mix homogeneously to heat 3h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 135 DEG C, heats 2h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 50wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
5) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 150g of step 4 preparation；
Filler: titanium dioxide 40g；
Organic additive: CoatOSil75108g；
Height boils and reaches solvent: methyl isoamyl ketone 2g.
B) preparation technology
By filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Embodiment 10
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 40g
Gamma-aminopropyl-triethoxy-silane: 26g
Toluene: 350g
B) preparation technology
Adding ultra-fine alumina and toluene in the reactor equipped with condensing tube, thermometer and agitator, high speed dispersion uniformly adds gamma-aminopropyl-triethoxy-silane afterwards, is heated to reflux 5h；Decompression filters, and dries and obtains amination ultra-fine alumina 61g.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL detection, and result is 65nm；
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and the ammonia value of the amination ultra-fine alumina of above-mentioned preparation is 1.76mmol/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
After reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into siloxanes and 4.5mmol hydrochloric acid by proportioning, start stirring and heat up, keeping temperature constant after being warmed up to 60 DEG C, under agitation dropping 31.7g distilled water, after dropwising, again after isothermal reaction 3h, starting decompression distillation, Stress control is at 0.06MPa, boil off the little molecule produced in course of reaction, being cooled to room temperature, adjustment solid content is 60wt%, obtains silicone oligomer 287g.
C) performance
The weight average molecular weight of silicone oligomer adopts gel permeation chromatography detection, and result is 802；The hydroxy radical content of silicone oligomer adopts acetic anhydride method to measure, and result is 10.6wt%；The methoxyl 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 epoxy terminated silicone oligomer
Silicone oligomer: the solid content of step 2 preparation is 60wt% silicone oligomer 100g
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 0.6g
B) preparation technology
Reactor equipped with condensing tube, thermometer, Dropping funnel and agitator is sequentially added into silicone oligomer by proportioning, after 0.01g tetramethyl ammonium hydroxide and 20g toluene, start stirring and heat up, temperature constant is kept after being warmed up to 90 DEG C, it is added slowly with stirring γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 1h, start decompression distillation, Stress control, at 0.06MPa, boils off the little molecule produced in course of reaction, is cooled to room temperature, adjustment solid content is 70wt%, obtains epoxy terminated silicone oligomer 98g.
C) performance
The weight average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography detection, and result is 1005；The epoxide number content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 20mmol/100g.
4) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,3,5-benzenetricarboxylic acid 10.5g (0.05mol)；1,2,4 benzenetricarboxylic acid 10.5g (0.05mol)；
Diamine: 1,6-hexamethylene diamine 6.96g (0.06mol)；Two amidos diphenyl sulphone (DPS) 9.94g (0.04mol)；
Amination ultra-fine alumina: the amination ultra-fine alumina 33.8g of step 1 preparation
Dimethylbenzene: 134g
Epoxy terminated silicone oligomer: the solid content of step 2 preparation is the epoxy terminated silicone oligomer 56.3g of 60wt%
Crosslinking catalyst: butyl titanate 0.168g
Organic solvent: propylene glycol methyl ether acetate 1g
B) synthesis step:
By diamine, ternary acid, amination ultra-fine alumina, crosslinking catalyst and after being warming up at 180 DEG C after dimethylbenzene mix homogeneously to heat 4h, it is cooled to 90 DEG C, adds epoxy terminated silicone oligomer；Heating, to 140 DEG C, heats 2h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 40wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
5) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 120g of step 4 preparation；
Filler: titanium dioxide 20g；Carborundum 40g；
Organosilicon auxiliary agent: CoatOSil7510:2g；
High boiling solvent: methyl isoamyl ketone 18g.
B) preparation technology
By filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Comparative example 1
The preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,3,5-benzenetricarboxylic acid 29.4g (0.14mol)；1,2,4 benzenetricarboxylic acid 12.6g (0.06mol)；
Diamine: 1,6-hexamethylene diamine 4.64g (0.04mol)；Isophorone diamine 6.8g (0.04mol)；4,4 '-MDA 3.96g (0.02mol)；
Epoxy resin: epoxy resin E-125g
Silicone oligomer: the silicone oligomer 25.7g of embodiment 2 preparation
Crosslinking catalyst: butyl titanate 0.13g
Organic solvent: dipropylene glycol methyl ether acetate 63g butanol 35g
B) synthesis step:
By diamine, ternary acid and crosslinking catalyst uniformly after be warming up at 190 DEG C to heat 3h after, be cooled to 90 DEG C, add epoxy resin and silicone oligomer；Heating, to 130 DEG C, heats 2.5h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 45wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
2) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 160g of step 1 preparation；
Filler: titanium dioxide 20g, carborundum 8g
Organosilicon auxiliary agent: silicone oil/350cst1g。
High boiling solvent: ethylene glycol ether acetate (CAC): 10g.
B) preparation technology
By filler, polyamide modified organic siliconresin, high boiling solvent, auxiliary agent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Comparative example 2:
1) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,2,4 benzenetricarboxylic acid 29.4g (0.14mol)；
Diamine: 1,6-is diamidogen 8.12g (0.05mol)；4,4 '-DADPS 7.44g (0.03mol)
Epoxy resin: epoxy resin E-514g
Silicone oligomer: the silicone oligomer 41g of embodiment 3 preparation
Crosslinking catalyst: butyl titanate 0.3g
Organic solvent: dipropylene glycol methyl ether acetate 50g, dipropylene acetate 10g
B) synthesis step:
By diamine, ternary acid and crosslinking catalyst uniformly after be warming up at 210 DEG C to heat 2h after, be cooled to 90 DEG C, add epoxy resin and silicone oligomer；Heating, to 135 DEG C, heats 3h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 50wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
4) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 100g of step 3 preparation；
Filler: titanium dioxide 10g, carborundum 30g
Organosilicon auxiliary agent: CoatOSil70014g；Silicone oil/350cst6g；
High boiling solvent: butyl acetate 5g；Butyl acetate 5g.
B) preparation technology
By filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Comparative example 3:
1) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,3,5-benzenetricarboxylic acid 37.8g (0.18mol)；
Diamine: isophorone diamine 3.4g (0.02mol)；1,6-is diamidogen 5.81g (0.05mol)；4,4 '-DADPS 7.44g (0.03mol)
Epoxy resin: epoxy resin E-44 3g
Silicone oligomer: the 307455.5g of Dow Corning Corporation
Butyl acetate: 33.3g
Connection catalyst: butyl titanate 0.64g
Organic solvent: propylene glycol methyl ether acetate 41.3g, butanol 8g, dipropylene glycol methyl ether acetate 8g, dipropylene acetate 20g
B) synthesis step:
By diamine, ternary acid and crosslinking catalyst uniformly after be warming up at 220 DEG C to heat 1h after, be cooled to 90 DEG C, add epoxy resin and silicone oligomer；Heating, to 140 DEG C, heats 2h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 50wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
2) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 120g of step 1 preparation；
Filler: carborundum 10g；Titanium dioxide 10g；
Organosilicon auxiliary agent: CoatOSil35004g；Silicone oil/350cst4g；
High boiling solvent: propanoic acid-3-ether ethyl ester (EEP) 10g；Methyl isoamyl ketone 10g.
B) preparation technology
By filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Comparative example 4
1) preparation of polyamide modified organic siliconresin
A) composition:
Ternary acid: 1,2,4 benzenetricarboxylic acid 25.2g (0.12mol)；
Diamine: 1,6-is diamidogen 6.38g (0.025mol)；4,4 '-DADPS 11.16g (0.045mol)；
Epoxy terminated silicone oligomer: the 23320g of Dow Corning Corporation, the 24910g of Dow Corning Corporation, Dow Corning Corporation the IC8366.6g of Z-610810g, Wa Ke company
Crosslinking catalyst: butyl titanate 0.24g
Organic solvent: propylene glycol methyl ether acetate 76g, butanol 6.5g
B) synthesis step:
By diamine, ternary acid and crosslinking catalyst uniformly after be warming up at 200 DEG C to heat 3.5h after, be cooled to 90 DEG C, add epoxy resin and silicone oligomer；Heating, to 120 DEG C, heats 3h；It is cooled to 90 DEG C, adds organic solvent and make solid content be 50wt%.
C) polyamide modified organic siliconresin performance
The combination property of polyamide modified organic siliconresin
2) coating
A) composition
Polyamide modified organic siliconresin: the polyamide modified organic siliconresin 140g of step 1 preparation；
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
By pigment, filler, polyamide modified organic siliconresin, organosilicon auxiliary agent, high boiling solvent mix homogeneously, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance indications of coating
Resin in contrast coating is to adopt silicone intermediate that polyamide is modified, and this resin has good heat resistance, and its heat resisting temperature reaches 400 DEG C.But in preparing polyamide process, it is not added with amino modified superfine silicon dioxide prepares modified ultra-branching polyamide, and by modified ultra-branching polyamide with containing the reaction of epoxy silicones oligomer, cause that the hardness of film is low, only 3H.
The coating heat resistance of resin Preparation of the present invention reaches 500～520 DEG C, and hardness reaches 6～7H.Its heat resistance and hardness are far better than contrast coating.
Claims (4)
1. a preparation method for the polyamide modified organic siliconresin of high rigidity, the method is made up of following steps:
1～4h will be heated under 180～220 DEG C of conditions after diamine, the ternary acid of diamine molal quantity 1～2.0 times, the amination ultra-fine alumina of diamine weight 1～2 times, the crosslinking catalyst of 1～5% of diamine weight and the dimethylbenzene mix homogeneously of diamine weight 3～8 times；Then it is cooled to 90 DEG C, adds the epoxy terminated silicone oligomer of diamine weight 1.5～2.0 times, under 120～140 DEG C of conditions, heat 2～3h；Finally it is cooled to 90 DEG C, adds organic solvent and make solid content be 40～50wt%；
Described diamine is the one in isophorone diamine, 4,4 '-MDA, 4,4 '-DADPS and 1,6-diamidogen or two or more；
Described ternary acid is the one in 1,2,4 benzenetricarboxylic acid and 1,3,5-benzenetricarboxylic acid or two kinds；
The particle diameter of described amination ultra-fine alumina is 30～150nm, and amino content is 1.2～2mmol/g；
The weight average molecular weight of described epoxy terminated silicone oligomer is 2000～3000, and every epoxy terminated silicone oligomer of 100g contains 60～120mmol epoxy radicals；Described epoxy terminated silicone oligomer is by the γ-(2 of silicone oligomer and silicone oligomer weight 1～10%, 3-epoxy the third oxygen) propyl trimethoxy silicane or γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane hydrolysis-condensation reaction obtains, the molecular weight of wherein said silicone oligomer is 800～2000, and contains the methoxy or ethoxy of 2.5～15wt% and the hydroxyl of 3～20wt%；
Described crosslinking catalyst is butyl titanate；
Described organic solvent is one or more in butanol, isobutanol, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate and dipropylene acetate.
2. the preparation method of the polyamide modified organic siliconresin of a kind of high rigidity according to claim 1, it is characterized in that, wherein said amination ultra-fine alumina is prepared by following methods, the gamma-aminopropyl-triethoxy-silane of ultra-fine alumina and ultra-fine alumina weight 0.4～0.8 times is added in dry toluene, is heated to reflux 3～5h；Product at reduced pressure sucking filtration, vacuum drying obtains alkylation ultra-fine alumina.
3. the preparation method of the polyamide modified organic siliconresin of a kind of high rigidity according to claim 1, it is characterised in that the particle diameter of described amination ultra-fine alumina is 50～100nm, and amino content is 1.4～1.8mmol/g.
4. a coating, this coating contains the polyamide modified organic siliconresin of 60～80wt%, 10～20wt% high-temperature resisting pigment filler and 5～20wt% high boiling solvent；Wherein, described high boiling solvent refers to the one in ethylene glycol ether acetate, butyl acetate, isobutyl isobutyrate, propanoic acid-3-ether ethyl ester and methyl isoamyl ketone or two or more, it is characterized in that, described polyamide modified organic siliconresin is prepared by the described method of one of claims 1 to 3.
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| JPH04126719A (en) * | 1990-09-18 | 1992-04-27 | Tomoegawa Paper Co Ltd | Polyamide-polysiloxane-based block copolymer and production thereof |
| CN102964592A (en) * | 2012-11-27 | 2013-03-13 | 南方医科大学 | Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin |
| CN103113578A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Modified carboxyl-terminated hyperbranched polyamide resin, as well as preparation method and application thereof |
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| JPS6440527A (en) * | 1987-08-07 | 1989-02-10 | Toshiba Silicone | Siloxane-amide block copolymer having terminal alkenyl group and production thereof |
| JPH04126719A (en) * | 1990-09-18 | 1992-04-27 | Tomoegawa Paper Co Ltd | Polyamide-polysiloxane-based block copolymer and production thereof |
| CN102964592A (en) * | 2012-11-27 | 2013-03-13 | 南方医科大学 | Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin |
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