CN102964592B - 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
- Publication number
- CN102964592B CN102964592B CN201210492484.7A CN201210492484A CN102964592B CN 102964592 B CN102964592 B CN 102964592B CN 201210492484 A CN201210492484 A CN 201210492484A CN 102964592 B CN102964592 B CN 102964592B
- Authority
- CN
- China
- Prior art keywords
- diamine
- silicone oil
- epoxy
- weight
- polyamide resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyamides (AREA)
- Silicon Polymers (AREA)
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 organic high molecular compound field, relate to the macromolecular compound that amidate action obtains, be specifically related to polyamide resin.
Background technology
Polyamide resin has good thermotolerance, wearability, chemical proofing and good mechanical property and processing characteristics, and frictional coefficient is low, has certain flame retardant resistance, is easy to processing, is widely used as engineering plastics.The consistency of polymeric amide and various kinds of resin is good, in coating industry, is used widely.But polyamide resin molecular weight is large, poorly soluble, and viscosity is high, more difficult and other resins carry out chemical modification.In order to obtain low viscosity, the polyamide resin that solvability is good, conventional use dimeracid and diamine polymerization.Such as Wu Jianliang etc. (Wu Jianliang, the development of low-molecular-weight polyamide resin, Zhejiang chemical industry, 2004,35(03), 19), with Rice pollard oil raw material of fatty acid synthesis of dimmer acid, then obtain lower molecular weight with polyethylene polyamine polymerization, low viscous polymeric amide.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 epoxy resin.
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 makes hyperbranched polymer be applicable to being applied to high solid component coating, can reduce system viscosity with the blend of line polymer coating, improves system mobility; High solvability can reduce the consumption of solvent, reduces costs, and reduces noxious gas emission; It is less that highly branched structure tangles hyperbranched polymer molecule interchain, is difficult for crystallization, makes coating have good film forming properties; Numerous terminal functionality makes Hyperbranched Polymer have very strong correctability ability, can prepare and be applicable to multi-purpose coating.For example Chinese patent CN102382314A, by end carboxyl super branched polyamide modified silicone resin, improves mechanical property, chemical resistance and the acidproof water resistance of silicone resin.But the snappiness of the end carboxyl super branched polyamide modified silicone resin of above-mentioned preparation is poor, under high low temperature alternation condition, can ftracture, limit its application.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method of the super cladodification polyamide resin of end carboxyl of modification, modified polyamide prepared by the method have advantages of resistance toheat and snappiness good.
The scheme of the technical problem that the present invention is above-mentioned is:
A preparation method for the super cladodification polyamide resin of end carboxyl of modification, the method is comprised of following steps:
The triprotic acid that is 1 ~ 2.0 times of diamine by diamine and molar weight mixes post-heating to 70 ~ 90 ℃, adds 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; At 180 ~ 210 ℃, heat after 1 ~ 3h, be warming up to 220 ~ 240 ℃, after 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 ℃, finally adding organic solvent to adjust 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 1,6-hexanediamine;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3,5-benzene tricarboxylic acid or two kinds;
The 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 the hydroxyl of the methoxy or ethoxy that contains 2.5 ~ 15w% and 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 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 dipropylene glycol monobutyl ether acetate.
Above-mentioned preparation method, wherein said epoxy-terminated silicone oil can be prepared by following methods:
The vitriol oil of the tetramethyl disiloxane of octamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane weight 0.01 ~ 0.05% and octamethylcyclotetrasiloxane weight 2 ~ 6% is added in reactor to 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% adds in reactor; Be warming up to 70 ~ 90 ℃, nitrogen protection reaction 8 ~ 10h, underpressure distillation, except 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 the conventional siloxanes in this area, and its technique and reaction conditions are the routine techniquess that those skilled in the art should grasp.
Above-mentioned preparation method, wherein said silicone oligomer can also be the KR211 of company of SHIN-ETSU HANTOTAI, the KR214 of the KR212 of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAI, the IC836 of the KR216 of company of SHIN-ETSU HANTOTAI, Wa Ke company, the KR9218 of the KR213 of company of SHIN-ETSU HANTOTAI, company of SHIN-ETSU HANTOTAI, the KR217 of company of SHIN-ETSU HANTOTAI, 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 is better 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 modification prepared by method of the present invention, has the following advantages:
Diamine, triprotic acid and epoxy-terminated silicone oil are reacted to the end carboxyl super branched polyamide resin of preparation, wherein the carboxyl on triprotic acid and the amino on diamine carry out amidate action, the amino of diamine and the epoxy group(ing) in epoxy-terminated silicone oil react simultaneously, flexible organosilicon segment is embedded in ultrabranching polyamide, improve the resistance toheat of polymeric amide, snappiness and the cold-and-heat resistent of filming change performance.
On the other hand, by the super cladodification polyamide resin of end carboxyl of end carboxyl super branched polyamide resin and silicone oligomer reaction preparation modification, the hydroxyl on end carboxyl super branched polyamide resin wherein, under 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 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, the super cladodification polyamide resin of end carboxyl that this coating contains the obtained modification of 60 ~ 80w% aforesaid method, 10 ~ 20w% is high temperature resistant filler and 5 ~ 20w% high boiling solvent, 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 methyl isoamyl ketone;
Described high temperature resistant filler is the conventional high temperature resistant filler in this area, can be one or more in titanium dioxide, silicon-dioxide and silicon carbide.
In above-mentioned coating, also can add the conventional high-temperature resisting pigment in this area, described high-temperature resisting pigment can be the inorganic high-temperature resistant pigment such as carbon black, iron oxide red, can be also the organic high temperature-resistant pigment such as phthalocyanine blue.
In above-mentioned coating, can also add the conventional organosilicon auxiliary agent in this area, as, play the effects such as levelling, froth breaking, pigment wetting, viscosity adjustment.Above-mentioned organosilicon auxiliary agent can also be silicone oil, organic silicon modified by polyether auxiliary agent, as, the CoatOSil series organic silicon modified by polyether auxiliary agent of Mai Tu new high-tech material company limited.Those skilled in the art can be according to the kind and the consumption that require to determine organic silicon additive, and the consumption that the inventor recommends is 1 ~ 5w%.
The preparation method of above-mentioned coating is the conventional preparation method in this area, 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 end carboxyl of above-mentioned modification, so there is high heat resistance energy and good snappiness.
Embodiment
It is below the non-limiting example of technical scheme of the present invention.
Embodiment 1:
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 90 ℃, nitrogen protection reaction 10h, underpressure distillation, except 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 result is 303; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and 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 to post-heating to 70 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 180 ℃, heat after 1h, be warming up to 240 ℃, after heating 1h; Be cooled to 90 ℃, add the organic solvent of 1.0 times of diamine weight, silicone oligomer and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Be cooled to 90 ℃, finally add 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
1* resistance toheat: test piece is toasted after 2h in 180 ℃, put into the Ovenized electric furnace that potentiometer is checked, by 5 ℃/min rising temperature, with furnace temperature, to requirement of experiment temperature, start timing, sample, after continuous high temperature, takes out, be chilled to room temperature (25 ℃), with magnifying glass, observe coatingsurface situation, as without be full of cracks, obscission, illustrate that coating heat resistance can be good.
2) coating
A) form
The super cladodification polyamide resin of 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 2:
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 85 ℃, nitrogen protection reaction 8.5h, underpressure distillation, except 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 result is 587; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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 to post-heating to 80 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 200 ℃, heat after 3h, be warming up to 220 ℃, after 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 ℃, finally add 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 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 the end carboxyl of paint filler, modification, high boiling solvent, auxiliary agent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 3:
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 80 ℃, nitrogen protection reaction 10h, underpressure distillation, except 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 result is 987; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, by proportioning, add successively after siloxanes and 4.5mmol hydrochloric acid, start to stir and heat up, keep homo(io)thermism after being warmed up to 60 ℃, under agitation drip 31.7g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool to room temperature, 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 result is 802; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 10.6w%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and 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 to post-heating to 85 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 210 ℃, heat after 2.5h, be warming up to 235 ℃, after 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 ℃, finally add 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 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive 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) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 90 ℃, nitrogen protection reaction 10h, underpressure distillation, except 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 result is 313; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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 to post-heating to 80 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 220 ℃, heat after 2.5h, be warming up to 230 ℃, after 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 ℃, finally add 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 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
The performance index of coating
Embodiment 5
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 80 ℃, nitrogen protection reaction 8h, underpressure distillation, except 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 result is 653; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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 to post-heating to 80 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 190 ℃, heat after 3h, be warming up to 220 ℃, after 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 ℃, finally add 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 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 6
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 90 ℃, nitrogen protection reaction 10h, underpressure distillation, except 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 result is 833; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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; At 210 ℃, heat after 1h, be warming up to 220 ℃, after heating 3h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer and crosslinking catalyst; Be heated to 120 ℃, heating 3h; Finally add 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 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 7
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 75 ℃, nitrogen protection reaction 8h, underpressure distillation, except 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 result is 533; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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 to post-heating to 75 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 180 ℃, heat after 1h, be warming up to 240 ℃, after heating 1h; Be cooled to 90 ℃, add 1-Methoxy-2-propyl acetate, silicone oligomer and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Finally add 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 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 8
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 75 ℃, nitrogen protection reaction 8.5h, underpressure distillation, except 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 result is 708; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, by proportioning, add successively after siloxanes and 7.0mmol hydrochloric acid, start to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃, under agitation drip 43.1g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool to room temperature, 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 result is 1986; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 15w%; The oxyethyl group content of silicone oligomer adopts perchloric acid acetyl method to measure, and 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 is prepared 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 to post-heating to 90 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 180 ℃, heat after 1h, be warming up to 240 ℃, after heating 1h; Be cooled to 90 ℃, add the organic solvent of 1.0 times of trivalent alcohol weight, silicone oligomer and crosslinking catalyst; Be heated to 110 ℃, heating 2h; Finally add 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 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 9
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 80 ℃, nitrogen protection reaction 9h, underpressure distillation, except 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 result is 492; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, by proportioning, add successively after siloxanes and 5.5mmol hydrochloric acid, start to stir and heat up, keep homo(io)thermism after being warmed up to 70 ℃, under agitation drip 42.7g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool to room temperature, 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 result is 1808; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 20w%; The oxyethyl group content of silicone oligomer adopts perchloric acid acetyl method to measure, and 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 to post-heating to 80 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 190 ℃, heat after 1.5h, be warming up to 230 ℃, after 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 ℃, finally add 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 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Embodiment 10
1) preparation of epoxy-terminated silicone oil
A) formula
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, by proportioning, add successively octamethylcyclotetrasiloxane, after 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 reactor; Be warming up to 90 ℃, nitrogen protection reaction 10h, underpressure distillation, except 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 result is 303; The oxirane value content of epoxy-terminated silicone oil adopts hydrochloric acid-acetone method to measure, and result is that every 100g epoxy-terminated silicone oil contains 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
In the reactor that prolong, thermometer, dropping funnel and agitator are housed, by proportioning, add successively after siloxanes and 4.5mmol hydrochloric acid, start to stir and heat up, keep homo(io)thermism after being warmed up to 60 ℃, under agitation drip 31.7g distilled water, after dropwising, after isothermal reaction 3h, start underpressure distillation again, pressure-controlling is at 0.06MPa, boil off the small molecules producing in reaction process, cool to room temperature, 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 result is 802; The hydroxy radical content of silicone oligomer adopts diacetyl oxide method to measure, and result is 10.6w%; The methoxy content of silicone oligomer adopts perchloric acid acetyl method to measure, and 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 to post-heating to 90 ℃, add epoxy-terminated silicone oil and dimethylbenzene; At 190 ℃, heat after 3h, be warming up to 230 ℃, after heating 3h; Be cooled to 90 ℃, add the 1-Methoxy-2-propyl acetate of 1.2 times of trivalent alcohol weight, silicone oligomer and crosslinking catalyst; Be heated to 115 ℃, heating 3h; Be cooled to 80 ℃, finally add 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 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 the end carboxyl of paint filler, modification, organosilicon auxiliary agent, high boiling solvent are mixed, add grinding machine for grinding to arrive required particle diameter, both.
C) performance
The performance index of coating
Comparative example
Contrast coating 1 is prepared according to document (CN102382314A)
The performance index of coating
Resin in contrast coating 1 is to adopt silicone intermediate to carry out modification to polyamide resin, and this resin has good resistance toheat, and its heat resisting temperature reaches 370 ℃.But only adopt 4 in preparing polyamide resin process, the diamines such as 4-diaminodiphenylsulfone(DDS), isophorone diamine react with triprotic acid, do not add lower molecular weight epoxy-terminated silicone oil, and the snappiness that causes filming is 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. a preparation method for organic-silicon-modified end carboxyl polyamides resin, the method is comprised of following steps:
The triprotic acid that is 1～2.0 times of diamine by diamine and molar weight mixes post-heating to 70～90 ℃, adds 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; At 180～210 ℃, heat after 1～3h, be warming up to 220～240 ℃, after 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 ℃, finally adding organic solvent to adjust solid content is 60～70wt%;
Described diamine is Isosorbide-5-Nitrae-cyclohexanediamine, isophorone diamine, 4, and 4 '-diaminodiphenylmethane, DDS and 1,6-be a kind of or two or more in diamines;
Described triprotic acid is a kind of in 1,2,4-benzene tricarboxylic acid and 1,3,5-benzene tricarboxylic acid or two kinds;
The weight-average molecular weight of described epoxy-terminated silicone oil is 300～1000, and every 100g epoxy-terminated silicone oil contains epoxy group(ing) 8～100mmol;
The weight-average molecular weight of described silicone oligomer is 800～2000, and the hydroxyl of the methoxy or ethoxy that contains 2.5～15wt% and 3～20wt%;
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 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 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. a coating, this coating contains 60～80wt% modified polyamide resin, 10～20wt% high-temperature resisting pigment filler and 5～20wt% high boiling solvent; Wherein, described high boiling solvent refers to a kind of or two or more in divalent ester mixture, ethylene glycol ether acetate, Diethylene Glycol monobutyl ether acetate, isobutyl isobutyrate, propionic acid-3-ether ethyl ester and methyl isoamyl ketone, it is characterized in that described modified polyamide resin is to be prepared by method described in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210492484.7A CN102964592B (en) | 2012-11-27 | 2012-11-27 | Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210492484.7A CN102964592B (en) | 2012-11-27 | 2012-11-27 | Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102964592A CN102964592A (en) | 2013-03-13 |
| CN102964592B true CN102964592B (en) | 2014-08-27 |
Family
ID=47795045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210492484.7A Expired - Fee Related CN102964592B (en) | 2012-11-27 | 2012-11-27 | Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102964592B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104004197B (en) * | 2014-06-11 | 2016-08-24 | 南方医科大学 | The preparation method of a kind of polyamide modified organic siliconresin and the standby coating of this resin-made |
| 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 |
| 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 |
| 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 |
| CN109824909B (en) * | 2019-02-27 | 2020-10-27 | 济南大学 | Preparation and application of organic silicon modified hyperbranched polyester-amide resin |
| CN111234255B (en) * | 2020-03-10 | 2021-11-02 | 齐鲁工业大学 | Hyperbranched organic silicon wetting agent for waterborne polyurethane and preparation method thereof |
| CN113429782B (en) * | 2021-06-24 | 2022-04-22 | 华峰集团有限公司 | Transparent polyamide resin and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6440527A (en) * | 1987-08-07 | 1989-02-10 | Toshiba Silicone | Siloxane-amide block copolymer having terminal alkenyl group and production thereof |
| JP2961620B2 (en) * | 1990-09-18 | 1999-10-12 | 株式会社巴川製紙所 | Polyamide-polysiloxane block copolymer and method for producing the same |
| CN101792574B (en) * | 2010-03-30 | 2012-02-08 | 中科院广州化学有限公司 | Modified epoxy resin composite material of prereacted material of epoxy-terminated silicone oil and preparation method and application thereof |
| CN102382314B (en) * | 2011-06-25 | 2013-01-09 | 南方医科大学 | Preparation method and application of modified organic silicon resin |
-
2012
- 2012-11-27 CN CN201210492484.7A patent/CN102964592B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102964592A (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102964592B (en) | Preparation method of modified terminal-carboxyl-hyperbranched polyamide resin and paint containing resin | |
| CN103113578B (en) | Modified carboxyl-terminated hyperbranched polyamide resin, as well as preparation method and application thereof | |
| CN102977363B (en) | Preparation method of modified amino-terminated hyper-branched polyamide resin and coating comprising resin | |
| CN103113566B (en) | Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof | |
| CN102504265B (en) | Method for preparing polyester modified organic silicon resin and coating containing the resin | |
| CN102504293B (en) | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin | |
| CN103881104B (en) | A kind of preparation method of modified polyester resin and application | |
| CN102977350B (en) | Preparation method of modified carboxyl-terminated hyperbranched polyester resin and coating containing resin | |
| CN102382314B (en) | Preparation method and application of modified organic silicon resin | |
| CN102344569B (en) | Preparation method of modified organic silicon resin and paint containing prepared modified organic silicon resin | |
| CN102504271A (en) | Method for preparing hyperbranched polyester modified organic silicon resin | |
| CN103435779B (en) | A kind of preparation method, the epoxy anticorrosion protective paint using this solidifying agent and preparation method thereof of polyamino organosilicon solidifying agent | |
| CN103113570B (en) | Amino-terminated silicon oil modified carboxyl-terminated hyperbranched polyester resin, and preparation method and application thereof | |
| CN102977352B (en) | Preparation method of modified polyester resin and coating containing polyester resin obtained by same | |
| CN103073718B (en) | Amino-terminated silicon oil modified amino-terminated hyperbranched polyamide resin and preparation method and application of polyamide resin | |
| CN104558578B (en) | A kind of preparation method of nano silicon composite organic modified ultra-branching vibrin and the coating containing this resin | |
| JP3263177B2 (en) | Epoxy group-containing silicone resin and method for producing the same | |
| CN103992474B (en) | A kind of preparation method of ultrabranching polyamide modified organic silicone resin and the standby coating of this resin-made | |
| CN103113567B (en) | Epoxy-terminated silicon oil modified carboxyl-terminated hyperbranched polyester, and preparation method and application thereof | |
| CN102977351B (en) | Preparation method of modified polyester resin and coating containing polyester resin | |
| CN103193986A (en) | Epoxy-terminated silicone oil-modified hydroxyl-terminated hyperbranched polyester, and preparation method and application thereof | |
| CN104558571B (en) | A kind of preparation method of nano zine oxide composite organic modified ultra-branching mylar and containing the coating of this resin | |
| CN104558577B (en) | A kind of preparation method of nano aluminium oxide composite organic modified ultra-branching vibrin and the coating containing this resin | |
| CN104004197B (en) | The preparation method of a kind of polyamide modified organic siliconresin and the standby coating of this resin-made | |
| CN104004198B (en) | The preparation method of the polyamide modified organic siliconresin of a kind of high rigidity and the coating containing this resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140827 Termination date: 20201127 |