CN102964592A - Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin - Google Patents
Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin Download PDFInfo
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Abstract
The invention relates to a preparation method of modified terminal-carboxyl-hyperbranched polyamide resin. The method comprises the following steps of: uniformly mixing diamine and ternary acid with the mole number of 1-2.0 times that of the diamine, then heating to 70-90 DEG C, and adding terminal epoxy group silicone oil with the weight of 0.05-0.1 times that of the diamine and dimethylbenzene with the weight of 0.02-0.1 times that of the diamine; heating for 1-3 hours at the temperature of 180-210 DEG C, warming to 220-240 DEG C, and heating for 1-3 hours; cooling to 90 DEG C, adding an organic solvent with the weight of 1.0-1.5 times that of the diamine, an organic silicon low polymer with the weight of 1.5-2.0 times that of the diamine and a crosslinking catalyst with the weight of 1-5% that of the diamine; warming to 110-120 DEG C, and heating for 2-3 hours; and cooling to 90 DEG C, and finally adding the organic solvent to adjust solid content to 60-70%, so that the modified terminal-carboxyl-hyperbranched polyamide resin is obtained. The resin prepared by adopting the preparation method provided by the invention can be used for preparing high temperature resistant low-surface-energy paint. According to the preparation method provided by the invention, when the terminal-carboxyl-hyperbranched polyamide resin is synthesized, the terminal epoxy group silicon oil is added, so as to improve the heat-resisting performance and flexibility of polyamide; and crosslinking reaction is carried out on the organic silicon low polymer and the polyamide, so as to improve the heat-resisting performance of the polyamide.
Description
Technical field
The present invention relates to the 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, 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 etc. (Wu Jianliang, the development of low-molecular-weight polyamide resin, Zhejiang chemical industry, 2004,35(03), 19).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., is widely used in paint field.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; Numerous terminal functionality can prepare and be fit to multi-purpose coating so that Hyperbranched Polymer has very strong correctability ability.For example Chinese patent CN102382314A improves mechanical property, chemical resistance and the acidproof water resistance of silicone resin with end carboxyl super branched polyamide modified silicone resin.But the snappiness of the end carboxyl super branched polyamide modified silicone resin of above-mentioned preparation is poor, can ftracture under the high low temperature alternation condition, limits its application.
Summary of the invention
The technical problem that the present invention solves provides a kind of preparation method of the super cladodification polyamide resin of end carboxyl of modification, and the modified polyamide of the method preparation has resistance toheat and the good advantage of snappiness.
The scheme of the technical problem that the present invention is above-mentioned is:
A kind of preparation method of the super cladodification polyamide resin of end carboxyl of modification, the method is comprised of following steps:
Be that the triprotic acid of 1 ~ 2.0 times of diamine mixes post-heating to 70 ~ 90 ℃ with diamine and molar weight, add the dimethylbenzene of 0.02 ~ 0.1 times of the epoxy-terminated silicone oil of 0.05 ~ 0.1 times of diamine weight and diamine weight; Behind 180 ~ 210 ℃ of lower heating 1 ~ 3h, be warming up to 220 ~ 240 ℃, behind heating 1 ~ 3h; Be cooled to 90 ℃, add the organic solvent of 1.0 ~ 1.5 times of diamine weight, 1 ~ 5% crosslinking catalyst of the silicone oligomer that diamine weight is 1.5 ~ 2.0 times and diamine weight; Be heated to 110 ~ 120 ℃, heating 2 ~ 3h; Be cooled to 90 ℃, adding at last organic solvent adjustment solid content is 60 ~ 70%;
Described diamine is Isosorbide-5-Nitrae-cyclohexanediamine, isophorone diamine, 4, a kind of or two or more in 4 '-diaminodiphenylmethane, DDS and 1, the 6-hexanediamine;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3, the 5-benzene tricarboxylic acid or two kinds;
The weight-average molecular weight of described epoxy-terminated silicone oil is 300 ~ 1000, and every 100g epoxy-terminated silicone oil contains 8 ~ 100mmol epoxy group(ing);
The weight-average molecular weight of described silicone oligomer is 800 ~ 2000, and contains the methoxy or ethoxy of 2.5 ~ 15w% and the hydroxyl of 3 ~ 20w%;
Described crosslinking catalyst is a kind of or two or more in tetrabutyl titanate, tetrabutyl titanate, dioctyl tin oxide, diisooctyl stannic oxide, dioctyl zinc oxide and the diisooctyl zinc oxide;
Described organic solvent is one or more in 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 the dipropylene glycol monobutyl ether acetate.
Above-mentioned preparation method, wherein said epoxy-terminated silicone oil can be prepared by following methods:
The tetramethyl disiloxane of octamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane weight 0.01 ~ 0.05% and the vitriol oil of octamethylcyclotetrasiloxane weight 2 ~ 6% are added in the reactor nitrogen protection reaction 7 ~ 10h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, the glycidyl allyl ether of octamethylcyclotetrasiloxane weight 1 ~ 10%, the Platinic chloride of the toluene of octamethylcyclotetrasiloxane weight 1 ~ 2 and octamethylcyclotetrasiloxane weight 0.01 ~ 0.05% add in the reactor; Be warming up to 70 ~ 90 ℃, nitrogen protection reaction 8 ~ 10h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
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 this area siloxanes commonly used, 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 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, the Z-6108 of Dow Corning Corporation, Dow Corning Corporation 3074, Dow Corning Corporation 3037 in a kind of or two or more.
Above-mentioned preparation method, wherein,
Described crosslinking catalyst better is tetrabutyl titanate;
Described epoxy-terminated silicone oil weight-average molecular weight is 300 ~ 1000, and every 100g epoxy-terminated silicone oil contains 30 ~ 50mmol epoxy group(ing).
The super cladodification polyamide resin of end carboxyl of the modification of method preparation of the present invention has the following advantages:
Diamine, triprotic acid and epoxy-terminated silicone oil are reacted the end carboxyl super branched polyamide resin of preparation, wherein the carboxyl on the triprotic acid and the amino on the diamine carry out amidate action, the amino of diamine and the epoxy group(ing) on the epoxy-terminated silicone oil react simultaneously, flexible organosilicon segment is embedded in the ultrabranching polyamide, improve the resistance toheat of polymeric amide, snappiness and the cold-and-heat resistent of filming change performance.
On the other hand, the super cladodification polyamide resin of end carboxyl with end carboxyl super branched polyamide resin and silicone oligomer reaction preparation modification, the hydroxyl on the end carboxyl super branched polyamide resin wherein, under the crosslinking catalyst effect can with silicone oligomer on alkoxyl group or silicon hydroxyl generation crosslinking reaction, improve the resistance toheat of polyamide resin.
The super cladodification polyamide resin of the end carboxyl of modification 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 water resistance.
Coating of the present invention, this coating contain the super cladodification polyamide resin of end carboxyl, the high temperature resistant filler of 10 ~ 20w% and 5 ~ 20w% high boiling solvent of the obtained modification of 60 ~ 80w% aforesaid method, wherein,
Described high boiling solvent is a kind of or two or more in divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and the methyl isoamyl ketone;
Described high temperature resistant filler is this area high temperature resistant filler commonly used, can be in titanium dioxide, silicon-dioxide and the silicon carbide one or more.
Also can add this area high-temperature resisting pigment commonly used in the above-mentioned coating, described high-temperature resisting pigment 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.
Can also add this area organosilicon auxiliary agent commonly used in the above-mentioned coating, as, play the effects such as levelling, froth breaking, pigment wetting, viscosity adjustment.Above-mentioned organosilicon auxiliary agent can also be silicone oil, organic silicon modified by polyether auxiliary agent, as, step the CoatOSil series organic silicon modified by polyether auxiliary agent of figure 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 ~ 5w%.
The preparation method of above-mentioned coating is this area preparation method commonly used, and the super cladodification polyamide resin of end carboxyl, pigment, filler, organosilicon auxiliary agent and the high boiling solvent that are about to modification are mixed to get.
Because coating of the present invention adopts the super cladodification polyamide resin preparation of the end carboxyl of above-mentioned modification, therefore has high heat resistance energy and good snappiness.
Embodiment
It below is the non-limiting example of technical scheme of the present invention.
Embodiment 1:
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.1g
The vitriol oil: 12g
Glycidyl allyl ether: 20g
Platinic chloride: 0.1g
Toluene: 400g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 9h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 90 ℃, nitrogen protection reaction 10h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 303; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is 1.01mmol/g.
2) preparation of the super cladodification polyamide resin of end carboxyl of modification
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-is diamines 11.6g(0.1mol)
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 8.4g of step 1 preparation
Dimethylbenzene: 3.3g
Silicone oligomer: the silicone resin KR 150168g of SHIN-ETSU HANTOTAI
Crosslinking catalyst: tetrabutyl titanate 1.68g
Organic solvent: 1-Methoxy-2-propyl acetate 300g
B) synthesis step:
Diamine and triprotic acid are mixed post-heating to 70 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 180 ℃ of lower heating 1h, be warming up to 240 ℃, behind the heating 1h; Be cooled to 90 ℃, add 1.0 times organic solvent of diamine weight, silicone oligomer and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Be cooled to 90 ℃, add at last the residue organic solvent.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
The 1* 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.
2) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 100g of the modification of above-mentioned preparation;
Paint filler: carbon black 40g; Titanium dioxide 20g;
Organosilicon auxiliary agent: silicone oil
8g;
High boiling solvent: divalent ester mixture (DBE) 5g.
B) preparation technology
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 2:
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.05g
The vitriol oil: 6g
Glycidyl allyl ether: 11g
Platinic chloride: 0.05g
Toluene: 320g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 8h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 85 ℃, nitrogen protection reaction 8.5h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 587; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 53mmol epoxy group(ing).
2) preparation of the super cladodification polyamide resin of end carboxyl of modification
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);
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 13.7g of step 1 preparation
Dimethylbenzene: 13.7g
Silicone oligomer: the silicone resin KR150100g of SHIN-ETSU HANTOTAI, the KR212174.6g of company of SHIN-ETSU HANTOTAI
Crosslinking catalyst: tetrabutyl titanate 6.9g
Organic solvent: 1-Methoxy-2-propyl acetate 205g butanols 40g
B) synthesis step:
Diamine and triprotic acid are mixed post-heating to 80 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 200 ℃ of lower heating 3h, be warming up to 220 ℃, behind the heating 2h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer and crosslinking catalyst; Be heated to 115 ℃, heating 3h; Be cooled to 90 ℃, add at last butanols.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
2) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 160g of the modification of step 1 preparation; Paint filler: carbon black 20g; Silicon whisker 3g, wilkinite 5g
Organosilicon auxiliary agent: silicone oil
1g.
High boiling solvent: divalent ester mixture (DBE) 5g; Ethylene glycol ether acetate (CAC): 5g.
B) preparation technology
The super cladodification polyamide resin of end carboxyl, high boiling solvent, the auxiliary agent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 3:
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.03g
The vitriol oil: 3g
Glycidyl allyl ether: 3g
Platinic chloride: 0.02g
Toluene: 240g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 8h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 80 ℃, nitrogen protection reaction 10h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 987; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 13mmol epoxy group(ing).
2) preparation of silicone oligomer
A) form
Monomethyl Trimethoxy silane: 42.0g(0.28mol)
Dimethyldimethoxysil,ne: 18.7g(0.14mol)
One phenyltrimethoxysila,e: 123.0g(0.58mol),
B) preparation technology
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 oligomer 290g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and the result is 802; The hydroxy radical content of silicone oligomer adopts the diacetyl oxide method to measure, and the result is 10.6w%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and the result is 7.4w%; R/Si=1.14; Ph/Me=1.04.
3) preparation of the super cladodification polyamide resin of end carboxyl of modification
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)
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 12g of step 1 preparation
Dimethylbenzene: 8g
Silicone oligomer: the silicone oligomer 120g of step 2 preparation, the 249120g of Dow Corning Corporation
Crosslinking catalyst: tetrabutyl titanate 2.9g, tetrabutyl titanate 2.0g
Organic solvent: dipropylene glycol methyl ether acetate 225g, dipropylene glycol monobutyl ether acetate 40g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 85 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 210 ℃ of lower heating 2.5h, be warming up to 235 ℃, behind the heating 3h; Be cooled to 90 ℃, add dipropylene glycol methyl ether acetate, silicone oligomer and crosslinking catalyst; Be heated to 120 ℃, heating 2.5h; Be cooled to 90 ℃, add at last the dipropylene glycol monobutyl ether acetate.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
4) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 100g of the modification of step 3 preparation; Paint filler: phthalocyanine blue 20g; Silicon-dioxide 20g;
Organosilicon auxiliary agent: CoatOSil 70014g; Silicone oil
6g;
High boiling solvent: Diethylene Glycol monobutyl ether acetate 5g; N-BUTYL ACETATE 5g.
B) preparation technology
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) be coated with performance
The performance index of coating
The performance index of coating
Embodiment 4:
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.1g
The vitriol oil: 10g
Glycidyl allyl ether: 20g
Platinic chloride: 0.08g
Toluene: 360g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 9h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 90 ℃, nitrogen protection reaction 10h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 313; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 98mmol epoxy group(ing).
2) preparation of the super cladodification polyamide resin of end carboxyl of modification
A) form:
Triprotic acid: 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)
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 9g of step 1 preparation
Dimethylbenzene: 5.8g
Silicone oligomer: the 307460g of Dow Corning Corporation, the 303755g of Dow Corning Corporation, the KR921865g of company of SHIN-ETSU HANTOTAI, the KR21790g of company of SHIN-ETSU HANTOTAI
Crosslinking catalyst: tetrabutyl titanate 6.3g
Organic solvent: 1-Methoxy-2-propyl acetate 95g, butanols 100g, dipropylene glycol methyl ether acetate 30g, dipropylene glycol monobutyl ether acetate 20g
B) synthesis step:
Diamine and triprotic acid are mixed post-heating to 80 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 220 ℃ of lower heating 2.5h, be warming up to 230 ℃, behind the heating 2.5h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, butanols, silicone oligomer and crosslinking catalyst; Be heated to 110 ℃, heating 3h; Be cooled to 70 ℃, add at last dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
2) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 120g of the modification of step 1 preparation;
Paint filler: silicon carbide 10g; Silica 1 0g;
Organosilicon auxiliary agent: CoatOSil 35004g; Silicone oil
4g;
High boiling solvent: propionic acid-3-ether ethyl ester (EEP) 10g; Divalent ester mixture (DBE) 10g.
B) preparation technology
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
The performance index of coating
Embodiment 5
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.07g
The vitriol oil: 7g
Glycidyl allyl ether: 16g
Platinic chloride: 0.05g
Toluene: 310g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 8h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 80 ℃, nitrogen protection reaction 8h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 653; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 67mmol epoxy group(ing).
2) preparation of the super cladodification polyamide resin of end carboxyl of modification
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);
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 3.8g of step 1 preparation
Dimethylbenzene: 4.8g
Silicone oligomer: the Z-610820g of the 23330g of Dow Corning Corporation, the 24920g of Dow Corning Corporation, Dow Corning Corporation, the KR21780g of the KR21340g of the IC83620g of Wa Ke company, company of SHIN-ETSU HANTOTAI, the KR9218100g of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAI
Crosslinking catalyst: tetrabutyl titanate 4.7g
Organic solvent: 1-Methoxy-2-propyl acetate 310g, butanols 34g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 80 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 190 ℃ of lower heating 3h, be warming up to 220 ℃, behind the heating 2h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, the oligomeric and crosslinking catalyst of organosilicon; Be heated to 115 ℃, heating 3h; Be cooled to 90 ℃, add at last butanols.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
2) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 140g of the modification of step 1 preparation; Paint filler: carbon black 20g; Silica 1 4g;
Organosilicon auxiliary agent: CoatOSil 35004g; CoatOSil 76502g;
High boiling solvent: methyl isoamyl ketone (MIAK) 2g; Isobutyl isobutyrate 4g.
B) preparation technology
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 6
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.04g
The vitriol oil: 5g
Glycidyl allyl ether: 5g
Platinic chloride: 0.04g
Toluene: 240g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 9h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 90 ℃, nitrogen protection reaction 10h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 833; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 32mmol epoxy group(ing).
2) preparation of the super cladodification polyamide resin of end carboxyl of modification
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);
Epoxy-terminated silicone oil: the hydroxy silicon oil 9.5g of step 1 preparation
Dimethylbenzene: 5.3g
Silicone oligomer: the silicone resin KR15045g of SHIN-ETSU HANTOTAI, the KR21150g of company of SHIN-ETSU HANTOTAI, the KR21270g of company of SHIN-ETSU HANTOTAI, the KR21465g of company of SHIN-ETSU HANTOTAI, the KR21680g of company of SHIN-ETSU HANTOTAI
Crosslinking catalyst: tetrabutyl titanate 3.6g
Organic solvent: 1-Methoxy-2-propyl acetate 218g, dipropylene glycol methyl ether acetate 20g, dipropylene glycol monobutyl ether acetate 10g
B) preparation technology
Just diamine and triprotic acid mix post-heating to 70 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 210 ℃ of lower heating 1h, be warming up to 220 ℃, behind the heating 3h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer and crosslinking catalyst; Be heated to 120 ℃, heating 3h; Add at last dipropylene glycol methyl ether acetate and dipropylene glycol monobutyl ether acetate.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
3) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 120g of the modification of step 2 preparation; Paint filler: carbon black 20g; Silicon-dioxide 5g; Titanium dioxide 5g;
Organosilicon auxiliary agent: CoatOSil 35004g; CoatOSil 75102g; Silicone oil
4g;
High boiling solvent: divalent ester mixture (DBE) 12g.
B) preparation technology
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 7
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.04g
The vitriol oil: 4g
Glycidyl allyl ether: 8g
Platinic chloride: 0.04g
Toluene: 210g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 7h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 75 ℃, nitrogen protection reaction 8h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 533; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 41mmol epoxy group(ing).
2) preparation of the super cladodification polyamide resin of end carboxyl of modification
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)
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 13.4g of step 1 preparation
Dimethylbenzene: 10.4g
Silicone oligomer: the silicone resin KR150168g of SHIN-ETSU HANTOTAI, the IC836100g of Wa Ke company
Crosslinking catalyst: tetrabutyl titanate 2.12g, dioctyl zinc oxide 2.0g
Organic solvent: 1-Methoxy-2-propyl acetate 208g butanols 25g
B) synthesis step:
Diamine and triprotic acid are mixed post-heating to 75 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 180 ℃ of lower heating 1h, be warming up to 240 ℃, behind the heating 1h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Add at last butanols.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
3) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 110g of the modification 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
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 8
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.04g
The vitriol oil: 6g
Glycidyl allyl ether: 12g
Platinic chloride: 0.05g
Toluene: 350g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 7.5h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 75 ℃, nitrogen protection reaction 8.5h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 708; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 52mmol epoxy group(ing).
2) preparation of silicone oligomer
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 oligomer 230g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and the result is 1986; The hydroxy radical content of silicone oligomer adopts the diacetyl oxide method to measure, and the result is 15w%; The oxyethyl group content of silicone oligomer adopts perchloric acid acetyl method to measure, and the result is 3w%; R/Si=1.34; Ph/Me=0.44.
3) preparation of the super cladodification polyamide resin of end carboxyl of modification
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)
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 10.7g of step 1 preparation
Dimethylbenzene: 7.2g
Silicone oligomer: step 2 preparation silicone oligomer 305
Crosslinking catalyst: tetrabutyl titanate 1.5g dioctyl tin oxide 0.5g, tetrabutyl titanate 1.5g, dioctyl zinc oxide 1.0g, diisooctyl zinc oxide 2.5g;
Organic solvent: 1-Methoxy-2-propyl acetate 250g
B) synthesis step:
Diamine and triprotic acid are mixed post-heating to 90 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 180 ℃ of lower heating 1h, be warming up to 240 ℃, behind the heating 1h; Be cooled to 90 ℃, add 1.0 times organic solvent of trivalent alcohol weight, silicone oligomer and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Add at last the residue organic solvent.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
4) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 150g of the modification of step 3 preparation; Paint filler: carbon black 10g; Silicon-dioxide 5g; Titanium dioxide 5g;
Organosilicon auxiliary agent: CoatOSil 35005g; Silicone oil
5g;
High boiling solvent: divalent ester mixture (DBE) 10g.
B) preparation technology
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 9
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.06g
The vitriol oil: 10g
Glycidyl allyl ether: 18g
Platinic chloride: 0.07g
Toluene: 300g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 8h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 80 ℃, nitrogen protection reaction 9h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 492; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 77mmol epoxy group(ing).
2) silicone oligomer
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 oligomer 322g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and the result is 1808; The hydroxy radical content of silicone oligomer adopts the diacetyl oxide method to measure, and the result is 20w%; The oxyethyl group content of silicone oligomer adopts perchloric acid acetyl method to measure, and the result is 2.5w%; R/Si=1.21; Ph/Me=0.55.
3) preparation of the super cladodification polyamide resin of end carboxyl of modification
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)
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 10.8g of step 1 preparation
Dimethylbenzene: 9g
Silicone oligomer: the silicone resin KR15090g of SHIN-ETSU HANTOTAI, the Z-6108100g of Dow Corning Corporation, the IC836100g of Wa Ke company
Crosslinking catalyst: tetrabutyl titanate 2.0g diisooctyl zinc oxide 1.2g, diisooctyl stannic oxide 2.4g
Organic solvent: 1-Methoxy-2-propyl acetate 235g, propandiol butyl ether acetic ester 30g
B) synthesis step:
Dibasic alcohol and triprotic acid are mixed post-heating to 80 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 190 ℃ of lower heating 1.5h, be warming up to 230 ℃, behind the heating 2h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer and crosslinking catalyst; Be heated to 120 ℃, heating 2h; Cool to 90 ℃, add at last the propandiol butyl ether acetic ester.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
4) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 150g of the modification of step 3 preparation;
Paint filler: phthalocyanine blue 20g; Titanium dioxide 20g;
Organic additive: CoatOSil 75108g;
Height boils and reaches solvent: divalent ester mixture (DBE) 2g.
B) preparation technology
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
Embodiment 10
1) preparation of epoxy-terminated silicone oil
A) prescription
Octamethylcyclotetrasiloxane: 200g
Tetramethyl ammonium hydroxide: 0.1g
The vitriol oil: 12g
Glycidyl allyl ether: 20g
Platinic chloride: 0.1g
Toluene: 400g
B) preparation technology
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, add successively octamethylcyclotetrasiloxane by proportioning, behind tetramethyl ammonium hydroxide and the vitriol oil, nitrogen protection reaction 9h; Be warming up to 180 ℃, low-boiling-point substance is removed in underpressure distillation, obtains holding hydrogen silicone oil; To hold hydrogen silicone oil, glycidyl allyl ether, toluene and Platinic chloride add in the reactor; Be warming up to 90 ℃, nitrogen protection reaction 10h, the underpressure distillation desolventizing obtains epoxy-terminated silicone oil.
C) performance
The weight-average molecular weight of epoxy-terminated silicone oil adopts gel permeation chromatography to detect, and the result is 303; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and the result is that every 100g epoxy-terminated silicone oil contains the 86mmol epoxy group(ing).
2) silicone oligomer
A) form
Monomethyl Trimethoxy silane: 42.0g(0.28mol)
Dimethyldimethoxysil,ne: 18.7g(0.14mol)
One phenyltrimethoxysila,e: 123.0g(0.58mol),
B) preparation technology
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 oligomer 290g.
C) performance
The weight-average molecular weight of silicone oligomer adopts gel permeation chromatography to detect, and the result is 802; The hydroxy radical content of silicone oligomer adopts the diacetyl oxide method to measure, and the result is 10.6w%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and the result is 7.4w%; R/Si=1.14; Ph/Me=1.04.
3) preparation of the super cladodification polyamide resin of end carboxyl of modification
A) form:
Triprotic acid: 1,2,4-benzene tricarboxylic acid 231g(1.1mol);
Diamine: DDS 149g(0.5mol); Isophorone diamine 85g(0.5mol)
Epoxy-terminated silicone oil: the epoxy-terminated silicone oil 16.8g of step 1 preparation
Dimethylbenzene: 14g
Silicone oligomer: the silicone intermediate 187g of KR212210g step 2 preparation of company of SHIN-ETSU HANTOTAI
Crosslinking catalyst: tetrabutyl titanate 7.6g dioctyl zinc oxide 2.0g
Organic solvent: 1-Methoxy-2-propyl acetate 400g
B) synthesis step:
Diamine and triprotic acid are mixed post-heating to 90 ℃, add epoxy-terminated silicone oil and dimethylbenzene; Behind 190 ℃ of lower heating 3h, be warming up to 230 ℃, behind the heating 3h; Be cooled to 90 ℃, add 1.2 times 1-Methoxy-2-propyl acetate of trivalent alcohol weight, silicone oligomer and crosslinking catalyst; Be heated to 115 ℃, heating 3h; Be cooled to 80 ℃, add at last the residue 1-Methoxy-2-propyl acetate.
C) the super cladodification polyamide resin of the end carboxyl performance of modification
The over-all properties of the super cladodification polyamide resin of end carboxyl of modification
4) coating
A) form
The super cladodification polyamide resin of the end carboxyl of modification: the super cladodification polyamide resin of the end carboxyl 120g of the modification of step 3 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
The super cladodification polyamide resin of end carboxyl, organosilicon auxiliary agent, the high boiling solvent of paint filler, modification are mixed, add grinding machine for grinding to required particle diameter, both.
C) performance
The performance index of coating
The comparative example
Contrast coating 1 prepares according to document (CN102382314A)
The performance index of coating
Resin in the contrast coating 1 is to adopt silicone intermediate that polyamide resin is carried out modification, and this resin has good resistance toheat, and its heat resisting temperature reaches 370 ℃.But in preparation polyamide resin process, only adopt 4, the lower molecular weight epoxy-terminated silicone oil is not added in diamine and the triprotic acid reactions such as 4-diaminodiphenylsulfone(DDS), isophorone diamine, and the snappiness that causes filming is relatively poor, 8mm only, cold-hot changes performance only 32 times.
The standby coating resistance toheat of resin of the present invention reaches 500 ℃, and snappiness reaches 3mm.Its resistance toheat and snappiness are better than contrast coating 1 far away.
Claims (3)
1. the preparation method of an organic-silicon-modified end carboxyl polyamides resin, the method is comprised of following steps:
Be that the triprotic acid of 1 ~ 2.0 times of diamine mixes post-heating to 70 ~ 90 ℃ with diamine and molar weight, add the dimethylbenzene of 0.02 ~ 0.1 times of the epoxy-terminated silicone oil of 0.05 ~ 0.1 times of diamine weight and diamine weight; Behind 180 ~ 210 ℃ of lower heating 1 ~ 3h, be warming up to 220 ~ 240 ℃, behind heating 1 ~ 3h; Be cooled to 90 ℃, add the organic solvent of 1.0 ~ 1.5 times of diamine weight, 1 ~ 5% crosslinking catalyst of the silicone oligomer that diamine weight is 1.5 ~ 2.0 times and diamine weight; Be heated to 110 ~ 120 ℃, heating 2 ~ 3h; Be cooled to 90 ℃, adding at last organic solvent adjustment solid content is 60 ~ 70%;
Described diamine is Isosorbide-5-Nitrae-cyclohexanediamine, isophorone diamine, 4, a kind of or two or more in 4 '-diaminodiphenylmethane, DDS and 1, the 6-hexanediamine;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3, the 5-benzene tricarboxylic acid or two kinds;
The weight-average molecular weight of described epoxy-terminated silicone oil is 300 ~ 1000, and every 100g epoxy-terminated silicone oil contains epoxy group(ing) 0.1 ~ 1mmol;
The weight-average molecular weight of described silicone oligomer is 800 ~ 2000, and contains the methoxy or ethoxy of 2.5 ~ 15w% and the hydroxyl of 3 ~ 20w%;
Described crosslinking catalyst is a kind of or two or more in tetrabutyl titanate, tetrabutyl titanate, dioctyl tin oxide, diisooctyl stannic oxide, dioctyl zinc oxide and the diisooctyl zinc oxide;
Described organic solvent is one or more in 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 the dipropylene glycol monobutyl ether acetate.
2. the preparation method of organic-silicon-modified end carboxyl polyamides resin claimed in claim 1 is characterized in that, the weight-average molecular weight of described epoxy-terminated silicone oil is 300 ~ 800, and every 100g epoxy-terminated silicone oil contains 30 ~ 50mmol epoxy group(ing).
3. coating, this coating contains 60 ~ 80w% modified polyamide resin, 10 ~ 20w% high-temperature resisting pigment filler and 5 ~ 20w% high boiling solvent; Wherein, described high boiling solvent refers to a kind of or two or more in divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and the methyl isoamyl ketone it is characterized in that described modified polyamide resin is to be prepared by claim 1 or 2 described methods.
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| CN103333346B (en) * | 2013-06-14 | 2015-08-26 | 华南理工大学 | A kind of can the hyperbranched resilient material and preparation method thereof of self-healing |
| CN103333346A (en) * | 2013-06-14 | 2013-10-02 | 华南理工大学 | Hyperbranched elastic material capable of self-healing and preparation method thereof |
| CN104004198B (en) * | 2014-06-11 | 2016-07-06 | 南方医科大学 | The preparation method of the polyamide modified organic siliconresin of a kind of high rigidity and the coating containing this resin |
| CN104004197A (en) * | 2014-06-11 | 2014-08-27 | 南方医科大学 | Method for preparing polyamide modified organic silicon resin and paint prepared from resin |
| CN104004198A (en) * | 2014-06-11 | 2014-08-27 | 南方医科大学 | Preparation method of high-hardness polyamide modified organic silicon resin and coatings containing high-hardness polyamide modified organic silicon resin |
| CN103992474B (en) * | 2014-06-11 | 2016-03-30 | 南方医科大学 | A kind of preparation method of ultrabranching polyamide modified organic silicone resin and the standby coating of this resin-made |
| CN103992474A (en) * | 2014-06-11 | 2014-08-20 | 南方医科大学 | Preparation method of hyperbranched polyamide modified organic silicon resin and paint prepared from resin |
| CN108084447A (en) * | 2016-11-22 | 2018-05-29 | 武汉超支化树脂科技有限公司 | End carboxyl super branched polymer and its application in the preparation of high performance plastics composite material |
| CN108084447B (en) * | 2016-11-22 | 2021-03-02 | 武汉超支化树脂科技有限公司 | Carboxyl-terminated hyperbranched polymer and application thereof in preparation of high-performance plastic composite material |
| CN109824909A (en) * | 2019-02-27 | 2019-05-31 | 济南大学 | A kind of preparation and its application of organic-silicon-modified hyper-branched polyester-amide resin |
| CN109824909B (en) * | 2019-02-27 | 2020-10-27 | 济南大学 | Preparation and application of organic silicon modified hyperbranched polyester-amide resin |
| CN111234255A (en) * | 2020-03-10 | 2020-06-05 | 齐鲁工业大学 | Hyperbranched organic silicon wetting agent for waterborne polyurethane and preparation method thereof |
| CN113429782A (en) * | 2021-06-24 | 2021-09-24 | 华峰集团有限公司 | Transparent polyamide resin and preparation method thereof |
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