CN104004198A - Preparation method of high-hardness polyamide modified organic silicon resin and coatings containing high-hardness polyamide modified organic silicon resin - Google Patents
Preparation method of high-hardness polyamide modified organic silicon resin and coatings containing high-hardness polyamide modified organic silicon resin Download PDFInfo
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Abstract
The invention relates to a preparation method of high-hardness polyamide modified organic silicon resin. The method comprises the following steps that diamine, tribasic acid, aminated ultrafine alumina, a crosslinking catalyst and xylene are mixed evenly and heated at 180 DEG C-220 DEG C for 1 h-4 h, wherein the mole number of the tribasic acid is 1-2.0 times that of the diamine, the weight of the aminated ultrafine alumina is 1-2 times that of the diamine, the weight of the crosslinking catalyst is 1 percent-5 percent that of the diamine, and the weight of the xylene is 3-8 times that of the diamine; afterwards, the temperature is reduced to 90 DEG C, end-epoxy group organosilicone oligomer is added, and the mixture is heated at 120 DEG C-140 DEG C for 2 h-3 h, wherein the weight of the end-epoxy group organosilicone oligomer is 1.5-2.0 times that of the diamine; finally, the temperature is reduced to 90 DEG C, and an organic solvent is added, so that the solid content is 40 percent-50 percent by weight. The resin prepared through the method can be used for manufacturing high-temperature-resistant low-surface-energy coatings. According to the method, the aminated ultrafine alumina, the diamine and the tribasic acid react together to prepare modified hyperbranched polyamide, and the heat resistance and the hardness of polyamide are enhanced; as the modified hyperbranched polyamide and the epoxy-group-containing organosilicone oligomer are in a cross-linking reaction, the heat resistance and the hardness of the polyamide are further enhanced.
Description
Technical field
The present invention relates to organic high molecular compound field, relate to the macromolecular compound that amidate action obtains, be specifically related to polyamide resin.
Background technology
Polyamide resin has good thermotolerance, wearability, chemical proofing and good mechanical property and processing characteristics, and frictional coefficient is low, has certain flame retardant resistance, is easy to processing, is widely used as engineering plastics.The consistency of polymeric amide and various kinds of resin is good, in coating industry, is used widely.But polyamide resin molecular weight is large, poorly soluble, and viscosity is high, more difficult and other resins carry out chemical modification.Ultrabranching polyamide resin has highly branched structure and a large amount of end group active groups, has high resolution, low viscosity and higher chemical reactivity, and these make ultrabranching polyamide resin demonstrate in many aspects tempting application prospect.
Have in silicone resin-Si-O-Si-structure, demonstrates the performances such as good weathering resistance, thermotolerance, anti-stain characteristic and chemically stable.But pure silicone resin needs hot setting, and long construction inconvenience set time, simultaneously with the poor adhesive force of metallic substance, poor solvent resistance, physical strength is not high, expensive, so its use is subject to restriction to a certain extent, therefore conventional other resins carry out modification to it.Publication number be the patent application of CN103113578 A disclosed by ultrabranching polyamide modified organic silicone resin, improve the mechanical property of silicone resin and the scheme of chemical resistance.
Ultra-fine alumina is nonpoisonous and tasteless ceramic, is widely used in coating, rubber, plastics etc. as filler, can improve mechanical property, thermal property and the electric property of polymer materials.Ultra-fine alumina has higher polarity, and Surface binding energy is strong, is easy to reunite, and is difficult to infiltrate and disperse in organic medium.When ultra-fine alumina joins in non-polar polymer material, the two polarity differs larger, cause ultra-fine alumina to be assembled, and interface binding power is poor, is difficult to play the enhancement to polymer materials.(the Fu Jifang such as Fu Jifang, Xiao Yinglin, Chen Yi, Shi Liyi, Chen Liya, Zhong Qingdong, insulating material 2011,44 (2), 4) adopt hyper-branched polyester functionalization ultra-fine alumina modification impregnating varnish, find that the Al2O3 of hyper-branched polyester graft modification can improve thermal conductivity, mechanical property and the volume specific resistance of insulating impregnating varnish effectively.The ultrabranching polyamide modified nano-alumina such as Yu Jinhong, finds that this modified aluminas can improve the thermomechanical property of epoxy resin.(Jinhong?Yu,Xingyi?Huang,Lichun?Wang,Peng?Peng,Chao?Wu,Xinfeng?Wu?and?Pingkai?Jiang,Preparation?of?hyperbranched?aromatic?polyamide?grafted?nanoparticles?for?thermal?properties?reinforcement?of?epoxy?composites,Polymer?Chemistry,2011,2,1380-1388.)
But the hardness of the silicone resin that above-mentioned prior art obtains is still not ideal enough.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the polyamide modified silicone resin of a kind of high rigidity, polyamide modified silicone resin prepared by the method have advantages of resistance toheat and hardness good.
The scheme that the present invention solves above-mentioned technical problem is:
A preparation method for the polyamide modified silicone resin of high rigidity, the method is made up of following steps:
After being mixed, the dimethylbenzene of 3～8 times of 1～5% crosslinking catalyst of the amination ultra-fine alumina of 1～2 times of triprotic acid, the diamine weight of 1～2.0 times of diamine, diamine mole number, diamine weight and diamine weight heats 1～4h under 180～220 DEG C of conditions; Then be cooled to 90 DEG C, add the epoxy terminated silicone oligomer of 1.5～2.0 times of diamine weight, under 120～140 DEG C of conditions, heat 2～3h; Finally be cooled to 90 DEG C, adding organic solvent to make solid content is 40～50wt%;
Described diamine is isophorone diamine, 4,4 '-diaminodiphenylmethane, DDS and 1,6-a kind of or two or more in diamines;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3,5-benzene tricarboxylic 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 the epoxy terminated silicone oligomer of every 100g contains 20～200mmol epoxy group(ing);
Described crosslinking catalyst is tetrabutyl titanate;
Described organic solvent is one or more in butanols, isopropylcarbinol, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate.
In above-mentioned preparation method, described epoxy terminated silicone oligomer can be 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) propyl group methyl dimethoxysilane hydrolysis-condensation reaction obtains, the molecular weight of wherein said silicone oligomer is for being 800～2000, and the hydroxyl of the methoxy or ethoxy that contains 2.5～15wt% and 3～20wt%; Wherein, described hydrolysis-condensation reaction is the conventional hydrolysis-condensation reaction in this area, and its technique and reaction conditions are the routine techniquess that those skilled in the art should grasp.
Above-mentioned preparation method, wherein said silicone oligomer can be obtained by the condensation reaction that is hydrolyzed of the siloxanes such as methltriethoxysilone, dimethyldiethoxysilane and a phenyl triethoxy, also can be obtained by the condensation reaction that is hydrolyzed of the siloxanes such as monomethyl Trimethoxy silane, dimethyldimethoxysil,ne and a phenyl trimethoxy.Wherein, the condensation reaction that is hydrolyzed of described siloxanes is the condensation reaction that is hydrolyzed of the conventional siloxanes in this area, and its technique and reaction conditions are the routine techniquess that those skilled in the art should grasp.
Above-mentioned preparation method, wherein said silicone oligomer can also be 233 of Dow Corning Corporation, 249 of Dow Corning Corporation, the Z-6108 of Dow Corning Corporation, the IC836 of Wa Ke company, 3074 of Dow Corning Corporation, the silicone resin KR150 of SHIN-ETSU HANTOTAI, the KR211 of company of SHIN-ETSU HANTOTAI, the KR212 of company of SHIN-ETSU HANTOTAI, the KR214 of company of SHIN-ETSU HANTOTAI, the KR216 of company of SHIN-ETSU HANTOTAI, the one in the KR213 of company of SHIN-ETSU HANTOTAI or two or more.
Above-mentioned preparation method, wherein said amination ultra-fine alumina is prepared by following methods, the γ-aminopropyl triethoxysilane of 0.4～0.8 times of ultra-fine alumina and ultra-fine alumina weight is added in dry toluene to reflux 3～5h; Product decompress filter, 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 the epoxy terminated silicone oligomer of every 100g contains 60～120mmol epoxy group(ing).
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 silicone resin prepared by method of the present invention, has the following advantages:
Diamine, triprotic acid and amination ultra-fine alumina are reacted to the alumina modified ultrabranching polyamide resin of preparation, wherein diamine and triprotic acid carry out ultrabranching polyamide prepared by amidate action and are grafted to the surface of amination ultra-fine alumina, ultra-fine alumina is embedded in ultrabranching polyamide, improve resistance toheat and the hardness of polymeric amide.
On the other hand, alumina modified ultrabranching polyamide resin and epoxy terminated silicone oligomer are carried out to crosslinking reaction and prepare polyamide resin modified organic silicone resin, improve resistance toheat and the hardness of polyamide modified silicone resin.
A kind of coating, this coating contains the above-mentioned polyamide modified silicone resin of weight part 60～80wt%, 10～20wt% is high temperature resistant filler and 5～20wt% high boiling solvent, wherein,
Described high boiling solvent is 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;
Described filler is the conventional high temperature resistant filler in this area, can be titanium dioxide or silicon carbide.
In above-mentioned coating, also can add the conventional high-temperature resisting pigment in this area, described high-temperature resisting pigment can be the inorganic high-temperature resistant such as carbon black, iron oxide red 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 the effects such as levelling, froth breaking, pigment wetting, viscosity adjustment.Above-mentioned organosilicon auxiliary agent can also be silicone oil, organic silicon modified by polyether auxiliary agent, as, the CoatOSil series organic silicon modified by polyether auxiliary agent of Mai Tu new high-tech material company limited.Those skilled in the art can be according to the kind and the consumption that require to determine organic silicon additive, and the consumption that the inventor recommends is 1～5wt%.
The preparation method of above-mentioned coating is the conventional preparation method in this area, is mixed to get by polyamide modified silicone resin, pigment, filler, organosilicon auxiliary agent and high boiling solvent.
Because coating of the present invention adopts above-mentioned polyamide modified silicone resin preparation, therefore there is high heat resistance energy and good hardness.
Embodiment
It is below 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
γ-aminopropyl triethoxysilane: 12g
Toluene: 500g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 3h; Decompression filters, the dry amination ultra-fine alumina 39g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, and result is 100nm;
The ammonia value of amination ultra-fine alumina adopts determination of acid-basetitration, and its concrete steps are as follows: the amination ultra-fine alumina that first accurately takes about 1.5g, in Erlenmeyer flask, adds 20mL tetrahydrofuran (THF) and toluene, stirs it is uniformly dispersed; Add again 3～4 methyl orange indicators, the salt acidometric titration taking concentration as 0.2mol/L, color is titration end point in the time that yellow becomes lightcoral.Ammonia value is calculated as follows
A＝(V-V0)*c/m
A: ammonia value is mole number 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively after siloxanes and 4.5mmol hydrochloric acid by proportioning, start to stir and heat up, keep homo(io)thermism after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules and the water that in reaction process, produce, cool to room temperature, adding dimethylbenzene to adjust solid content 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 914; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 12wt%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 7.1wt%.
3) preparation of epoxy terminated silicone oligomer
Silicone oligomer: silicone oligomer 100g prepared by step 2
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 3.5g
γ-(2,3-epoxy the third oxygen) propyl group methyl dimethoxysilane 1.5g
B) preparation technology
Prolong is being housed, thermometer, in the reactor of dropping funnel and agitator, add successively silicone oligomer by proportioning, after 0.05g tetramethyl ammonium hydroxide and 30g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane and γ-(2, 3-epoxy the third oxygen) propyl group methyl dimethoxysilane, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool 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 to detect, and result is 2588; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 110mmol/100g.
4) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 31.5g (0.15mol);
Diamine: DDS 2.88g (0.012mol); Isophorone diamine 6.8g (0.04mol); 4,4 '-diaminodiphenylmethane 7.54g (0.038mol); 1,6-is diamines 1.16g (0.01mol);
Amination ultra-fine alumina: amination ultra-fine alumina 28.6g prepared by step 1
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 48g that solid content prepared by step 3 is 60wt%
Dimethylbenzene: 95g
Crosslinking catalyst: tetrabutyl titanate 0.17g
Organic solvent: 1-Methoxy-2-propyl acetate 15g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 180 DEG C and heats after 4h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated silicone oligomer; Be heated to 130 DEG C, heating 3.5h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
1* resistance toheat: test piece is toasted after 2h in 180 DEG C, put into the Ovenized electric furnace that potentiometer is checked, by 5 DEG C/min rising temperature, start timing with furnace temperature to requirement of experiment temperature, sample, after continuous high temperature, takes out, be chilled to room temperature (25 DEG C), observe coatingsurface situation with magnifying glass, as without be full of cracks, obscission, illustrate that coating heat resistance can be good.
5) coating
A) composition
The end polyamide resin of modification: the polyamide modified silicone resin 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
Filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 2:
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 40g
γ-(2,3-epoxy the third oxygen) propyl group methyl dimethoxysilane: 32g
Toluene: 600g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-(2,3-epoxy the third oxygen) propyl group methyl dimethoxysilane, reflux 5h; Decompression filters, the dry amination ultra-fine alumina 68g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively after siloxanes and 4.5mmol hydrochloric acid by proportioning, start to stir and heat up, keep homo(io)thermism after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules and the water that in reaction process, produce, cool 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 to detect, and result is 802; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 10.6wt%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 7.4wt%; R/Si=1.14; Ph/Me=1.04.
3) preparation of 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) propyl group methyl dimethoxysilane 0.5g
B) preparation technology
Prolong is being housed, thermometer, in the reactor of dropping funnel and agitator, add successively silicone oligomer by proportioning, after 0.03g tetramethyl ammonium hydroxide and 10g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane and γ-(2, 3-epoxy the third oxygen) propyl group methyl dimethoxysilane, again after isothermal reaction 4h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool 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 to detect, and result is 2457; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 87mmol/100g.
4) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 29.4g (0.14mol);
Diamine: 1,6-is diamines 8.12g (0.05mol); DDS 7.44g (0.03mol)
Amination ultra-fine alumina: amination ultra-fine alumina 22.5g prepared by step 1
Dimethylbenzene: 120g
Epoxy terminated silicone oligomer: epoxy terminated silicone oligomer 41g prepared by step 2
Crosslinking catalyst: tetrabutyl titanate 0.3g
Organic solvent: dipropylene glycol methyl ether acetate 10g, dipropylene glycol monobutyl ether acetate 10g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 210 DEG C and heats after 2h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated silicone oligomer; Be heated to 135 DEG C, heating 3h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 40wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
5) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 160g prepared by step 4;
Filler: titanium dioxide 20g, silicon carbide 8g
Organosilicon auxiliary agent: silicone oil
/ 350cst1g.
High boiling solvent: ethylene glycol ether acetate (CAC): 10g.
B) preparation technology
Filler, polyamide modified silicone resin, high boiling solvent, auxiliary agent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 3:
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 40g
γ-aminopropyl triethoxysilane: 20g
Toluene: 400g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 3h; Decompression filters, the dry amination ultra-fine alumina 57g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively after siloxanes and 4.5mmol sulfuric acid by proportioning, start to stir and heat up, keep homo(io)thermism after being warmed up to 60 DEG C, under agitation drip 28g distilled water, after dropwising, after isothermal reaction 4h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool to room temperature, adding dimethylbenzene to adjust solid content is 60wt%, obtains silicone oligomer 252g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 1986; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 12wt%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 6.7wt%.
3) preparation of epoxy terminated silicone oligomer
A) composition
Silicone oligomer: solid content prepared by step 2 is 60wt% silicone oligomer 100g
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 6g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively silicone oligomer by proportioning, after 0.2g tetramethyl ammonium hydroxide and 30g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling, at 0.06MPa, boils off the small molecules producing in reaction process, cool 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 to detect, and result is 2635; Oxirane value content adopts hydrochloric acid-acetone method to measure, and result is 197mmol/100g.
4) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 23.1g (0.11mol);
Diamine: DDS 14.9g (0.05mol); Isophorone diamine 8.5g (0.05mol)
Amination ultra-fine alumina: amination ultra-fine alumina 37.4g prepared by step 1
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 62.4g that solid content prepared by step 2 is 60wt%
Dimethylbenzene: 94g
Crosslinking catalyst: tetrabutyl titanate 0.33g
Organic solvent: 1-Methoxy-2-propyl acetate 28g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 190 DEG C and heats after 3h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated silicone oligomer; Be heated to 135 DEG C, heating 2h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 45wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
5) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 100g prepared by step 4;
Filler: titanium dioxide 10g, silicon carbide 30g
Organosilicon auxiliary agent: CoatOSil70014g; Silicone oil
/ 350cst6g;
High boiling solvent: Diethylene Glycol monobutyl ether acetate 5g; N-BUTYL ACETATE 5g.
B) preparation technology
Filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 4:
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
γ-aminopropyl triethoxysilane: 21g
Toluene: 350g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 3.5h; Decompression filters, the dry amination ultra-fine alumina 48.6g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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) propyl group methyl dimethoxysilane 3g
B) preparation technology
Prolong is being housed, thermometer, in the reactor of dropping funnel and agitator, add successively silicone oligomer by proportioning, after 0.03g tetramethyl ammonium hydroxide and 20g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2, 3-epoxy the third oxygen) propyl group methyl dimethoxysilane, again after isothermal reaction 3.5h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool to room temperature, adjustment solid content is 60wt%, obtain epoxy terminated silicone oligomer 114g.
C) performance
The weight-average molecular weight of epoxy terminated silicone oligomer adopts gel permeation chromatography to detect, and result is 1958; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 108mmol/100g.
3) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 37.8g (0.18mol);
Diamine: isophorone diamine 3.4g (0.02mol); 1,6-is diamines 5.81g (0.05mol); DDS 7.44g (0.03mol)
Amination ultra-fine alumina: amination ultra-fine alumina 21.6g prepared by step 1
Epoxy terminated silicone oligomer: epoxy terminated silicone oligomer 55.5g prepared by step 2
Dimethylbenzene: 50g
Crosslinking catalyst: tetrabutyl titanate 0.64g
Organic solvent: 1-Methoxy-2-propyl acetate 7g, butanols 10g, dipropylene glycol methyl ether acetate 10g, dipropylene glycol monobutyl ether acetate 10g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 220 DEG C and heats after 1h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated silicone oligomer; Be heated to 140 DEG C, heating 2h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
4) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 120g prepared by step 3;
Filler: silicon carbide 20g;
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, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 5
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
γ-aminopropyl triethoxysilane: 19.5g
Toluene: 310g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 4.5h; Decompression filters, the dry amination ultra-fine alumina 47.6g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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 Z-610820g of the 23330g of Dow Corning Corporation, the 24920g of Dow Corning Corporation, Dow Corning Corporation, the IC83620g of Wa Ke company, the KR21310g of company of SHIN-ETSU HANTOTAI
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 4g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively silicone oligomer by proportioning, after 0.03g tetramethyl ammonium hydroxide and 20g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling, at 0.06MPa, boils off the small molecules producing in reaction process, cool 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 to detect, and result is 1555; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 145mmol/100g.
3) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 25.2g (0.12mol);
Diamine: 1,6-is diamines 6.38g (0.055mol); DDS 11.16g (0.045mol);
Amination ultra-fine alumina: amination ultra-fine alumina 24.4g prepared by step 1
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 46.6g that solid content prepared by step 2 is 60wt%
Dimethylbenzene: 70g
Crosslinking catalyst: tetrabutyl titanate 0.24g
Organic solvent: 1-Methoxy-2-propyl acetate 3g, isopropylcarbinol 3g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 200 DEG C and heats after 3.5h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated 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) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
4) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 120g prepared by step 3;
Filler: silicon carbide 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
Pigment, filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 6
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
γ-aminopropyl triethoxysilane: 18g
Toluene: 440g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 3.5h; Decompression filters, the dry amination ultra-fine alumina 45g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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: the silicone resin KR15015g of SHIN-ETSU HANTOTAI, 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) propyl group methyl dimethoxysilane 3g
B) preparation technology
Prolong is being housed, thermometer, in the reactor of dropping funnel and agitator, add successively silicone oligomer by proportioning, after 0.03g tetramethyl ammonium hydroxide and 20g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2, 3-epoxy the third oxygen) propyl group methyl dimethoxysilane and γ-(2, 3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool 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 to detect, and result is 2865; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 162mmol/100g.
3) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 29.4g (0.14mol); 1,2,4-benzene tricarboxylic acid 12.6g (0.06mol);
Diamine: 1,6-hexanediamine 4.64g (0.04mol); Isophorone diamine 6.8g (0.04mol); 4,4 '-diaminodiphenylmethane 3.96g (0.02mol);
Amination ultra-fine alumina: amination ultra-fine alumina 27g prepared by step 1
Dimethylbenzene: 62g
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 25.7g that solid content prepared by step 3 is 80wt%
Crosslinking catalyst: tetrabutyl titanate 0.13g
Organic solvent: dipropylene glycol methyl ether acetate 10g, propylene glycol monomethyl ether 10g, butanols 8g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 190 DEG C and heats after 3h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated 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 45wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
4) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 110g prepared by step 3;
Filler: silicon carbide 15g; Titanium dioxide 5g;
Pigment: phthalocyanine blue 8g;
High boiling solvent: methyl isoamyl ketone 40g; Isobutyl isobutyrate 20g.
B) preparation technology
Pigment/filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 7
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
γ-aminopropyl triethoxysilane: 13.5g
Toluene: 330g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 5h; Decompression filters, the dry amination ultra-fine alumina 39g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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 silicone resin KR15050g of SHIN-ETSU HANTOTAI, the IC83650g of Wa Ke company
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 0.6g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively silicone oligomer by proportioning, after 0.01g tetramethyl ammonium hydroxide and 20g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling, at 0.06MPa, boils off the small molecules producing in reaction process, cool 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 to detect, and result is 997; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 19mmol/100g.
3) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 21g (0.10mol);
Diamine: DDS 9.19g (0.037mol); 1,6-hexanediamine 5.8g (0.05mol)
Amination ultra-fine alumina: amination ultra-fine alumina 26.8g prepared by step 1
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 38.5g that solid content prepared by step 2 is 70wt%
Dimethylbenzene: 60g
Crosslinking catalyst: tetrabutyl titanate 0.44g
Organic solvent: 1-Methoxy-2-propyl acetate 7g butanols 11g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 190 DEG C and heats after 3h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated silicone oligomer; Be heated to 135 DEG C, heating 2h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
4) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 140g prepared by step 3;
Filler: silicon carbide 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, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 8
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
γ-aminopropyl triethoxysilane: 16.5g
Toluene: 420g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 4.5h; Decompression filters, the dry amination ultra-fine alumina 43g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively after siloxanes and 7.0mmol hydrochloric acid by proportioning, start to stir and heat up, keep homo(io)thermism after being warmed up to 70 DEG C, under agitation drip 43.1g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool to room temperature, adding dimethylbenzene to adjust solid content is 60wt%, obtains silicone oligomer 220g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 1986; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 15wt%; The oxyethyl group 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: solid content prepared by step 2 is 60wt% silicone oligomer 100g
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 0.8g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively silicone oligomer by proportioning, after 0.02g tetramethyl ammonium hydroxide and 20g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling, at 0.06MPa, boils off the small molecules producing in reaction process, cool 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 to detect, and result is 3445; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 34mmol/100g.
4) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 4.2g (0.02mol); 1,3,5-benzene tricarboxylic acid 21g (0.1mol)
Diamine: DDS 14.9g (0.6mol); 1,6-hexanediamine 4.64g (0.04mol)
Amination ultra-fine alumina: amination ultra-fine alumina 33.9g prepared by step 1
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 37.2g that solid content prepared by step 2 is 80wt%
Dimethylbenzene: 140g
Crosslinking catalyst: tetrabutyl titanate 0.26g
Organic solvent: 1-Methoxy-2-propyl acetate 5g, dipropylene glycol methyl ether 5g, dipropylene glycol butyl ether 5g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 190 DEG C and heats after 3h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated silicone oligomer; Be heated to 135 DEG C, heating 2h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 40wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
5) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 150g prepared by step 4;
Filler: silicon carbide 20g;
Organosilicon auxiliary agent: CoatOSil35005g; Silicone oil
/ 350cst5g;
High boiling solvent: methyl isoamyl ketone 10g.
B) preparation technology
Paint filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 9
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 30g
γ-aminopropyl triethoxysilane: 15g
Toluene: 400g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 5h; Decompression filters, the dry amination ultra-fine alumina 41g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively after siloxanes and 7.0mmol hydrochloric acid by proportioning, start to stir and heat up, keep homo(io)thermism after being warmed up to 70 DEG C, under agitation drip 43.1g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool to room temperature, adding dimethylbenzene to adjust solid content is 60wt%, obtains silicone oligomer 220g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and result is 1986; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 15wt%; The oxyethyl group 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: solid content prepared by step 2 is 60wt% silicone oligomer 100g
γ-(2,3-epoxy the third oxygen) propyl group methyl dimethoxysilane 1.4g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively silicone oligomer by proportioning, after 0.02g tetramethyl ammonium hydroxide and 20g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2,3-epoxy the third oxygen) propyl group methyl dimethoxysilane, again after isothermal reaction 3h, start underpressure distillation, pressure-controlling, at 0.06MPa, boils off the small molecules producing in reaction process, cool 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 to detect, and result is 3985; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 44mmol/100g.
4) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 4.2g (0.02mol); 1,3,5-benzene tricarboxylic acid 21g (0.1mol)
Diamine: DDS 14.9g (0.6mol); 1,6-hexanediamine 4.64g (0.04mol)
Amination ultra-fine alumina: amination ultra-fine alumina 19.54g prepared by step 1
Epoxy terminated silicone oligomer: the epoxy terminated silicone oligomer 36.6g that solid content prepared by step 2 is 80wt%
Dimethylbenzene: 58.6g
Crosslinking catalyst: tetrabutyl titanate 0.26g
Organic solvent: 1-Methoxy-2-propyl acetate 26g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 190 DEG C and heats after 3h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated silicone oligomer; Be heated to 135 DEG C, heating 2h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
5) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 150g prepared by step 4;
Filler: titanium dioxide 40g;
Organic additive: CoatOSil75108g;
Height boils and reaches solvent: methyl isoamyl ketone 2g.
B) preparation technology
Filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 10
1) preparation of amination ultra-fine alumina
A) formula
Ultra-fine alumina: 40g
γ-aminopropyl triethoxysilane: 26g
Toluene: 350g
B) preparation technology
In the reactor that prolong, thermometer and agitator are housed, add ultra-fine alumina and toluene, after high speed dispersion is even, add γ-aminopropyl triethoxysilane, reflux 5h; Decompression filters, the dry amination ultra-fine alumina 61g that obtains.
C) performance
The particle diameter of amination ultra-fine alumina adopts DSL to detect, 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively after siloxanes and 4.5mmol hydrochloric acid by proportioning, start to stir and heat up, keep homo(io)thermism after being warmed up to 60 DEG C, under agitation drip 31.7g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool 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 to detect, and result is 802; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 10.6wt%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and result is 7.4wt%; R/Si=1.14; Ph/Me=1.04.
3) preparation of epoxy terminated silicone oligomer
Silicone oligomer: solid content prepared by step 2 is 60wt% silicone oligomer 100g
γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane 0.6g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively silicone oligomer by proportioning, after 0.01g tetramethyl ammonium hydroxide and 20g toluene, start to stir and heat up, after being warmed up to 90 DEG C, keep homo(io)thermism, under agitation slowly add γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, again after isothermal reaction 1h, start underpressure distillation, pressure-controlling, at 0.06MPa, boils off the small molecules producing in reaction process, cool 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 to detect, and result is 1005; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is 20mmol/100g.
4) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 10.5g (0.05mol); 1,2,4-benzene tricarboxylic acid 10.5g (0.05mol);
Diamine: 1,6-hexanediamine 6.96g (0.06mol); Two amido sulfobenzide 9.94g (0.04mol);
Amination ultra-fine alumina: amination ultra-fine alumina 33.8g prepared by step 1
Dimethylbenzene: 134g
Epoxy terminated silicone oligomer: solid content prepared by step 2 is the epoxy terminated silicone oligomer 56.3g of 60wt%
Crosslinking catalyst: tetrabutyl titanate 0.168g
Organic solvent: 1-Methoxy-2-propyl acetate 1g
B) synthesis step:
By diamine, triprotic acid, amination ultra-fine alumina, is warming up at 180 DEG C and heats after 4h after crosslinking catalyst and dimethylbenzene mix, and is cooled to 90 DEG C, adds epoxy terminated silicone oligomer; Be heated to 140 DEG C, heating 2h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 40wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
5) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 120g prepared by step 4;
Filler: titanium dioxide 20g; Silicon carbide 40g;
Organosilicon auxiliary agent: CoatOSil7510:2g;
High boiling solvent: methyl isoamyl ketone 18g.
B) preparation technology
Filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Comparative example 1
The preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 29.4g (0.14mol); 1,2,4-benzene tricarboxylic acid 12.6g (0.06mol);
Diamine: 1,6-hexanediamine 4.64g (0.04mol); Isophorone diamine 6.8g (0.04mol); 4,4 '-diaminodiphenylmethane 3.96g (0.02mol);
Epoxy resin: epoxy resin E-125g
Silicone oligomer 25.7g prepared by silicone oligomer: embodiment 2
Crosslinking catalyst: tetrabutyl titanate 0.13g
Organic solvent: dipropylene glycol methyl ether acetate 63g butanols 35g
B) synthesis step:
By diamine, after triprotic acid and crosslinking catalyst are even, are warming up at 190 DEG C and heat after 3h, be cooled to 90 DEG C, add epoxy resin and silicone oligomer; Be heated to 130 DEG C, heating 2.5h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 45wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
2) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 160g prepared by step 1;
Filler: titanium dioxide 20g, silicon carbide 8g
Organosilicon auxiliary agent: silicone oil
/ 350cst1g.
High boiling solvent: ethylene glycol ether acetate (CAC): 10g.
B) preparation technology
Filler, polyamide modified silicone resin, high boiling solvent, auxiliary agent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Comparative example 2:
1) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 29.4g (0.14mol);
Diamine: 1,6-is diamines 8.12g (0.05mol); DDS 7.44g (0.03mol)
Epoxy resin: epoxy resin E-514g
Silicone oligomer 41g prepared by silicone oligomer: embodiment 3
Crosslinking catalyst: tetrabutyl titanate 0.3g
Organic solvent: dipropylene glycol methyl ether acetate 50g, dipropylene glycol monobutyl ether acetate 10g
B) synthesis step:
By diamine, after triprotic acid and crosslinking catalyst are even, are warming up at 210 DEG C and heat after 2h, be cooled to 90 DEG C, add epoxy resin and silicone oligomer; Be heated to 135 DEG C, heating 3h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
4) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 100g prepared by step 3;
Filler: titanium dioxide 10g, silicon carbide 30g
Organosilicon auxiliary agent: CoatOSil70014g; Silicone oil
/ 350cst6g;
High boiling solvent: Diethylene Glycol monobutyl ether acetate 5g; N-BUTYL ACETATE 5g.
B) preparation technology
Filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Comparative example 3:
1) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 37.8g (0.18mol);
Diamine: isophorone diamine 3.4g (0.02mol); 1,6-is diamines 5.81g (0.05mol); DDS 7.44g (0.03mol)
Epoxy resin: epoxy resin E-44 3g
Silicone oligomer: the 307455.5g of Dow Corning Corporation
Diethylene Glycol monobutyl ether acetate: 33.3g
Connection catalyzer: tetrabutyl titanate 0.64g
Organic solvent: 1-Methoxy-2-propyl acetate 41.3g, butanols 8g, dipropylene glycol methyl ether acetate 8g, dipropylene glycol monobutyl ether acetate 20g
B) synthesis step:
By diamine, after triprotic acid and crosslinking catalyst are even, are warming up at 220 DEG C and heat after 1h, be cooled to 90 DEG C, add epoxy resin and silicone oligomer; Be heated to 140 DEG C, heating 2h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
2) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 120g prepared by step 1;
Filler: silicon carbide 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, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Comparative example 4
1) preparation of polyamide modified silicone resin
A) composition:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 25.2g (0.12mol);
Diamine: 1,6-is diamines 6.38g (0.025mol); DDS 11.16g (0.045mol);
Epoxy terminated silicone oligomer: the Z-610810g of the 23320g of Dow Corning Corporation, the 24910g of Dow Corning Corporation, Dow Corning Corporation, the IC8366.6g of Wa Ke company
Crosslinking catalyst: tetrabutyl titanate 0.24g
Organic solvent: 1-Methoxy-2-propyl acetate 76g, butanols 6.5g
B) synthesis step:
By diamine, after triprotic acid and crosslinking catalyst are even, are warming up at 200 DEG C and heat after 3.5h, be cooled to 90 DEG C, add epoxy resin and silicone oligomer; Be heated to 120 DEG C, heating 3h; Be cooled to 90 DEG C, adding organic solvent to make solid content is 50wt%.
C) polyamide modified silicone resin performance
The over-all properties of polyamide modified silicone resin
2) coating
A) composition
Polyamide modified silicone resin: polyamide modified silicone resin 140g prepared by step 1;
Filler: silicon-dioxide 25g; Titanium dioxide 10g;
Pigment: carbon black 10g;
Organosilicon auxiliary agent: CoatOSil35004g; CoatOSil76502g;
High boiling solvent: methyl isoamyl ketone (MIAK) 2g; Isobutyl isobutyrate 4g.
B) preparation technology
Pigment, filler, polyamide modified silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Resin in contrast coating is to adopt silicone intermediate to carry out modification to polyamide resin, and this resin has good resistance toheat, and its heat resisting temperature reaches 400 DEG C.But in polyamide resin process, do not add amino modified superfine silicon dioxide and prepare modified ultra-branching polymeric amide preparing, and by modified ultra-branching polymeric amide with containing the reaction of epoxy group(ing) silicone oligomer, cause the hardness of film low, only 3H.
The standby coating resistance toheat of resin of the present invention reaches 500～520 DEG C, and hardness reaches 6～7H.Its resistance toheat and hardness are better than contrast coating far away.
Claims (6)
1. a preparation method for the polyamide modified silicone resin of high rigidity, the method is made up of following steps:
After being mixed, the dimethylbenzene of 3～8 times of 1～5% crosslinking catalyst of the amination ultra-fine alumina of 1～2 times of triprotic acid, the diamine weight of 1～2.0 times of diamine, diamine mole number, diamine weight and diamine weight heats 1～4h under 180～220 DEG C of conditions; Then be cooled to 90 DEG C, add the epoxy terminated silicone oligomer of 1.5～2.0 times of diamine weight, under 120～140 DEG C of conditions, heat 2～3h; Finally be cooled to 90 DEG C, adding organic solvent to make solid content is 40～50wt%;
Described diamine is isophorone diamine, 4,4 '-diaminodiphenylmethane, DDS and 1,6-a kind of or two or more in diamines;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3,5-benzene tricarboxylic 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 the epoxy terminated silicone oligomer of every 100g contains 20～200mmol epoxy group(ing);
Described crosslinking catalyst is tetrabutyl titanate;
Described organic solvent is one or more in butanols, isopropylcarbinol, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate.
2. the preparation method of the polyamide modified silicone resin of a kind of high rigidity according to claim 1, it is characterized in that, 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) propyl group methyl dimethoxysilane hydrolysis-condensation reaction obtains, the molecular weight of wherein said silicone oligomer is for being 800～2000, and the hydroxyl of the methoxy or ethoxy that contains 2.5～15wt% and 3～20wt%.
3. the preparation method of the polyamide modified silicone resin 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 γ-aminopropyl triethoxysilane of 0.4～0.8 times of ultra-fine alumina and ultra-fine alumina weight is added in dry toluene to reflux 3～5h; Product decompress filter, vacuum-drying obtains alkylation ultra-fine alumina.
4. the preparation method of the polyamide modified silicone resin of a kind of high rigidity according to claim 1, it is characterized in that, the weight-average molecular weight of described epoxy terminated silicone oligomer is 2000～3000, and the epoxy terminated silicone oligomer of every 100g contains 60～120mmol epoxy group(ing).
5. the preparation method of the polyamide modified silicone resin of a kind of high rigidity according to claim 1, is characterized in that, the particle diameter of described amination ultra-fine alumina is 50～100nm, and amino content is 1.4～1.8mmol/g.
6. a coating, this coating contains the polyamide modified silicone resin of 60～80wt%, 10～20wt% high-temperature resisting pigment filler and 5～20wt% high boiling solvent; Wherein, 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, it is characterized in that, described polyamide modified silicone resin is prepared by the described method of one of claim 1 to 5.
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| CN106010235A (en) * | 2016-05-06 | 2016-10-12 | 哈尔滨宇瀚科技有限公司 | Silver ion and ytterbium ion compound titanium dioxide nanoparticle modified organic silicon resin interior wall antibacterial coating and preparation method thereof |
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