CN104072784A - Surface treatment method for improving compatibility of polyaniline and epoxy resin - Google Patents
Surface treatment method for improving compatibility of polyaniline and epoxy resin Download PDFInfo
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- CN104072784A CN104072784A CN201410327079.9A CN201410327079A CN104072784A CN 104072784 A CN104072784 A CN 104072784A CN 201410327079 A CN201410327079 A CN 201410327079A CN 104072784 A CN104072784 A CN 104072784A
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Abstract
The invention discloses a surface treatment method for improving the compatibility of polyaniline and epoxy resin. The surface treatment method comprises the following step of carrying out surface treatment on polyaniline by using isocyanate epoxy resin and alkoxysilane epoxy resin for chemically bonding epoxy functional groups on the surface of polyaniline to enhance the compatibility of polyaniline and epoxy resin. Epoxy resin surface modified polyaniline is obtained through the following steps of adding 10-30 parts of isocyanate epoxy resin, 10-30 parts of alkoxysilane epoxy resin, 100-200 parts of polyaniline isocyanate and 20-600 parts of solvent into a reaction vessel, stirring for 1-2h, grinding by using a coating grinding machine until the fineness is smaller than 60mu m, and then, discharging. The compatibility of epoxy resin surface modified polyaniline obtained by the invention and epoxy resin is good, so that the problem of poor interface compatibility of resin and polyaniline in an anticorrosive coating is solved, the compatibility of polyaniline and epoxy resin is remarkably improved, the anticorrosion effect of the anticorrosive coating is improved, and the service life of the anticorrosive coating is prolonged.
Description
Technical field
The invention belongs to material surface modifying technology field, particularly a kind of surface treatment method that improves polyaniline and epoxy resin compatibility, is intended to improve the consistency of polyaniline and epoxy resin, improves interface performance, improves barrier propterty.
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Background technology
Conducting polymer appear as the starting material that anticorrosion engineering provides excellent performance.In numerous conductive polymerss, polyaniline (PANI) is a kind of intrinsically conducting polymer with conjugated electrons structure, has the advantages such as good conductivity, cheap and easy to get and environmental stability be good, is considered to have most the conducting polymer composite of practical application foreground.As protective system, polyaniline is anticorrosive, scratch resistance, can effectively stop air, water and salinity to play a role, check metal rusting and corrosion, and cost is low, usage is easy, can welding, there is larger practical prospect, for the anticorrosion industry in China ocean provides the base resin kind of a brand-new excellent performance.Polyaniline can be made polyaniline/epoxy co-mixing system, polyaniline/polyurethane comixing system, polyaniline/polyimide co-mixing system, polyaniline/styrene acrylic copolymer (SAA) co-mixing system and polyaniline/poly-butyl isobutyrate co-mixing system etc. in addition, and these blends can be used for the surface protection of various occasions.Epoxy coat has good solidity to corrosion and chemical proofing, and sticking power is good, can adopt multiple solidifying agent to solidify and the paint film of acquisition different performance, in Marine Gravity And is anticorrosion, occupies an leading position.Polyaniline and epoxy composite, expection has better preservative effect, but in use, polyaniline and epoxy resin compatibility are poor, Presence of an interface defect, easily causes corrosive medium along polyaniline and epoxy resin interface infiltration, thereby reduces coating antiseptic effect.Therefore need improve the consistency between polyaniline and epoxy resin, to improve coating integral protection performance.
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Summary of the invention
The object of the invention is to provides a kind of surface treatment method that improves polyaniline and epoxy resin compatibility in order to overcome above the deficiencies in the prior art.
The present invention is achieved by the following technical solutions:
A kind of surface treatment method that improves polyaniline and epoxy resin compatibility, by isocyanic ester epoxy resin and alkoxyl silicone epoxy resin p-poly-phenyl amine, carry out surface treatment, at polyaniline surface chemistry bonding epoxy-functional, thus the consistency of enhancing and epoxy resin, and concrete steps are as follows:
(1), by mass parts, 1 part of epoxy resin and 0.2-3 part vulcabond are used respectively to the identical dissolution with solvents of 0.1-0.5 part and be placed in respectively different reaction vessels; Under stirring and nitrogen protection, with 20-90 drip/minute speed epoxy resin solution is dropwise added in vulcabond solution, ultrasonic being uniformly dispersed, room temperature reaction 1-2 hour, be warming up to subsequently 60 ℃-120 ℃ reaction 1-8 hour, underpressure distillation, removes unreacted vulcabond, obtains isocyanic ester epoxy resin;
(2) by mass parts, under nitrogen protection, 1 part of epoxy resin is dissolved in 0.1-0.5 part solvent, and is placed in reaction vessel, again 0.2-3 part silane coupling agent is dissolved in 0.1-0.5 part homogeneous solvent, by silane coupler solution with 20-90 drip/minute speed join in epoxy resin solution, ultrasonic being uniformly dispersed, room temperature reaction 1-2 hour, be warming up to subsequently 60 ℃-120 ℃ reaction 1-8 hour, underpressure distillation, suction filtration, except desolventizing, obtains alkoxyl silicone epoxy resin;
(3) by mass parts, 1 part of polyaniline and 0.1-0.5 part solvent are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid, standby; 0.2-1 part vulcabond is dissolved and to obtain vulcabond solution with 0.1-0.5 part homogeneous solvent, and with 10-90 drip/minute speed join in suspension liquid, drip off rear ultrasonic being uniformly dispersed, and at 0-40 ℃ of reaction 1-24 hour; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
(4) by mass parts, by step (1) gained isocyanic ester epoxy resin 10-30 part, step (2) gained alkoxyl silicone epoxy resin 10-30 part, step (3) gained isocyanic ester polyaniline 100-200 part and solvent 20-600 part are placed in reaction vessel, stir 1-2 hour, discharging after using paint mill to be milled to fineness to be less than 60 microns, obtains the polyaniline of epoxy resin surface modification.
Described raising polyaniline and the surface treatment method of epoxy resin compatibility, what solvent described in step (1), (2), (3), (4) can be in toluene, acetone, N-Methyl pyrrolidone, dimethylbenzene, vinylbenzene, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, butanone, pimelinketone is a kind of.
The surface treatment method of above-described raising polyaniline and epoxy resin compatibility, purification can dewater before described solvent use.
Described raising polyaniline and the surface treatment method of epoxy resin compatibility, at least contain a hydroxy functional group in described epoxy resin molecular structure.
Described raising polyaniline and the surface treatment method of epoxy resin compatibility, what described epoxy resin can be in bisphenol A type epoxy resin, phenol aldehyde modified epoxy resin or bisphenol f type epoxy resin is a kind of.
Described raising polyaniline and the surface treatment method of epoxy resin compatibility, what described vulcabond can be in tolylene diisocyanate, hexamethylene-diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, dicyclohexyl methane diisocyanate or hexahydrotoluene vulcabond is a kind of.
Described raising polyaniline and the surface treatment method of epoxy resin compatibility, silane coupling agent can be for containing R-SiX
3structure, wherein X is a kind of in methoxyl group, oxyethyl group, R is aliphatics, aromatic series, alicyclic structure, and contains a kind of in active function groups hydroxyl, carboxyl, primary amino, secondary amino group.
The raw materials used isocyanic ester epoxy resin of the present invention can be by isocyano and polyaniline chemical bonding, alkoxyl silicone epoxy resin can be by alkoxy-functional and polyaniline chemical bonding, make polyaniline surface coated epoxy resin, thereby improved the consistency of polyaniline and epoxy resin, improved the boundary defect between polyaniline and epoxy resin.Owing to being chemical bonding effect between polyaniline and epoxy resin, its boundary defect and compatibility problem have obtained good solution.Isocyanic ester epoxy resin, alkoxyl silicone epoxy resin is difficult to obtain commercially available prod, and therefore, the present invention provides isocyanic ester epoxy resin simultaneously, the preparation method of alkoxyl silicone epoxy resin and isocyanic ester polyaniline.A kind of surface treatment method that improves polyaniline and epoxy resin compatibility provided by the invention yet there are no bibliographical information at home and abroad, and prepared epoxy resin surface modified polyaniline can be used as coating functional stuffing and uses.
The present invention to polyaniline molecule, obtains the polyaniline that surface grafting has epoxy resin by epoxy resin chemical graft, to improve the consistency of polyaniline and epoxy resin, reduces the interface binding deficient of base-material and resin.The polyaniline of processing through the method and epoxy resin compatibility are good, in conjunction with firmly, can be used as the polyaniline padding of the anticorrosion epoxy coating of Marine Gravity And, improve antiseptic property and the work-ing life of epoxy resin.
The present invention adopts the advantage of technique scheme to be:
1, polyaniline surface chemistry of the present invention is grafted with epoxide group, good with epoxy resin compatibility, can improve the homogeneity of polyaniline component and coating resin, the boundary defect of resin and filler in minimizing coating, the protective of raising coating.
2, the present invention adopts the polyaniline of epoxy resin surface modification, contains part carboxyl functional group, can with the hydroxyl generation esterification bonding of metallic surface, can improve coating interface bonding force, thereby greatly improve coating protection performance.
3, raw material type of the present invention is many, wide material sources.
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embodiment:
Below in conjunction with embodiment, technique scheme of the present invention is further described, but never limits the scope of the invention, unless outside specializing in the embodiment of the present invention, related ratio is mass ratio, related umber is mass parts.
Embodiment 1
In four-hole boiling flask, with 0.5 part of dry toluene, 0.2 part of tolylene diisocyanate (TDI) is dissolved to nitrogen protection; With 0.4 part of dry toluene, 1 part of E44 epoxy resin is dissolved and moved in constant pressure funnel; under room temperature, stirring and nitrogen protection condition; with the speed of 30 droplets/minute, E44 epoxy resin solution is dropwise added in TDI toluene solution; ultrasonic dispersion 20 minutes; room temperature ℃ reaction 2 hours, heat up 120 ℃ and react 5 hours, underpressure distillation subsequently; remove unreacted TDI, obtain TDI epoxy resin.
In reaction vessel, with 0.4 part of dry toluene, 1 part of E44 epoxy resin is dissolved, be filled with nitrogen protection; With 0.5 part of dry toluene, 0.2 part of 3-aminopropyl triethoxysilane is dissolved, in nitrogen protection, be displaced downwardly to constant pressure funnel, speed with 20 droplets/minute of per minutes adds in the toluene solution of epoxy resin, ultrasonic dispersion 20 minutes, stirring at room 2 hours, is warming up to subsequently 120 ℃ and continues reaction 2 hours, cooling, underpressure distillation, except desolventizing, obtains alkoxyl silicone epoxy resin;
1 part of anhydrous polyaniline and 0.3 part of anhydrous N-Methyl pyrrolidone are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid A; 0.2 part of tolylene diisocyanate is dissolved in to 0.5 part of N-Methyl pyrrolidone solution, with constant pressure funnel, with 50 droplets/minute, adds in suspension liquid A, after dripping off, carry out ultrasonic dispersion 20 minutes, and 25 ℃ of reactions 4 hours; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
By mass parts, by 20 parts of gained isocyanic ester epoxy resin, 100 parts of 20 parts of alkoxyl silicone epoxy resin, 150 parts of isocyanic ester polyanilines and N-Methyl pyrrolidone are placed in reaction vessel, stir 1 hour, by discharging after using paint mill to be milled to fineness to be less than 60 microns, obtain the polyaniline of epoxy resin surface modification.
Embodiment 2
In four-hole boiling flask, with 0.4 part of anhydrous dimethyl benzene dewatering in advance after purifying, 0.3 part of hexamethylene-diisocyanate (HDI) is dissolved to nitrogen protection; With 0.2 part of anhydrous dimethyl benzene, the 1 part of E44 epoxy resin dewatering is in advance dissolved and moved in constant pressure funnel; under room temperature, stirring and nitrogen protection condition; with the speed of 50 droplets/minute, E44 epoxy resin solution is dropwise added in HDI anhydrous dimethyl benzole soln; ultrasonic dispersion 20 minutes; subsequently room temperature reaction 2 hours, the 100 ℃ of reactions 4 hours that heat up, underpressure distillation; remove unreacted HDI, obtain HDI epoxy resin.
Acetone, epoxy resin and 3-aminopropyl trimethoxysilane are dewatered, are dried and purify.In reaction vessel, with 0.5 part of anhydrous propanone, 1 part of E51 epoxy resin is dissolved, be filled with nitrogen protection; With 0.4 part of anhydrous propanone, 0.5 part of 3-aminopropyl trimethoxysilane is dissolved, in nitrogen protection, be displaced downwardly to constant pressure funnel, speed with 30 droplets/minute of per minutes adds in the acetone soln of epoxy resin, ultrasonic dispersion 20 minutes, stirring at room 2 hours, is warming up to subsequently 60 ℃ and continues reaction 4 hours, cooling, underpressure distillation, removes acetone, obtains alkoxyl silicone epoxy resin;
1 part of anhydrous polyaniline and 0.1 part of anhydrous N-Methyl pyrrolidone are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid A; 0.3 part of hexamethylene-diisocyanate is dissolved in to 0.4 part of N-Methyl pyrrolidone solution, with constant pressure funnel, with 60 droplets/minute, adds in suspension liquid A, after dripping off, carry out ultrasonic dispersion 20 minutes, and 30 ℃ of reactions 5 hours; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
By mass parts, by 10 parts of gained isocyanic ester epoxy resin, 300 parts of 10 parts of alkoxyl silicone epoxy resin, 100 parts of isocyanic ester polyanilines and anhydrous N-Methyl pyrrolidone are placed in reaction vessel, stir 1.5 hours, discharging after being milled to fineness in universal lacquer runner milling and being less than 60 microns, obtains the polyaniline of epoxy resin surface modification.
Embodiment 3
Thermometer is being housed, in the four-hole boiling flask of agitator, condenser, by 0.5 part of dry isobutanol, 1 part of isophorone diisocyanate (IPDI) is being dissolved to nitrogen protection; By 0.2 part of dry isobutanol, the 1 part of E44 epoxy resin dewatering is in advance dissolved and moved in constant pressure funnel; under room temperature, stirring and nitrogen protection condition; with the speed of 20 droplets/minute, E44 epoxy resin solution is added in IPDI dry isobutanol solution; subsequently room temperature ℃ reaction 2 hours; 120 ℃ of reactions 4 hours heat up; underpressure distillation, removes unreacted IPDI, obtains IPDI epoxy resin.
By butanone, epoxy resin and N-(β aminoethyl)-γ-aminopropyl methyl-dimethoxy silane dewaters, dry purification.Thermometer is being housed, in the reaction vessel of agitator, condenser, with 0.1 part of anhydrous butanone, 1 part of E21 epoxy resin is being dissolved, be filled with nitrogen protection; With 0.4 part of anhydrous butanone by 0.3 part of N-(β aminoethyl)-γ-aminopropyl methyl-dimethoxy silane dissolves, in nitrogen protection, be displaced downwardly to constant pressure funnel, speed with 50 droplets/minute of per minutes adds in the butanone solution of epoxy resin, stirring at room 2 hours, be warming up to subsequently 85 ℃ and continue reaction 3 hours, cooling, underpressure distillation, remove butanone, obtain alkoxyl silicone epoxy resin;
1 part of anhydrous polyaniline and 0.5 part of anhydrous N-Methyl pyrrolidone are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid A; 0.4 part of isophorone diisocyanate is dissolved in to 0.4 part of N-Methyl pyrrolidone solution, with constant pressure funnel, with 50 droplets/minute, adds in suspension liquid A, after dripping off, carry out ultrasonic dispersion 20 minutes, and 0 ℃ of reaction 6 hours; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
By mass parts, by 30 parts of gained isocyanic ester epoxy resin, 200 parts of 10 parts of alkoxyl silicone epoxy resin, 200 parts of isocyanic ester polyanilines and N-Methyl pyrrolidone are placed in reaction vessel, stir 2 hours, discharging after being milled to fineness in universal lacquer runner milling and being less than 60 microns, obtains the polyaniline of epoxy resin surface modification.
Embodiment 4
Thermometer is being housed, in the four-hole boiling flask of agitator, condenser, with 0.3 part of anhydrous pimelinketone, 1 part of diphenylmethanediisocyanate (MDI) is being dissolved to nitrogen protection; With 0.1 part of anhydrous pimelinketone, the 1 part of E21 epoxy resin dewatering is in advance dissolved and moved in constant pressure funnel; under room temperature, stirring and nitrogen protection condition; with the speed of 20 droplets/minute, E21 epoxy resin solution is dropwise added in the anhydrous pimelinketone solution of MDI; subsequently room temperature reaction 2 hours; 100 ℃ of reactions 4 hours heat up; underpressure distillation, removes unreacted MDI, obtains MDI epoxy resin.
By isopropylcarbinol, epoxy resin and N-2-(aminoethyl)-3-aminopropyl trimethoxysilane dewaters, dry purification.Thermometer is being housed, in the reaction vessel of agitator, condenser, by 0.4 part of dry isobutanol, 1 part of E44 epoxy resin is being dissolved, be filled with nitrogen protection; By 0.5 part of dry isobutanol by 0.6 part of N-2-(aminoethyl)-3-aminopropyl trimethoxysilane dissolves; in nitrogen protection, be displaced downwardly to constant pressure funnel; speed with 60 droplets/minute of per minutes adds in the isobutanol solution of epoxy resin; stirring at room 2 hours; be warming up to subsequently 110 ℃ and continue reaction 6 hours, cooling, underpressure distillation; remove isopropylcarbinol, obtain alkoxyl silicone epoxy resin.
1 part of anhydrous polyaniline and 0.5 part of anhydrous propanone are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid A; 1 part of diphenylmethanediisocyanate is dissolved in to 0.5 part of acetone soln, with constant pressure funnel with 50/, minute add in suspension liquid A, after dripping off, carry out ultrasonic dispersion 20 minutes, and 25 ℃ of reactions 4 hours; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
By mass parts, by 10 parts of gained isocyanic ester epoxy resin, 100 parts of 30 parts of alkoxyl silicone epoxy resin, 200 parts of isocyanic ester polyanilines and N-Methyl pyrrolidone are placed in reaction vessel, stir 2 hours, discharging after being milled to fineness in universal lacquer runner milling and being less than 60 microns, obtains the polyaniline of epoxy resin surface modification.
Embodiment 5
Thermometer is being housed, in the four-hole boiling flask of agitator, condenser, with 0.5 part of dry-out benzene ethene, 2 parts of dicyclohexyl methane diisocyanates (HMDI) is being dissolved to nitrogen protection; With 0.4 part of dry-out benzene ethene, the 1 part of E21 epoxy resin dewatering is in advance dissolved and moved in constant pressure funnel; under room temperature, stirring and nitrogen protection condition; with the speed of 90 droplets/minute, the dry-out benzene vinyl solution of E21 is dropwise added in the dry-out benzene vinyl solution of HMDI; subsequently room temperature reaction 1 hour; 100 ℃ of reactions 8 hours heat up; underpressure distillation, removes unreacted HMDI, obtains HMDI epoxy resin.
Pimelinketone, epoxy resin and 3-aminopropyl trimethoxysilane are dewatered, are dried and purify.In reaction vessel, with 0.3 part of anhydrous pimelinketone, 1 part of E51 epoxy resin is dissolved, be filled with nitrogen protection; With 0.4 part of anhydrous pimelinketone, 0.3 part of 3-aminopropyl trimethoxysilane is dissolved, in nitrogen protection, be displaced downwardly to constant pressure funnel, speed with 40 droplets/minute of per minutes adds in the pimelinketone solution of epoxy resin, stirring at room 2 hours, the temperature that is warming up to subsequently pimelinketone backflow continues reaction 8 hours, cooling, underpressure distillation, remove pimelinketone, obtain alkoxyl silicone epoxy resin;
Anhydrous 1 part of polyaniline and anhydrous 0.4 part of acetone are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid A; 0.6 part of dicyclohexyl methane diisocyanate is dissolved in to 0.5 part of acetone soln, with constant pressure funnel with 90/, minute add in suspension liquid A, after dripping off, carry out ultrasonic dispersion 20 minutes, and 25 ℃ of reactions 5 hours; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
By mass parts, gained isocyanic ester is connect to 30 parts of epoxy resins, 300 parts of 15 parts of alkoxyl silicone epoxy resin, 180 parts of isocyanic ester polyanilines and N-Methyl pyrrolidone are placed in reaction vessel, stir 2 hours, discharging after being milled to fineness in universal lacquer runner milling and being less than 60 microns, obtains the polyaniline of epoxy resin surface modification.
Embodiment 6
In four-hole boiling flask, with 0.1 part of anhydrous dimethyl benzene dewatering in advance after purifying, 0.3 part of hexamethylene-diisocyanate (HDI) is dissolved to nitrogen protection; With 0.4 part of anhydrous dimethyl benzene, the 1 part of E44 epoxy resin dewatering is in advance dissolved and moved in constant pressure funnel; under room temperature, stirring and nitrogen protection condition; with the speed of 60 droplets/minute, E44 epoxy resin solution is dropwise added in HDI anhydrous dimethyl benzole soln; ultrasonic dispersion 20 minutes; subsequently room temperature reaction 1 hour, the 110 ℃ of reactions 1 hour that heat up, underpressure distillation; remove unreacted HDI, obtain HDI epoxy resin.
Acetone, epoxy resin and 3-aminopropyl trimethoxysilane are dewatered, are dried and purify.In reaction vessel, with 0.5 part of anhydrous propanone, 1 part of E51 epoxy resin is dissolved, be filled with nitrogen protection; With 0.5 part of anhydrous propanone, 3 parts of 3-aminopropyl trimethoxysilane are dissolved, in nitrogen protection, be displaced downwardly to constant pressure funnel, speed with 90 droplets/minute of per minutes adds in the acetone soln of epoxy resin, ultrasonic dispersion 20 minutes, stirring at room 1 hour, is warming up to subsequently 90 ℃ and continues reaction 1 hour, cooling, underpressure distillation, removes acetone, obtains alkoxyl silicone epoxy resin;
1 part of anhydrous polyaniline and 0.3 part of anhydrous N-Methyl pyrrolidone are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid A; 0.2 part of hexamethylene-diisocyanate is dissolved in to 0.1 part of N-Methyl pyrrolidone solution, with constant pressure funnel, with 10 droplets/minute, adds in suspension liquid A, after dripping off, carry out ultrasonic dispersion 20 minutes, and 40 ℃ of reactions 1 hour; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
By mass parts, by 30 parts of gained isocyanic ester epoxy resin, 600 parts of 20 parts of alkoxyl silicone epoxy resin, 180 parts of isocyanic ester polyanilines and anhydrous N-Methyl pyrrolidone are placed in reaction vessel, stir 1 hour, discharging after being milled to fineness in universal lacquer runner milling and being less than 60 microns, obtains the polyaniline of epoxy resin surface modification.
Embodiment 7
Thermometer is being housed, in the four-hole boiling flask of agitator, condenser, with 0.5 part of anhydrous pimelinketone, 3 parts of grams of diphenylmethanediisocyanates (MDI) is being dissolved to nitrogen protection; With 0.4 part of anhydrous pimelinketone, the 1 part of E21 epoxy resin dewatering is in advance dissolved and moved in constant pressure funnel; under room temperature, stirring and nitrogen protection condition; with the speed of 35 droplets/minute, E21 epoxy resin solution is dropwise added in the anhydrous pimelinketone solution of MDI; subsequently room temperature reaction 2 hours; 60 ℃ of reactions 7 hours heat up; underpressure distillation, removes unreacted MDI, obtains MDI epoxy resin.
By isopropylcarbinol, epoxy resin and N-2-(aminoethyl)-3-aminopropyl trimethoxysilane dewaters, dry purification.Thermometer is being housed, in the reaction vessel of agitator, condenser, by 0.3 part of dry isobutanol, 1 part of E44 epoxy resin is being dissolved, be filled with nitrogen protection; By 0.1 part of dry isobutanol by 0.3 part of N-2-(aminoethyl)-3-aminopropyl trimethoxysilane dissolves; in nitrogen protection, be displaced downwardly to constant pressure funnel; speed with 40 droplets/minute of per minutes adds in the isobutanol solution of epoxy resin; stirring at room 2 hours; be warming up to subsequently 100 ℃ and continue reaction 7 hours, cooling, underpressure distillation; remove isopropylcarbinol, obtain alkoxyl silicone epoxy resin.
1 part of anhydrous polyaniline and 0.4 part of anhydrous propanone are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid A; 0.6 part of diphenylmethanediisocyanate is dissolved in to 0.4 part of acetone soln, with constant pressure funnel with 50/, minute add in suspension liquid A, after dripping off, carry out ultrasonic dispersion 20 minutes, and 10 ℃ of reactions 24 hours; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
By mass parts, by 10 parts of gained isocyanic ester epoxy resin, 20 parts of 10 parts of alkoxyl silicone epoxy resin, 100 parts of isocyanic ester polyanilines and N-Methyl pyrrolidone are placed in reaction vessel, stir 2 hours, discharging after being milled to fineness in universal lacquer runner milling and being less than 60 microns, obtains the polyaniline of epoxy resin surface modification.
The above, be only the embodiment that the present invention is feasible, can not limit to this interest field of the present invention, according to technical scheme of the present invention and technical thought, makes other various corresponding changes and distortion, still belongs to the protection domain that the present invention is contained.
Claims (7)
1. a surface treatment method that improves polyaniline and epoxy resin compatibility, it is characterized in that, by isocyanic ester epoxy resin and alkoxyl silicone epoxy resin p-poly-phenyl amine, carry out surface treatment, at polyaniline surface chemistry bonding epoxy-functional, thereby the consistency of enhancing and epoxy resin, concrete steps are as follows:
(1), by mass parts, 1 part of epoxy resin and 0.2-3 part vulcabond are used respectively to the identical dissolution with solvents of 0.1-0.5 part and be placed in respectively different reaction vessels; Under stirring and nitrogen protection, with 20-90 drip/minute speed epoxy resin solution is dropwise added in vulcabond solution, ultrasonic being uniformly dispersed, room temperature reaction 1-2 hour, be warming up to subsequently 60 ℃-120 ℃ reaction 1-8 hour, underpressure distillation, removes unreacted vulcabond, obtains isocyanic ester epoxy resin;
(2) by mass parts, under nitrogen protection, 1 part of epoxy resin is dissolved in 0.1-0.5 part solvent, and is placed in reaction vessel, again 0.2-3 part silane coupling agent is dissolved in 0.1-0.5 part homogeneous solvent, by silane coupler solution with 20-90 drip/minute speed join in epoxy resin solution, ultrasonic being uniformly dispersed, room temperature reaction 1-2 hour, be warming up to subsequently 60 ℃-120 ℃ reaction 1-8 hour, underpressure distillation, suction filtration, except desolventizing, obtains alkoxyl silicone epoxy resin;
(3) by mass parts, 1 part of polyaniline and 0.1-0.5 part solvent are placed in dry, airtight container, under nitrogen protection, stir 20 minutes, make suspension liquid, standby; 0.2-1 part vulcabond is dissolved and to obtain vulcabond solution with 0.1-0.5 part homogeneous solvent, and with 10-90 drip/minute speed join in suspension liquid, drip off rear ultrasonic being uniformly dispersed, and at 0-40 ℃ of reaction 1-24 hour; Suction filtration, except desolventizing and unreacted vulcabond, obtains isocyanic ester polyaniline;
(4) by mass parts, by step (1) gained isocyanic ester epoxy resin 10-30 part, step (2) gained alkoxyl silicone epoxy resin 10-30 part, step (3) gained isocyanic ester polyaniline 100-200 part and solvent 20-600 part are placed in reaction vessel, stir 1-2 hour, discharging after using paint mill to be milled to fineness to be less than 60 microns, obtains the polyaniline of epoxy resin surface modification.
2. the surface treatment method of raising polyaniline according to claim 1 and epoxy resin compatibility, it is characterized in that, solvent described in step (1), (2), (3), (4) is a kind of in toluene, acetone, N-Methyl pyrrolidone, dimethylbenzene, vinylbenzene, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, butanone, pimelinketone.
3. the surface treatment method of raising polyaniline according to claim 1 and 2 and epoxy resin compatibility, is characterized in that, purification dewaters before described solvent use.
4. the surface treatment method of raising polyaniline according to claim 1 and epoxy resin compatibility, is characterized in that, at least contains a hydroxy functional group in described epoxy resin molecular structure.
5. the surface treatment method of raising polyaniline according to claim 1 and epoxy resin compatibility, is characterized in that, described epoxy resin is a kind of in bisphenol A type epoxy resin, phenol aldehyde modified epoxy resin or bisphenol f type epoxy resin.
6. the surface treatment method of raising polyaniline according to claim 1 and epoxy resin compatibility, it is characterized in that, described vulcabond is a kind of in tolylene diisocyanate, hexamethylene-diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, dicyclohexyl methane diisocyanate or hexahydrotoluene vulcabond.
7. the surface treatment method of raising polyaniline according to claim 1 and epoxy resin compatibility, is characterized in that, silane coupling agent is for containing R-SiX
3structure, wherein X is a kind of in methoxyl group, oxyethyl group, R is aliphatics, aromatic series, alicyclic structure, and contains a kind of in active function groups hydroxyl, carboxyl, primary amino, secondary amino group.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107099219A (en) * | 2017-05-09 | 2017-08-29 | 中国科学院海洋研究所 | A kind of polyaniline-modified epoxy zinc powder composite coating and preparation method |
| CN107201070A (en) * | 2017-06-23 | 2017-09-26 | 河海大学 | A kind of preparation method of polyaniline padding for epoxy coating |
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| CN107201070A (en) * | 2017-06-23 | 2017-09-26 | 河海大学 | A kind of preparation method of polyaniline padding for epoxy coating |
| CN108573764A (en) * | 2018-05-04 | 2018-09-25 | 芜湖天科生物科技有限公司 | A kind of crosslinking polythiophene additives for battery and preparation method thereof |
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