CN102382314B - Preparation method and application of modified organic silicon resin - Google Patents
Preparation method and application of modified organic silicon resin Download PDFInfo
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- CN102382314B CN102382314B CN 201110174525 CN201110174525A CN102382314B CN 102382314 B CN102382314 B CN 102382314B CN 201110174525 CN201110174525 CN 201110174525 CN 201110174525 A CN201110174525 A CN 201110174525A CN 102382314 B CN102382314 B CN 102382314B
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Abstract
The invention relates to the field of organic high-molecular compounds, particularly a preparation method of a modified organic silicon resin. The method comprises the following steps: sequentially heating 40-60 w% carboxyl-terminated hyperbranched polyamide, 1-10 w% epoxy resin, 30-50 w% organic silicon resin and crosslinking catalyst which accounts for 1-10% by weight of the carboxyl-terminated hyperbranched polyamide at 110-120 DEG C, 150-170 DEG C and 200-210 DEG C respectively for 1-3 hours; and finally, cooling to room temperature, and adding an organic solvent to adjust the solid content to 60-70%, thereby obtaining the modified organic silicon resin. The method combines the advantages of carboxyl-terminated hyperbranched polyamide, epoxy resin and organic silicon resin to obtain excellent heat resistance, favorable metal adhesive force, low surface energy, excellent water boiling resistance and acid resistance. The resin prepared by the method provided by the invention can be used for preparing high-temperature-resistant low-surface energy paint.
Description
Technical field
The present invention relates to the organic high molecular compound field, relate to the macromolecular compound that only obtains with the silica reaction, be specifically related to silicone resin.
Background technology
Have in the silicone resin-the Si-O-Si-structure, demonstrate 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, and with the poor adhesive force of metallic substance, poor solvent resistance, physical strength are not high, and be expensive, so its use is subject to restriction to a certain degree simultaneously.Other resins commonly used carry out modification to it.Other resins such as use Resins, epoxy carry out modification to silicone resin, can improve the metal adhesion of resin, hardness and mechanical property.Carry out modification such as use bisphenol A epoxide resin p-methylphenyl silicone resins such as Deng Mingshan, obtain fire resistant epoxy modified organic silicone resin (Deng Mingshan, golden double happiness, the Huanghai Sea, the development of epoxy modified silicone high-temperature resistant coating, Anhui chemical industry, 2000,103 (2), 27-29).But the epoxy modified silicone resin difference of hardness, mechanical property can not the satisfying the market requirement.
Polyamide resin has good thermotolerance, wearability, chemical proofing and good mechanical property and processing characteristics, and frictional coefficient is low, and certain flame retardant resistance is arranged, and is easy to processing, is widely used to be engineering plastics.The consistency of polymeric amide and various kinds of resin is good, is used widely in coating industry.But the polyamide resin molecular weight is large, and is poorly soluble, and viscosity is high, and difficult and other resins carry out chemical modification.In order to obtain low viscosity, the polyamide resin that solvability is good, use dimeracid commonly used and diamine polymerization.With Rice pollard oil raw material of fatty acid synthesis of dimmer acid, obtain lower molecular weight with the polyethylene polyamine polymerization again, low viscous polymeric amide such as (Wu Jianliang, the development of low-molecular-weight polyamide resin, Zhejiang chemical industry, 2004,35 (03), 19) such as Wu Jianliang.But the low-molecular-weight polyamide resin poor heat resistance of preparation, end group activation functional group content is few, can not improve the resistance toheat of other resins such as Resins, epoxy.
Hyperbranched polymer has highly branched structure and a large amount of end group active groups, has high resolution, low viscosity and higher chemical reactivity etc.These are so that hyperbranched polymer demonstrates tempting application prospect in many aspects.Low viscosity can reduce system viscosity with the blend of line polymer coating so that hyperbranched polymer is fit to be applied to high solid component coating, and the improvement system is mobile; High solvability can reduce the consumption of solvent, reduces cost, reduces noxious gas emission; Highly branched structure is difficult for crystallization so that the entanglement of hyperbranched polymer molecule interchain is less, makes coating have good film forming properties.But the molecular weight of filming that forms after the hyperbranched polymer film forming is low, and cross-linking density is little to cause the bad mechanical property of filming, and chemical-resistant can meet the demands; The film coated surface that forms after the hyperbranched polymer film forming simultaneously contains abundant active group, reduces the water resistance of filming.
Summary of the invention
The technical problem that the present invention solves provides a kind of preparation method of modified organic silicone resin, and the modified organic silicone resin of the method preparation has the low and good advantage of acidproof water resistance of heat-resisting low surface energy.
For solving technical problem of the present invention, solution provided by the invention is: a kind of preparation method of modified organic silicone resin, and the method is comprised of following steps:
The crosslinking catalyst that silicone resin and the weight of the end carboxyl super branched polymeric amide of 40～60w%, 1～10w% Resins, epoxy and 30～50w% is amine-terminated hyperbrancedization polymeric amide consumption 1～10% adds in the reactor; Under 110～120 ℃, 150～170 ℃ and 200～210 ℃, heated respectively 1～3 hour successively; Be down at last room temperature, adding organic solvent adjustment solid content is 60～70%; In the above-mentioned steps,
The weight-average molecular weight of described end carboxyl super branched polymeric amide is 2000～6000, and it is with diamine, triprotic acid and to contain the aminoalkyl group carboxylic acid be diamine according to the amount of substance ratio: triprotic acid: contain aminoalkyl group carboxylic acid=1: 1～2: 0～0.1 and carry out amidate action and obtain; Wherein, described diamine is 1,3-propylene diamine, 1,2-propylene diamine, Isosorbide-5-Nitrae-cyclohexanediamine, Putriscine, isophorone diamine, 4, and 4 '-diaminodiphenylmethane, DDS and 1,6-hexanediamine are wherein a kind of or two or more; Described triprotic acid is wherein a kind of or mixture of 1,2,4-benzene tricarboxylic acid and 1,3,5-benzene tricarboxylic acid; The described aminoalkyl group carboxylic acid that contains is that glycine, 3-alanine and 3-amino-2-methyl propionic acid are wherein a kind of or two or more;
Described Resins, epoxy is bicyclopentadiene dioxide, 3,4-epoxidation naphthenic acid 3 ', 4 '-epoxidation hexanaphthene methyl esters, two ((3, the 4-epoxycyclohexyl) methyl) adipic acid ester, two (2,3-oxirane ring amyl group) ether, bisphenol-s epoxy resin and TriMethylolPropane(TMP) glycidyl ether are wherein a kind of or two or more;
The weight-average molecular weight of described silicone resin is 800～2000, and contains 2.5～15% methoxy or ethoxy and 3～20% hydroxyl;
Described crosslinking catalyst is that tetrabutyl titanate, tetrabutyl titanate, two octyloxy tin, two different octyloxy tin, two octyloxy zinc and two different octyloxy zinc are wherein a kind of or two or more;
Described organic solvent be butanols, isopropylcarbinol, propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate wherein one or more.
Silicone resin of the present invention can be by methltriethoxysilone, dimethyldiethoxysilane, the condensation reaction that is hydrolyzed of the siloxanes such as one phenyl triethoxy obtains, also can be by the monomethyl Trimethoxy silane, dimethyldimethoxysil,ne, the condensation reaction that is hydrolyzed of the siloxanes such as one phenyl trimethoxy obtains, the mixture of one or more in the following specific product of all right directly use: 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 IC836 of Wa Ke company, the KR213 of company of SHIN-ETSU HANTOTAI, the KR9218 of company of SHIN-ETSU HANTOTAI, the KR217 of company of SHIN-ETSU HANTOTAI, 233 of Dow Corning Corporation, 249 of Dow Corning Corporation, the Z-6108 of Dow Corning Corporation, 3074 of Dow Corning Corporation, 3037 of Dow Corning Corporation.The hydrolysis-condensation reaction of above-mentioned siloxanes is the condensation reaction that is hydrolyzed of this area siloxanes commonly used, and its technique and reaction conditions are the routine techniquess that those skilled in the art should grasp.
The weight-average molecular weight of end carboxyl super branched polymeric amide of the present invention is preferably 3000～4000, and it better is to be prepared by following methods: with triprotic acid, diamine with to contain the aminoalkyl group carboxylic acid be diamine according to the amount of substance ratio: triprotic acid: contain aminoalkyl group carboxylic acid=1: 1～1.4: 0.05～0.1 and add in the reactor; Per hour to heat up 20 ℃ rate of heating, be heated to 240 ℃, under 0.67～1.33kPa, be incubated 2～4h; Cool to room temperature; Wherein, described diamine is Isosorbide-5-Nitrae-cyclohexanediamine, isophorone diamine, 4, and 4 '-diaminodiphenylmethane, DDS and 1,6-hexanediamine are wherein a kind of or two or more; Described triprotic acid is wherein a kind of or mixture of 1,3,5-benzene tricarboxylic acid and 1,2,4-benzene tricarboxylic acid; The described aminoalkyl group carboxylic acid that contains is wherein a kind of or mixture of 3-alanine and 3-amino-2-methyl propionic acid.
Silicone resin of the present invention better be KR9218, the company of SHIN-ETSU HANTOTAI of KR213, the company of SHIN-ETSU HANTOTAI of IC836, the company of SHIN-ETSU HANTOTAI of KR216, the Wa Ke company of KR214, the company of SHIN-ETSU HANTOTAI of KR212, the company of SHIN-ETSU HANTOTAI of KR211, the company of SHIN-ETSU HANTOTAI of company of SHIN-ETSU HANTOTAI KR217, Dow Corning Corporation 233, Dow Corning Corporation 249,3037 one or more kinds of mixtures wherein of 3074 and Dow Corning Corporation of the Z-6108 of Dow Corning Corporation, Dow Corning Corporation.
Resins, epoxy of the present invention is preferably bicyclopentadiene dioxide, 3,4-epoxidation naphthenic acid 3 ', 4 '-epoxidation hexanaphthene methyl esters, two ((3, the 4-epoxycyclohexyl) methyl) adipic acid ester, two (2,3-oxirane ring amyl group) ether, bisphenol-s epoxy resin, TriMethylolPropane(TMP) glycidyl ether are wherein a kind of or two or more.
It is wherein a kind of or two or more that crosslinking catalyst of the present invention is preferably two octyloxy tin, two different octyloxy tin, two octyloxy zinc and two different octyloxy zinc.
Organic solvent of the present invention be preferably propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate one or more.
Among the preparation method of modified organic silicone resin of the present invention, end carboxyl super branched polymeric amide consumption is preferably 50～60w%, content of epoxy resin is preferably 1～8w%, the silicone resin consumption is preferably 35～50w%, and the crosslinking catalyst consumption is preferably amine-terminated hyperbrancedization polymeric amide weight 1～5%.
Three kinds of crosslinking reactions occur among the preparation method of the present invention, the first is that carboxyl and the epoxy group(ing) on the Resins, epoxy on the end carboxyl super branched polymeric amide carried out crosslinking reaction, the second is that silanol base on the silicone resin and the epoxy group(ing) on the Resins, epoxy are carried out condensation reaction, and the third is that the hydroxyl that forms of carboxyl on the end carboxyl super branched polymeric amide and the epoxy reaction on the Resins, epoxy and the alkoxyl group on the silicone resin or silanol base carry out crosslinking reaction.End carboxyl super branched polymeric amide like this, Resins, epoxy and silicone resin carry out in twos crosslinking reaction, form multiple cross-linked IPN pore network structure, the advantages of end carboxyl super branched polymeric amide, Resins, epoxy and silicone resin is got up, and the modified organic silicone resin that obtains has the following advantages:
(1) hyperbranched polymer has highly branched structure, so that the hyperbranched polymer molecule interchain tangles is less, the ultrabranching polyamide modified organic silicone resin of giving the present invention's preparation has the advantage of low viscosity and good film forming properties.
(2) polymeric amide has good wear resisting property, acid resistance and excellent mechanical property, and the ultrabranching polyamide modified organic silicone resin of giving the method for the invention preparation has good mechanical property and acid resistance.
Modified organic silicone resin of the present invention can be applied in the high temperature resistant low surface energy coatings of preparation, and this coating has good acid resistance and wear resisting property.
Coating of the present invention, this coating contain the described modified organic silicone resin of 60～80w%, 10～20w% high-temperature resisting pigment filler and 5～20w% high boiling solvent.
High boiling solvent of the present invention refers to that divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester, methyl isoamyl ketone are wherein a kind of or two or more.
In the coating of the present invention, pigment is this area high-temperature resisting pigment commonly used, can be the inorganic high-temperature resistant pigment such as carbon black, iron oxide red, also can be the organic high temperature-resistant pigment such as phthalocyanine blue.
In the coating of the present invention, filler is this area high temperature resistant filler commonly used, can be titanium dioxide, silicon-dioxide and silicon carbide.
Coating of the present invention can also contain the organosilicon auxiliary agent.
In the coating of the present invention, the organosilicon auxiliary agent is this area organosilicon auxiliary agent commonly used, plays the effects such as levelling, froth breaking, pigment wetting, viscosity adjustment.Those skilled in the art can be according to the kind and the consumption that require to determine organic silicon additive.Organosilicon auxiliary agent of the present invention can have silicone oil, organic silicon modified by polyether auxiliary agent etc.Organic silicon modified by polyether auxiliary agent of the present invention is this area organic silicon modified by polyether auxiliary agent commonly used, can be the CoatOSil series organic silicon modified by polyether auxiliary agent that steps figure new high-tech material company limited.
In the coating of the present invention, the consumption of organosilicon auxiliary agent is 1～5w%.
In the coating of the present invention, can also contain other auxiliary agents such as flow agent, viscosity modifier and dispersion agent.
The preparation method of coating of the present invention is this area preparation method commonly used, is about to modified organic silicone resin, pigment, filler, organosilicon auxiliary agent and high boiling solvent and is mixed to get.
Coating of the present invention has good resistance toheat, low surface energy, good water-fast solvent resistance and good metal adhesion, but applied metal surfacecti proteon, it is high temperature resistant to give metal, anti-solvent, characteristics easy to clean can be applied on the hardware products such as stove and accessory surface, barbecue grill, electric iron, cooker inside and outside wall.
The relative prior art of the present invention, have the following advantages: coating of the present invention with modified organic silicone resin as base resin, end carboxyl super branched polymeric amide in this resin preparation process, Resins, epoxy and silicone resin carry out in twos crosslinking reaction, form multiple cross-linked modified resin, the sticking power of end carboxyl super branched polymeric amide is good, the advantage that the pigment affinity is high, the good mechanical property of Resins, epoxy, the advantage that water-fast and solvent nature is good and the low surface energy of silicone resin, excellent heat resistance, the advantages that water resistance is good is got up, and therefore coating of the present invention has the high heat resistance energy, good metal adhesion, low surface energy, excellent water boiling resistance and the advantage of acid resistance.
Embodiment
It below is the non-limiting example of technical scheme of the present invention.
Embodiment 1:
1) end carboxyl super branched polymeric amide
A) form:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 105g (0.5mol); 1,2,4-benzene tricarboxylic acid 105g (0.5mol);
Diamine: Isosorbide-5-Nitrae-cyclohexanediamine 57.1g (0.5mol); Two amido sulfobenzide 99.4g (0.4mol); 1,6-hexanediamine 11.6g (0.1mol)
B) synthesis step:
Triprotic acid and diamine adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.33kPa, be incubated 4h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 344g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 6002.
2) modified organic silicone resin
A) form:
End carboxyl super branched polymeric amide: the end carboxyl super branched polyamide 6 0g of step 1 preparation;
Resins, epoxy: bicyclopentadiene dioxide 10g;
Silicone resin: the silicone resin KR216 30g of SHIN-ETSU HANTOTAI;
Two octyloxy tin: 1g.
B) preparation technology:
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 120 ℃ of insulations 2 hours; be warmed up to 160 ℃ of insulations 2 hours; last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 70%, obtains modified organic silicone resin 132g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
Resistance toheat: with test piece in 180 ℃ the baking 2h after, put into the Ovenized electric furnace that potentiometer is checked, by 5 ℃/min rising temperature, begin timing with furnace temperature to the requirement of experiment temperature, sample takes out through behind the continuous high temperature, be chilled to room temperature (25 ℃), observe the coatingsurface situation with magnifying glass, as without be full of cracks, obscission, illustrate that namely coating heat resistance can be good.
3) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 100g of step 2 preparation;
Paint filler: carbon black 40g; Titanium dioxide 20g;
Organosilicon auxiliary agent: silicone oil
/ 350cst 8g;
High boiling solvent: divalent ester mixture (DBE) 5g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
1* water boiling resistance performance: behind 180 ℃ of baking 2h, then cool to room temperature is positioned over test piece in 100 ℃ the distilled water with test piece, is heated to paint film and destroys, and occurs as bubbles loss of gloss, variable color, the phenomenons such as be full of cracks.
The 2* resistance toheat: with test piece in 180 ℃ the baking 2h after, put into the Ovenized electric furnace that potentiometer is checked, by 5 ℃/min rising temperature, begin timing with furnace temperature to the requirement of experiment temperature, sample takes out through behind the continuous high temperature, be chilled to room temperature (25 ℃), observe the coatingsurface situation with magnifying glass, as without be full of cracks, obscission, illustrate that namely coating heat resistance can be good.
3* surface tension: under 25 ℃, measured by surface tension measuring instrument.
Embodiment 2:
1) end carboxyl super branched polymeric amide
A) form:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 294g (1.4mol); 1,2,4-benzene tricarboxylic acid 126g (0.6mol);
Diamine: 1,2-propylene diamine 29.7g (0.4mol); Isophorone diamine 68g (0.4mol); 4,4 '-diaminodiphenylmethane 39.6g (0.2mol);
B) synthesis step:
Triprotic acid and diamine adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.66kPa, be incubated 2h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 522g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 1997.
2) modified organic silicone resin
A) form:
End carboxyl super branched polymeric amide: the end carboxyl super branched polymeric amide 40g of step 1 preparation;
Resins, epoxy: TriMethylolPropane(TMP) glycidyl ether 8g;
Silicone resin: DOW CORNING 3037 52g;
Catalyzer: two octyloxy tin 3g.
B) preparation technology:
Saturated end carboxyl super branched polymeric amide, Resins, epoxy and the silicone resin adding of step 1 preparation are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 110 ℃ of insulations 3 hours; be warmed up to 170 ℃ of insulations 1 hour; last cool to room temperature; adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains modified organic silicone resin 160g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
3) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 160g of step 2 preparation;
Paint filler: carbon black 20g;
High boiling solvent: divalent ester mixture (DBE) 5g; Ethylene glycol ether acetate (CAC): 5g.
B) preparation technology
Paint filler, modified organic silicone resin, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 3:
1) end carboxyl super branched polymeric amide
A) form:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 294g (1.4mol);
Diamine: Putriscine 17.63g (0.2mol); 1,6-hexanediamine 58.1g (0.5mol); DDS 74.4g (0.3mol)
Contain the aminoalkyl group carboxylic acid: glycine 3.75g (0.05mol); 3-alanine 4.45g (0.05mol)
B) synthesis step:
With triprotic acid, diamine with contain the aminoalkyl group carboxylic acid and add heating is housed, in the reactor of condensation and nitrogen protection, be warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.78kPa, be incubated 2.5h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 485g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 3004.
2) silicone resin intermediate
A) form
Monomethyl Trimethoxy silane: 42.0g (0.28mol)
Dimethyldimethoxysil,ne: 18.7g (0.14mol)
One phenyltrimethoxysila,e: 123.0g (0.58mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 4.5mmol hydrochloric acid by proportioning, begin to stir and heat up, keep homo(io)thermism after being warmed up to 60 ℃, under agitation drip 31.7g distilled water, after dropwising, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 60%, obtains silicone resin intermediate 290g.
C) performance
The weight-average molecular weight of silicone resin intermediate adopts gel permeation chromatography to detect, and the result is 802; The hydroxy radical content of silicone resin intermediate adopts the diacetyl oxide method to measure, and the result is 10.6%; The methoxy content of silicone resin intermediate adopts perchloric acid acetyl method to measure, and the result is 7.4%; R/Si=1.14; Ph/Me=1.04.
3) modified organic silicone resin
A) form
End carboxyl super branched polymeric amide: the end carboxyl super branched polymeric amide 50g of step 1 preparation;
Resins, epoxy: two ((3,4-epoxycyclohexyl) methyl) adipic acid ester 4g; Bisphenol-s epoxy resin 2g;
Silicone resin: the silicone resin 73.3g of the solid content 60% of step 2 preparation;
Catalyzer: two different octyloxy tin 2.7g.
B) preparation technology
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 115 ℃ of insulations 1.5 hours; be warmed up to 175 ℃ of insulations 1.5 hours; last cool to room temperature, adding dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate adjustment solid content is 65%, obtains modified organic silicone resin 141g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
4) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 100g of step 3 preparation;
Paint filler: phthalocyanine blue 20g; Silicon-dioxide 20g;
Organosilicon auxiliary agent: CoatOSil 7001 4g; Silicone oil
/ 350cst 6g;
High boiling solvent: Diethylene Glycol monobutyl ether acetate (DBA) 5g; Ethylene glycol ether acetate (CAC) 5g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) be coated with performance
The performance index of coating
Embodiment 4:
1) end carboxyl super branched polymeric amide
A) form:
Polyvalent alcohol: 1,3,5-benzene tricarboxylic acid 378g (1.8mol);
Diamine: isophorone diamine 34g (0.2mol); 1,6-hexanediamine 58.1g (0.5mol); DDS 74.4g (0.3mol)
Contain the aminoalkyl group carboxylic acid: glycine 0.75g (0.01mol); 3-alanine 1.78g (0.02mol); 3-amino-2-methyl propionic acid 3.63g (0.03mol);
B) synthesis step:
With triprotic acid, diamine with contain the aminoalkyl group carboxylic acid and add heating is housed, in the reactor of condensation and nitrogen protection, be warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.85kPa, be incubated 3.5h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 390g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 2245.
2) modified organic silicone resin
A) form
End carboxyl super branched polymeric amide: the end carboxyl super branched polymeric amide 58g of step 1 preparation;
Resins, epoxy: two (2,3-oxirane ring amyl group) ether 4g; 3,4-epoxidation naphthenic acid, 3 ', 4 '-epoxidation hexanaphthene methyl esters 3g;
Silicone resin: the silicone resin KR211 15g of SHIN-ETSU HANTOTAI; The silicone resin KR214 20g of SHIN-ETSU HANTOTAI;
Catalyzer: two different octyloxy zinc 2g; Two octyloxy tin 1.5g.
B) preparation technology:
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 120 ℃ of insulations 2 hours; be warmed up to 155 ℃ of insulations 2.5 hours; last cool to room temperature, adding 1-Methoxy-2-propyl acetate and butanols adjustment solid content is 70%, obtains modified organic silicone resin 125g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
3) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 120g of step 2 preparation;
Paint filler: silicon carbide 10g; Silica 1 0g;
Organosilicon auxiliary agent: CoatOSil 3500 4g; Silicone oil
/ 350cst 4g;
High boiling solvent: propionic acid-3-ether ethyl ester (EEP) 10g; Divalent ester mixture (DBE) 10g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 5
1) end carboxyl super branched polymeric amide
A) form:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 252g (1.2mol);
Diamine: Isosorbide-5-Nitrae-cyclohexanediamine 34.2g (0.3mol); 1,6-hexanediamine 29g (0.25mol); DDS 111.6g (0.45mol);
Contain the amino 2 Methylpropionic acid 6.06g (0.05mol) of aminoalkyl group carboxylic acid: 3-;
B) synthesis step:
With triprotic acid, diamine with contain the aminoalkyl group carboxylic acid and add heating is housed, in the reactor of condensation and nitrogen protection, be warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.66kPa, be incubated 2.5h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 400g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 4002.
2) modified organic silicone resin
A) form:
End carboxyl super branched polymeric amide: the end carboxyl super branched polymeric amide 45g of step 1 preparation;
Resins, epoxy: two ((3,4-epoxycyclohexyl) methyl) adipic acid ester 4g; 3,4-epoxidation naphthenic acid, 3 ', 4 '-epoxidation hexanaphthene methyl esters 4g; Bicyclopentadiene dioxide 2g;
Silicone resin: silicone resin 233 35g of Dow Corning Corporation; Silicone resin 249 10g of Dow Corning Corporation;
Catalyzer: two octyloxy tin 3.5g.
B) preparation technology:
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 130 ℃ of insulations 1 hour; be warmed up to 170 ℃ of insulations 1 hour; last cool to room temperature, adding isopropylcarbinol and propylene glycol monomethyl ether adjustment solid content is 65%, obtains modified organic silicone resin 141g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
3) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 140g of step 2 preparation;
Paint filler: carbon black 20g; Silica 1 4g;
Organosilicon auxiliary agent: CoatOSil 3500 4g; CoatOSil 7650 2g;
High boiling solvent: methyl isoamyl ketone (MIAK) 2g; Isobutyl isobutyrate 4g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 6
1) end carboxyl super branched polymeric amide
A) form:
Triprotic acid: 1,3,5-benzene tricarboxylic acid 315g (1.5mol);
Diamine: Ursol D 13g (0.12mol); Isophorone diamine 68g (0.4mol); 4,4 '-diaminodiphenylmethane 75.4g (0.38mol); 1,6-hexanediamine 11.6g (0.1mol);
Contain the aminoalkyl group carboxylic acid: 3-amino-2-methyl propionic acid 1.21g (0.01mol); 3-alanine 0.89g (0.01mol).
B) synthesis step:
With triprotic acid, diamine with contain the aminoalkyl group carboxylic acid and add heating is housed, in the reactor of condensation and nitrogen protection, be warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.33kPa, be incubated 4h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 448g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 3667.
2) modified organic silicone resin
A) form
End carboxyl super branched polymeric amide: the end carboxyl super branched polymeric amide 49g of step 1 preparation;
Resins, epoxy: bicyclopentadiene dioxide 1g;
Silicone resin: DOW CORNING silicone resin 3074 35g; The silicone resin KR212 15g of SHIN-ETSU HANTOTAI;
Catalyzer: two octyloxy tin 1g; Tetrabutyl titanate 1g.
B) preparation technology
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 125 ℃ of insulations 2 hours; be warmed up to 155 ℃ of insulations 2.5 hours; last cool to room temperature, adding 1-Methoxy-2-propyl acetate and dipropylene glycol methyl ether adjustment solid content is 60%, obtains modified organic silicone resin 144g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
3) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 120g of step 2 preparation;
Paint filler: carbon black 20g; Silicon-dioxide 5g; Titanium dioxide 5g;
Organosilicon auxiliary agent: CoatOSil 3500 4g; CoatOSil 7510 2g; Silicone oil
/ 350cst 4g;
High boiling solvent: divalent ester mixture (DBE) 12g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 7
1) end carboxyl super branched polymeric amide
A) form
Triprotic acid: 1,3,5-benzene tricarboxylic acid 210g (1.0mol);
Diamine: DDS 91.9g (0.37mol); Isosorbide-5-Nitrae-cyclohexanediamine 57.3g (0.50mol)
Contain the amino 2 Methylpropionic acid 1.21g (0.01mol) of aminoalkyl group carboxylic acid: 3-;
B) synthesis step:
With triprotic acid, diamine with contain the aminoalkyl group carboxylic acid and add heating is housed, in the reactor of condensation and nitrogen protection, be warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.03kPa, be incubated 3.5h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 354g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 5782.
2) modified organic silicone resin
A) form
End carboxyl super branched polymeric amide: the end carboxyl super branched polymeric amide 48g of step 1 preparation;
Resins, epoxy: TriMethylolPropane(TMP) glycidyl ether 2g; 3,4-epoxidation naphthenic acid, 3 ', 4 '-epoxidation hexanaphthene methyl esters 1g; Bisphenol-s epoxy resin 1g;
Silicone resin: the silicone resin IC836 20g of Wa Ke company; The silicone resin Z-6108 10g of Dow Corning Corporation; The silicone resin KR213 18g of company of SHIN-ETSU HANTOTAI;
Catalyzer: tetrabutyl titanate 0.3g; Two octyloxy tin 0.2g.
B) preparation technology
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 130 ℃ of insulations 1 hour; be warmed up to 150 ℃ of insulations 3 hours; last cool to room temperature, adding 1-Methoxy-2-propyl acetate and dipropylene glycol butyl ether adjustment solid content is 70%, obtains modified organic silicone resin 126g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
3) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 110g of step 2 preparation;
Paint filler: phthalocyanine blue 20g; Silicon-dioxide 5g; Titanium dioxide 5g;
High boiling solvent: divalent ester mixture (DBE) 40g; Isobutyl isobutyrate 20g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 8
1) end carboxyl super branched polymeric amide
A) form:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 42g (0.2mol); 1,3,5-benzene tricarboxylic acid 210g (1.0mol)
Diamine: DDS 149g (0.6mol); 1,3-propylene diamine 29.5g (0.4mol)
Contain the aminoalkyl group carboxylic acid: 3-alanine 8.9g (0.1mol).
B) synthesis step:
With triprotic acid, diamine with contain the aminoalkyl group carboxylic acid and add heating is housed, in the reactor of condensation and nitrogen protection, be warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.33kPa, be incubated 4h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 404g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 3833.
2) silicone resin
A) form
Methltriethoxysilone: 69.1g (0.36mol)
Dimethyldiethoxysilane: 34.0g (0.21mol)
Phenyltriethoxysilane: 109.24g (0.43mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 5.5mmol hydrochloric acid by proportioning, begin to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃, under agitation drip 42.7g distilled water, after dropwising, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 60%, obtains silicone resin intermediate 322g.
C) performance
The weight-average molecular weight of silicone resin intermediate adopts gel permeation chromatography to detect, and the result is 1808; The hydroxy radical content of silicone resin intermediate adopts the diacetyl oxide method to measure, and the result is 20%; The oxyethyl group content of silicone resin intermediate adopts perchloric acid acetyl method to measure, and the result is 2.5%; R/Si=1.21; Ph/Me=0.55.
3) modified organic silicone resin
A) form
End carboxyl super branched polymeric amide: the end carboxyl super branched polymeric amide 56g of step 1 preparation;
Resins, epoxy: bicyclopentadiene dioxide 9g;
Silicone resin: the silicone resin 35g that step 2 is synthetic
Catalyzer: two octyloxy zinc 2.5g; Two octyloxy tin 2g.
B) preparation technology
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 110 ℃ of insulations 3 hours; be warmed up to 150 ℃ of insulations 3 hours; last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 65%, obtains modified organic silicone resin 138g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
4) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 150g of step 2 preparation;
Paint filler: carbon black 10g; Silicon-dioxide 5g; Titanium dioxide 5g;
Organosilicon auxiliary agent: CoatOSil 3500 5g; Silicone oil
/ 350cst 5g;
High boiling solvent: divalent ester mixture (DBE) 10g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 9
1) end carboxyl super branched polymeric amide becomes
A) form
Triprotic acid: 1,2,4-benzene tricarboxylic acid 294g (1.4mol);
Diamine: DDS 124g (0.5mol); Isosorbide-5-Nitrae-cyclohexanediamine 57g (0.5mol)
B) synthesis step
Triprotic acid and diamine adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 1.33kPa, be incubated 4h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 439g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 3253.
2) silicone resin
A) form
Methltriethoxysilone: 44.5g (0.25mol)
Dimethyldiethoxysilane: 50.3g (0.34mol)
Phenyltriethoxysilane: 98.4g (0.41mol),
B) preparation technology
After in the reactor that prolong, thermometer, dropping funnel and agitator are housed, adding successively siloxanes and 7.0mmol hydrochloric acid by proportioning, begin to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃, under agitation drip 43.1g distilled water, after dropwising, behind the isothermal reaction 3h, begin underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules that produces in the reaction process, cool to room temperature, adjusting solid content is 80%, obtains silicone resin intermediate 230g.
C) performance
The weight-average molecular weight of silicone resin intermediate adopts gel permeation chromatography to detect, and the result is 1986; The hydroxy radical content of silicone resin intermediate adopts the diacetyl oxide method to measure, and the result is 15%; The oxyethyl group content of silicone resin intermediate adopts perchloric acid acetyl method to measure, and the result is 3%; R/Si=1.34; Ph/Me=0.44.
3) modified organic silicone resin
A) form
End carboxyl super branched polymeric amide: the end carboxyl super branched kymene 2g of step 1 preparation;
Resins, epoxy: bicyclopentadiene dioxide 8g;
Silicone resin: the 60% solid content silicone resin 100g that step 2 is synthetic;
Catalyzer: two octyloxy tin 1g, two different octyloxy tin 0.6g.
B) preparation technology
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 125 ℃ of insulations 2 hours; be warmed up to 160 ℃ of insulations 2 hours; last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 60%, obtains modified organic silicone resin 148g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
4) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 150g of step 2 preparation;
Paint filler: phthalocyanine blue 20g; Titanium dioxide 20g;
Organic additive: CoatOSil 7510 8g;
Height boils and reaches solvent: divalent ester mixture (DBE) 2g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 10
1) end carboxyl super branched polymeric amide
A) form:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 231g (1.1mol);
Diamine: DDS 149g (0.5mol); Isophorone diamine 85g (0.5mol)
B) synthesis step:
Triprotic acid and diamine adding are equipped with heating, in the reactor of condensation and nitrogen protection, are warmed up to 110 ℃ under the nitrogen protection, insulation 2h; Be heated to 240 ℃ with 20 ℃ of rate of heating per hour, under 0.66kPa, be incubated 2h; Cool off at last room temperature, obtain the end carboxyl super branched polymeric amide of 428g.
C) performance of end carboxyl super branched polymeric amide
The weight-average molecular weight of end carboxyl super branched polymeric amide adopts gel permeation chromatography to detect, and the result is 3907.
2) modified organic silicone resin
A) form:
End carboxyl super branched polymeric amide: the end carboxyl super branched polymeric amide 51g of step 1 preparation;
Resins, epoxy: TriMethylolPropane(TMP) glycidyl ether 1g; Two (2,3-oxirane ring amyl group) ether 3g;
Silicone resin: the silicone resin KR9218 25g of SHIN-ETSU HANTOTAI; DOW CORNING silicone resin Z-6108 20g;
Catalyzer: two octyloxy zinc 0.6g; Two different octyloxy zinc 0.41g.
B) preparation technology:
End carboxyl super branched polymeric amide with step 1 preparation; Resins, epoxy and silicone resin adding are equipped with in the reactor of heating, condensation and nitrogen protection device; add catalyzer; be warmed up to 120 ℃ of insulations 2 hours; be warmed up to 175 ℃ of insulations 2 hours; last cool to room temperature, adding 1-Methoxy-2-propyl acetate adjustment solid content is 65%, obtains modified organic silicone resin 136g.
C) modified organic silicone resin performance
The over-all properties of modified organic silicone resin
3) coating
A) form
Modified organic silicone resin: the modified organic silicone resin 120g of step 2 preparation;
Paint filler: iron oxide red 30g; Titanium dioxide 20g; Silica 1 0g;
Organosilicon auxiliary agent: CoatOSil 7510:2g;
High boiling solvent: divalent ester mixture (DBE): 18g.
B) preparation technology
Paint filler, modified organic silicone resin, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Claims (5)
1. the preparation method of a modified organic silicone resin, the method is comprised of following steps:
The crosslinking catalyst that silicone resin and the weight of the end carboxyl super branched polymeric amide of 40～60wt%, 1～10wt% Resins, epoxy and 30～50wt% is end carboxyl super branched polymeric amide consumption 1～10% adds in the reactor; Under 110～120 ℃, 150～170 ℃ and 200～210 ℃, heated respectively 1～3 hour successively; Be down at last room temperature, adding organic solvent adjustment solid content is 60～70%; In the above-mentioned steps,
The weight-average molecular weight of described end carboxyl super branched polymeric amide is 2000～6000, and it is with diamine, triprotic acid and to contain the aminoalkyl group carboxylic acid be diamine according to the amount of substance ratio: triprotic acid: contain aminoalkyl group carboxylic acid=1:1～2:0～0.1 and carry out amidate action and obtain; Wherein, described diamine is 1,3-propylene diamine, 1,2-propylene diamine, Isosorbide-5-Nitrae-cyclohexanediamine, Putriscine, isophorone diamine, 4, and 4 '-diaminodiphenylmethane, DDS and 1,6-hexanediamine are wherein a kind of or two or more; Described triprotic acid is wherein a kind of or mixture of 1,2,4-benzene tricarboxylic acid and 1,3,5-benzene tricarboxylic acid; The described aminoalkyl group carboxylic acid that contains is that glycine, 3-alanine and 3-amino-2-methyl propionic acid are wherein a kind of or two or more;
Described Resins, epoxy is bicyclopentadiene dioxide, 3,4-epoxidation naphthenic acid 3 ', 4 '-epoxidation hexanaphthene methyl esters, two ((3, the 4-epoxycyclohexyl) methyl) adipic acid ester, two (2,3-oxirane ring amyl group) ether, bisphenol-s epoxy resin and TriMethylolPropane(TMP) glycidyl ether are wherein a kind of or two or more;
The weight-average molecular weight of described silicone resin is 800～2000, and contains 2.5～15% methoxy or ethoxy and 3～20% hydroxyl;
Described crosslinking catalyst is that tetrabutyl titanate, tetrabutyl titanate, two octyloxy tin, two different octyloxy tin, two octyloxy zinc and two different octyloxy zinc are wherein a kind of or two or more;
Described organic solvent be butanols, isopropylcarbinol, propylene glycol monomethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate wherein one or more.
2. the preparation method of modified organic silicone resin claimed in claim 1, it is characterized in that, end carboxyl super branched polymeric amide consumption is 50～60wt%, content of epoxy resin is 1～8wt%, the silicone resin consumption is 35～50wt%, and the crosslinking catalyst consumption is 1～5% of end carboxyl super branched polymeric amide weight; Wherein, the consumption sum of described end carboxyl super branched polymeric amide, Resins, epoxy, silicone resin and crosslinking catalyst equals 100wt%.
3. the preparation method of modified organic silicone resin claimed in claim 1, it is characterized in that, described silicone resin be KR9218, the company of SHIN-ETSU HANTOTAI of KR213, the company of SHIN-ETSU HANTOTAI of IC836, the company of SHIN-ETSU HANTOTAI of KR216, the Wa Ke company of KR214, the company of SHIN-ETSU HANTOTAI of KR212, the company of SHIN-ETSU HANTOTAI of KR211, the company of SHIN-ETSU HANTOTAI of company of SHIN-ETSU HANTOTAI KR217, Dow Corning Corporation 233, Dow Corning Corporation 249,3037 wherein a kind of or two or more of 3074 and Dow Corning Corporation of the Z-6108 of Dow Corning Corporation, Dow Corning Corporation.
4. the preparation method of modified organic silicone resin claimed in claim 1, it is characterized in that, the weight-average molecular weight of end carboxyl super branched polymeric amide is 3000～5000, and it is with diamine, triprotic acid and to contain the aminoalkyl group carboxylic acid be diamine according to the amount of substance ratio: triprotic acid: contain aminoalkyl group carboxylic acid=1:1～1.4:0.05～0.1 and add in the reactor; Per hour to heat up 20 ℃ rate of heating, be heated to 240 ℃, under 0.67～1.33kPa, be incubated 2～4h; Cool to room temperature obtains; Wherein, described diamine is Isosorbide-5-Nitrae-cyclohexanediamine, isophorone diamine, 4, and 4 '-diaminodiphenylmethane, DDS and 1,6-hexanediamine are wherein a kind of or two or more; Described triprotic acid is wherein a kind of or mixture of 1,2,4-benzene tricarboxylic acid and 1,3,5-benzene tricarboxylic acid; The described aminoalkyl group carboxylic acid that contains is wherein a kind of or mixture of 3-alanine and 3-amino-2-methyl propionic acid.
5. coating, this coating contain modified organic silicone resin, 10～20wt% high-temperature resisting pigment filler and 5～20wt% high boiling solvent of one of them described method preparation of 60～80wt% claim 1 to 4; Wherein, described high boiling solvent refers to that divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and methyl isoamyl ketone are wherein a kind of or two or more.
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| CN102977363B (en) * | 2012-11-27 | 2015-01-21 | 南方医科大学 | Preparation method of modified amino-terminated hyper-branched polyamide resin and coating comprising resin |
| CN103113578B (en) * | 2013-01-31 | 2014-12-31 | 华南理工大学 | Modified carboxyl-terminated hyperbranched polyamide resin, as well as preparation method and application thereof |
| CN103113570B (en) * | 2013-01-31 | 2014-12-03 | 华南理工大学 | Amino-terminated silicon oil modified carboxyl-terminated hyperbranched polyester resin, and preparation method and application thereof |
| CN104177634B (en) * | 2014-08-27 | 2016-07-06 | 南方医科大学 | The preparation method of a kind of polyamide modified organic siliconresin and the coating containing this resin |
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| CN109694478A (en) * | 2018-12-28 | 2019-04-30 | 上海华谊树脂有限公司 | A kind of ultrabranching polyamide and its preparation method and application |
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