CN105086419B - A kind of electrodepositable fluorinated polyimide modified engineered plastic alloy and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy and preparation method thereof, engineering plastic alloy is made up of PA66 resins, PPO resins, FMPI resins, conductive filler, compatilizer and auxiliary agent.Preparation method includes：(1) FMPI resins are prepared；(2) conductive filler is handled with coupling agent aqueous solution；(3) PA66 resins, PPO resins, FMPI resins, conductive filler, compatilizer and auxiliary agent are mixed, carries out high-temperature fusion mixing, granulation is produced.Operating procedure of the present invention is simple, and production cost is low, and product has good electric property, mechanical property and resistance to elevated temperatures etc., and excellent combination property can be applied to the parts such as new-energy automobile beater or beat-up, door handle, bumper bar, have broad application prospects.

Description

A kind of electrodepositable fluorinated polyimide modified engineered plastic alloy and preparation method thereof

Technical field

The invention belongs to engineering plastic alloy field, more particularly to a kind of electrodepositable fluorinated polyimide is modified engineering plastic Expect alloy and preparation method thereof.

Background technology

The ecology potential of engineering plastics must be closely related with various new and high technologies, while being also national science and technology and industrial level Important symbol and material base.The consumption of automobile engineering plastics be weigh a national Trend of Auto Manufacturing Technologies level mark it One.Over nearly more than 30 years, the consumption of automobile plastic is being continuously increased in the world.

The development of current new-energy automobile just necessarily requires automotive light weight technology mainly with energy-saving for objective.And full generation It is Sabic companies that PA66/PPO alloy materials, which are mainly produced, in the range of boundary, and its trade mark is Noryl*GTX series, and it is polyamide (PA) and Noryl (PPO) alloy material.It combines the dimensional stability, heat resistance and PA polymer of PPO materials Chemical resistance and easy processing characteristic.This causes such material with excellent in chemical resistance itself, but also with good hard Heat resistance required by degree, impact resistance and on-line spray.

Body of a motor car, the plastic of beater or beat-up are exactly an important breakthrough of automotive light weight technology.Alloy work general at present Engineering plastics can not meet the production and processing of beater or beat-up as PC/ABS, PC/PBT, PA/ABS, PA66/PPO alloy etc., mainly lack Putting is：Strong and unyielding property is inadequate, it is impossible to electroplated, and heat-resisting low, size is unstable.

Nylon is most important auto industry engineering plastics.Auto parts and components are also the maximum consumption city of PA engineering plastics , more than 1/3rd of aggregate consumption.The continuous improvement required with people automotive performance and PA engineering plastics itself Development, automobile is with PA just in the trend risen year by year.The part that PA (including modified product) can be used to make on automobile has door knob Hand, shell, fan, wheelhouse portions, deflector, upholstery, water storage equipment lid, line card, various in-car electric connectors etc..

MODIFIED PP O is mainly used in making the auto parts and components with high-strength, high tenacity and good electrical property, and moisture absorption is small, It can be used as automobile valve bonnet, fuel tank conductive plate, transformer and wind motor vane etc..And PA66/PPO alloy processabilities are good It is good, high-strength, high tenacity, the small processing that can be used as automobile exterior trimming parts of moisture absorption.

About the research of PA66/PPO alloys, existing many disclosed document reports：

Beam literary riddles et al.【The research of the composition and performance relation of PPO/PA66 alloy system matrixes, Beijing University of Chemical Technology's machine The academic dissertation of electrical engineering institute】, it is primarily characterized in that：It has studied polyphenylene oxide (PPO) and the matrix group of nylon66 fiber (PA66) two The proportional relation between alloy property.As a result show, in the case where bulking agent TGDDM and SEBS-g-MA consumption is certain, The quality proportioning of two matrix components is 5:When 5, co-mixing system has preferable comprehensive mechanical property.

Zhang Wei Chinese invention patent CN20091018 2012.X disclose a kind of toughness PPE and PA66 of doing Plastic alloy and preparation method thereof, is primarily characterized in that：Synthesize high logarithmic viscosity number PPTA's the invention discloses a kind of Method, in ul-trasonic irradiation environment, is followed the steps below successively, a. prepare solution system, first by cosolvent stirring and dissolving in In polar solvent, then add p-phenylenediamine and continue stirring and dissolving, obtain solution system；B low-temperature polycondensations, by gained in a steps Solution system continues to stir, in low temperature environment, adds paraphthaloyl chloride and carries out polycondensation reaction, is subsequently added acid absorbent；c Curing, the system of gained in b step is transferred in water-bath and cured, and is stirred simultaneously, is finally given evengranular height more right than dense Number viscosity PPTA resins；The present invention improves PPTA combined coefficient and PPTA logarithmic viscosity number, and helps to reduce cost.

Xu Dong et al. Chinese invention patent ZL2010101405464 discloses a kind of high-strength PPO/PA66 alloy materials And preparation method thereof, it is primarily characterized in that：High-strength PPO/PA66 alloy materials are made up of following components by weight percentage： Polyphenylene oxide resin 20%-40%；Nylon 66 resin 20%-40%；Compatilizer 5%-10%；Toughener 5%-10%；Glass fibers Tie up 5%-15%；Glass microballoon 5%-15%；Mica powder 5%-15%；Antioxidant 0.2%-0.4%；Other auxiliary agent 0.5%- 1%.The present invention is integrated by using glass fibre compound glass microballon, mica powder enhancing PPO/PA66 alloys, obtained material Excellent performance, not only intensity is high, heat-resist, easily spraying, while also having splendid dimensional stability, warpage is low, is adapted to It is molded large scale structure product and heating part.

Polyimides is developed in the sixties, and the most frequently used one kind is by pyromellitic acid anhydride and aromatic diamine system .Contain multiple aromatic heterocycle construction unit in polyimide molecule, therefore its heat resistance is splendid, its usual glass transition temperature exists More than 260 DEG C.Polyimide resin is the family macromolecule material with extremely excellent heat resistance.Conventional polyimides knot Structure, its heat decomposition temperature is generally more than 500 DEG C, while also having obdurability.Therefore, thermosetting resin is also frequently utilized for, The heat-resisting plasticized modifier of such as epoxy resin, bimaleimide resin.

About the research of polyimide material, existing many disclosed document reports：

Chinese invention patent CN101921482A discloses a kind of thermoset polyimide resin and preparation method thereof, the tree Fat is made up of component A and B component, and its weight ratio is 1：2-6；Wherein component A is the thick dimaleoyl imino of homogeneous phase transparent Polyimide resin solution, solid content 10%-25%；B component is four dimaleoyl imino bisphenol-A solution, solid content 30%- 40%；The preparation method of dimaleoyl imino polyimide resin liquid (component A) includes following two steps：(1) it is 2,2- is double [4- (2,4- diamino phenoxy) phenyl] propane and highly polar aprotic organic solvent are put into reactor, at room temperature, stirring After dissolving completely, maleic anhydride solid powder is added, is stirred at room temperature to being completely dissolved, continues stirring reaction after 0.5 hour, plus Enter aromatic dicarboxylic anhydride, stirring reaction 5-8 hours at room temperature, obtain the thick resin solution of homogeneous phase transparent；(2) add altogether Dehydrating agent is boiled, azeotropic reflux water-dividing stirring reaction obtains the thick dimaleoyl imino polyamides of homogeneous phase transparent sub- after 6-8 hours Polyimide resin liquid；The preparation method of four dimaleoyl imino bisphenol-A solution (B component) includes following two steps：(1) it is 2,2- is double [4- (2,4- diamino phenoxy) phenyl] propane and highly polar aprotic organic solvent are put into reactor, at room temperature, stirring After dissolving completely, maleic anhydride solid powder is added, is stirred at room temperature to being completely dissolved, continues stirring reaction after 3 hours, obtains Homogeneous phase transparent solution；(2) azeotropy dehydrant is added, azeotropic reflux water-dividing stirring reaction obtains four horses of homogeneous phase transparent after 5 hours Carry out imide bisphenol-A solution.

The thermoset polyimide resin that the present invention is obtained can be applied not only to high-temperature resistance adhesive and glass fibre increases The matrix resin of strong composite, and it is fibre-reinforced advanced multiple to can also be applied to the high performance such as carbon fiber, aramid fiber The matrix resin of condensation material.

Chinese invention patent CN101973147A discloses a kind of preparation side of high-temperature resistant polyimide glass fabric laminated board Method, mainly comprises the following steps：(1) at room temperature, it is 1 by mol ratio:Double (2,4- diamino phenoxies) benzene of 2 1,4- and Malaysia Acid anhydrides is added in highly polar aprotic organic solvent, and stirring reaction adds aromatic diamine monomer, stirring after 1 hour at room temperature After dissolving completely, aromatic dicarboxylic anhydride is added, at room temperature stirring reaction 3 hours, add initiator, stirring and dissolving is obtained Mutually transparent thick resin solution, i.e. component A；(2) it is 1 by mol ratio:Double (2,4- diamino phenoxies) benzene of 4 1,4- and Maleic anhydride is added in highly polar aprotic organic solvent, and stirring reaction is after 2 hours at room temperature, and the resin for obtaining homogeneous phase transparent is molten Liquid, i.e. B component；(3) in use, being at room temperature well mixed A, B component, polyimide precursor resin solution is obtained, glass is used Cloth impregnating resin solution, preliminary drying semi-solid preparation obtains prepreg, and high-temperature high-pressure machine heat cure is entered after stacking, obtains high temperature resistant polyamides sub- Amine glass cloth laminated board.

Yu Xinhai, Xu Meifang, Fan Liangzi【The preparation of maleimide side base Kapton and performance study, insulation Material, 2011, (4)；1-3】Disclose preparation and its performance study of a kind of maleimide side base polyimides, principal character It is：Using double [4- (2,4- diamino phenoxies) phenyl] propane (BDAPPP) monomers of 2,2-, maleic anhydride (MA), 4,4 '- The poly- of maleamic acid side base is made in diaminodiphenyl ether (44ODA) and 3,3 ', 4,4 '-tetrabasic carboxylic acid biphenyl dianhydride (BPDA) synthesis Acid amides acid resin (MPAA) solution, through film, hot imidization obtains tough and tensile transparent maleimide side base Kapton (MPI), and to its performance study.

The Chinese invention patent CN101560298A (2009-10-21) in Yu Xin seas discloses a kind of thermoplastic fluorine-containing fully aromatic Type polyimide powder and preparation method thereof, is primarily characterized in that：In the presence of catalyst, by fluorinated aromatic binary primary Amine in phenol solvent, reacts -10 hours 5 hours, the precipitating poured into while hot under high-speed stirred state with aromatic dicarboxylic anhydride In agent, solid powder is separated out, filters, wash, soak, filter, dry, acquisition thermoplastic fluorine-containing fully aromatic polyimide powder. The thermoplastic fluorine-containing fully aromatic polyimide powder solubility of the present invention is good, is epoxy resin, unsaturated polyimides resin, no The high performance heat resistant plasticized modifier of the thermosetting resins such as saturated polyester resin, has a good application prospect, and simple to operate, Cost is low, environment-friendly, suitable for industrial production.

The content of the invention

The technical problems to be solved by the invention are to provide a kind of electrodepositable fluorinated polyimide modified engineered plastic and closed Gold and preparation method thereof, this method operating procedure is simple, and production cost is low, and product has good electric property, mechanical property With resistance to elevated temperatures etc., excellent combination property can be applied to the parts such as new-energy automobile beater or beat-up, door handle, bumper bar, have Wide application prospect.

A kind of electrodepositable fluorinated polyimide modified engineered plastic alloy of the present invention, by mass ratio 100:30-100: 5-15:10-50:10-30:1-5 PA66 resins, PPO resins, FMPI resins, conductive filler, compatilizer and auxiliary agent composition；Its In, FMPI resins are by mol ratio 1:2:7-12:Double [4- (2,4- diamino phenoxies) phenyl] HFC-236fas of 5-10 2,2-, Maleic anhydride, aromatic dianhydride, the obtained dimaleoyl imino polyimide resin of aromatic diamine reaction.

Described PA66 resins be as obtained by 1,6- hexamethylene diamines and 1,6- adipic acids by polycondensation reaction poly hexamethylene adipamide oneself Diamine resin.

Described PPO resins are the polyphenylene oxide resin by itself polycondensation reaction by 2,6- xylenols.

Described conductive filler is selected from graphene, conductive black, copper powder, aluminium powder, silver powder, nickel powder, silver-plated copper powder, silver-plated nickel One or more in powder, silver-plated glass beads.

Described compatilizer is selected from maleic anhydride grafting polyhexamethylene adipamide resin, maleic anhydride grafted polyphenylene ether tree One or more in fat, maleic anhydride graft phenylethene-ethylene-butadiene-styrene copolymer resin.

Described auxiliary agent is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, β-(3,5- bis- Tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three (2,4- di-tert-butyl-phenyls) phosphite esters, 2,6- di-t-butyls- 4- methylphenols, N, N '-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propiono] hexamethylene diamine, two (the tertiary fourths of 2- hydroxyls -3- Base -5- aminomethyl phenyls) methane, 4,4 '-thiobis (6- tert-butyl-m-cresols), the double (3,5- di-t-butyl -4- hydroxy benzenes of 1,2- Base) propionic acid hydrazine, dilauryl thiodipropionate, the polymer of succinic acid and 4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols, Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, double (3,5- di-tert-butyl-4-hydroxyl benzyls monoethyl phosphate) nickel, 2,4 dihydroxyl benzophenone, 2-hydroxy-4-n-octoxybenzophenone, ESCALOL 567,2- (2 '-hydroxyls Base -5 '-aminomethyl phenyl) BTA, 2- (2 '-hydroxyl -3 '-the tert-butyl group -5 '-aminomethyl phenyl) -5- chlorinated benzotriazoles, 2- (2 '-hydroxyl -3 ', 5 '-diamyl phenyl) BTA, 2- (2 '-hydroxyl -5 '-t-octyl phenyl) BTA, 2- phenyl benzene And imidazoles -5- sulfonic acid, 2- [2 '-hydroxyl -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] BTA, 2- (2H- benzos three Azoles -2-) one or more in -6- (dodecyl) -4- methylphenols.

Described aromatic dianhydride be selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 3,3 ', 4, 4 '-tetracarboxylic biphenyl dianhydride, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl sulfone dianhydride, 2, Double (3,4- dicarboxyphenyis) hexafluoropropane dianhydrides of 2-, 2,2- double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydride, 2, Double [4- (3,4- di carboxyl phenyloxies) phenyl] hexafluoropropane dianhydrides of 2-, 1,4- double (3,4- di carboxyl phenyloxies) benzene dianhydride, 1, Double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 3-, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl sulfone dianhydrides, 4,4 '-bis- (3,4- Di carboxyl phenyloxy) benzophenone dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) biphenyl dianhydrides, 4,4 '-bis- (3,4- dicarboxyls Phenoxyl) one or more in diphenyl ether dianhydride.

Described aromatic diamine is selected between p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, methylresorcinol diamines, trimethyl Phenylenediamine, dimethyl-p-phenylenediamine, 4,4 '-MDA, 3,3 '-dimethyl -4,4 '-MDA, 4,4 ' - Diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 4,4 '-diaminodiphenylsulfone, 3,3 '-diamino Double (4- amino-benzene oxygens) benzene of base diphenyl sulphone (DPS), 4,4 '-benzidine, 1,3-, double (4- amino-benzene oxygens) benzene of 1,4-, 1,3- are double Double (3- amino-benzene oxygens) benzene of (3- amino-benzene oxygens) benzene, 1,4-, 2,2- double [4- (4- amino-benzene oxygens) phenyl] propane, 2,2- Double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of double [4- (3- amino-benzene oxygens) phenyl] propane, 2,2-, the double [4- of 2,2- (3- amino-benzene oxygens) phenyl] HFC-236fa, 4,4 '-bis- (4- amino-benzene oxygens) -3,3 ', 5,5 '-tetramethyl biphenyl, 4,4 ' - Double (4- amino-benzene oxygens) biphenyl, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl ether, 4, 4 '-bis- (3- amino-benzene oxygens) diphenyl ether, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl-methanes, 4,4 '-bis- (3- amino-benzene oxygens) Diphenyl-methane, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulphone (DPS)s, 2,2 '-two (trifluoros Methyl) -4,4 '-benzidine, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,4-, the double (3- trifluoromethyls -4- of 1,4- Amino-benzene oxygen) benzene, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,3-, the double (3- trifluoromethyl -4- aminobenzene oxygen of 1,3- Base) benzene, double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane of 2,2-, the double [4- (3- trifluoromethyl -4- amino of 2,2- Phenoxy group) phenyl] propane, 2,2- double [4- (2- trifluoromethyl-4-aminophenoxyls) -2,6- 3,5-dimethylphenyls] propane, 2,2- Double [4- (2- trifluoromethyl -4- the ammonia of double [4- (3- trifluoromethyl-4-aminophenoxyls) -2,6- 3,5-dimethylphenyls] propane, 2,2- Phenoxyl) phenyl] HFC-236fa, double [4- (3- trifluoromethyl-4-aminophenoxyls) phenyl] HFC-236fas of 2,2-, 4,4 '- Double (2- trifluoromethyl-4-aminophenoxyls) diphenyl-methanes, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) -3,3 ', 5, 5 '-tetramethyl biphenyl, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl, 4,4 '-bis- (3- trifluoromethyl -4- amino Phenoxy group) -3,3 ', 5,5 '-tetramethyl biphenyl, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS)s, 4,4 '- Double (3- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS)s, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) -3,3 ', 5,5 ' - Tetramethyl diphenyl sulfone, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) -3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulfide, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) diphenyl sulfides, 4, 4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) hexichol first The one or more of ketone.

A kind of preparation method of electrodepositable fluorinated polyimide modified engineered plastic alloy of the present invention, including following step Suddenly：

(1) double [4- (2,4- diamino phenoxies) phenyl] HFC-236fas of 2,2- and highly polar aprotic organic solvent are added Enter in reactor, at room temperature after stirring and dissolving, ice-water bath is cooled to less than 5 DEG C, add maleic anhydride and aromatic dianhydride, stirring After reaction -2 hours 1 hour, aromatic diamine is added, continues stirring reaction -4 hours 2.5 hours, dehydrating agent is subsequently added and urges Agent, removes ice-water bath, is heated to 90 DEG C -100 DEG C, stirring reaction -8 hours 4 hours adds precipitating agent, and stirring 1 is small When, filtering is washed 2 times -3 times with acetone, and 90 DEG C of vacuum drying obtain FMPI resins；

(2) conductive filler is handled with coupling agent aqueous solution, its concrete technology is：Coupling agent aqueous solution and conductive filler are put Enter in reactor, after 60 DEG C -80 DEG C are stirred -2 hours 1 hour, be cooled to room temperature, filter, in dry 1 hour -2 at 100 DEG C Hour, that is, obtain the conductive filler of coupling agent treatment；Wherein, the mass ratio of coupling agent aqueous solution and conductive filler is 4-8:1；

(3) PA66 resins, PPO resins, FMPI resins, conductive filler, compatilizer and auxiliary agent are mixed, squeezed using twin-screw Go out machine, in 270 DEG C of -290 DEG C of progress high-temperature fusion mixing, granulation obtains electrodepositable fluorinated polyimide modified engineered plastic Alloy.

Highly polar aprotic organic solvent in the step (1) is selected from N,N-dimethylformamide, N, N- dimethyl second Acid amides, N- methyl -2-PyrrolePyrrolidone, N- ethyls -2-PyrroleOne or more in pyrrolidone, dimethyl sulfoxide (DMSO)；Wherein, it is highly polar Aprotic organic solvent and the mass ratio of total reactant are 3-5：1；The quality of total reactant refers to double [4- (the 2,4- diaminos of 2,2- Phenoxyl) phenyl] HFC-236fa, maleic anhydride, the quality sum of aromatic dianhydride and aromatic diamine.

Dehydrating agent in the step (1) is selected from acetic anhydride, propionic andydride, butyric anhydride, trifluoroacetic anhydride (TFAA), chloracetic acid acid anhydride, two One or more in carbodicyclo hexylimide；Wherein, the mol ratio of dehydrating agent and aromatic dianhydride is 2.5-3.5:1.

Catalyst in the step (1) is selected from triethylamine, tri-n-butylamine, pyridine, picoline, lutidines, connection pyrrole One or more in pyridine, methyl bipyridyl；Wherein, the mol ratio of catalyst and aromatic dianhydride is 0.01-0.1:1.

Precipitating agent in the step (1) is selected from methanol, ethanol, propyl alcohol, isopropanol, ethylene glycol, glycol monoethyl ether, second One or more in glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, MEK；Wherein, precipitating agent with it is highly polar The mass ratio of aprotic organic solvent is 2-5：1.

The mass ratio of acetone and highly polar aprotic organic solvent in the step (1) is 0.5-1:1.

The mass percent concentration of coupling agent aqueous solution in the step (2) is 1%~10%.

Described coupling agent is selected from 3- aminopropyl triethoxysilanes, 3- aminopropyl trimethoxysilanes, glycidoxy One or more in propyl-triethoxysilicane, glycidoxy trimethyl TMOS.

Beneficial effect

(1) preparation technology of the invention is simple, cost is low, easy to operate, reaction raw materials convenient sources, can be set general Standby middle completion preparation process, is advantageously implemented industrialized production；

(2) present invention has good combination property, with high temperature tolerance, molding processibility, excellent electric property With mechanical property etc.；

(3) present invention can apply to parts such as new-energy automobile beater or beat-up, door handle, bumper bars, with wide application Prospect.

Embodiment

With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.

Embodiment 1

By double [4- (2,4- diamino phenoxies) phenyl] HFC-236fas of 54.8 grams of (0.1 mole) 2,2- and 1180 grams of N, N- Dimethyl acetamide is added in reactor, at room temperature after stirring and dissolving, and ice-water bath is cooled to less than 5 DEG C, adds 19.6 gram (0.2 Mole) maleic anhydride and 217.0 grams (0.7 mole) 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, stirring reaction is after 1 hour, plus Enter 100.0 grams of (0.5 moles) 3,4 '-diaminodiphenyl ether continues stirring reaction 4 hours, and being subsequently added 183.6 grams, (1.8 rub You) acetic anhydride and 0.65 gram of (0.007 mole) picoline, ice-water bath is removed, 100 DEG C are heated to, stirring reaction 4 is small When, 2360 grams of methanol are added, quick stirring 1 hour, filtering is washed 2 times -3 times, 90 DEG C of vacuum drying 3 are small with 590 grams of acetone When, 354.1 grams of FMPI resins (theoretical yield is 366.2 grams) are obtained, FMPI-1 are denoted as, yield is 96.7%.

Embodiment 2

By 54.8 grams of (0.1 mole) 2,2- double [4- (2,4- diamino phenoxies) phenyl] HFC-236fa, 1560 grams of N- first Base -2-PyrrolePyrrolidone and 2000 grams of DMAs are added in reactor, at room temperature after stirring and dissolving, ice-water bath cooling To less than 5 DEG C, 19.6 grams of (0.2 mole) maleic anhydrides, 147.0 grams (0.5 moles) 3,3 ', 4,4 '-tetracarboxylic biphenyl two are added Acid anhydride and 217.0 grams (0.7 mole) 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, stirring reaction add 40.0 gram (0.2 after 2 hours Mole) 3,4 '-diaminodiphenyl ether and double (4- amino-benzene oxygens) benzene of 233.6 grams of (0.8 mole) 1,3- continue stirring reaction 2.5 hours, 428.4 grams of (4.2 moles) acetic anhydrides and 9.48 grams of (0.12 mole) pyridines are subsequently added, ice-water bath is removed, heated 90 DEG C are warming up to, stirring reaction 8 hours adds 17800 grams of ethanol, and quick stirring 1 hour, filtering washs 2 with 3560 grams of acetone Secondary -3 times, 90 DEG C are dried in vacuo 5 hours, obtain 662.8 grams of FMPI resins (theoretical yield is 668.8 grams), are denoted as FMPI-2, receive Rate is 99.1%.

Embodiment 3

The 3- aminopropyl triethoxysilanes aqueous solution, 400.0 grams of silver-plated coppers by 4000 gram mass percent concentrations for 1% Powder, 100.0 grams of conductive blacks and 500.0 grams of silver powder are put into reactor, after being stirred 1 hour at 60 DEG C, are cooled to room temperature, mistake Filter, in being dried 1 hour at 100 DEG C, that is, obtains the conductive filler of 1000.0 grams of coupling agent treatments, is denoted as ECF-1.

The 3- aminopropyl triethoxysilanes aqueous solution, 500.0 grams of silver-plated coppers by 4000 gram mass percent concentrations for 3% Powder and 500.0 grams of aluminium powders are put into reactor, after being stirred 2 hours at 80 DEG C, are cooled to room temperature, are filtered, in dry at 100 DEG C 2 hours, that is, the conductive filler of 1000.0 grams of coupling agent treatments is obtained, ECF-2 is denoted as.

By 8000 gram mass percent concentrations for 5% the glycidoxypropyl group triethoxysilane aqueous solution, 200.0 grams Graphene powder and 800.0 grams of silver-plated glass beads are put into reactor, after being stirred 2 hours at 70 DEG C, are cooled to room temperature, mistake Filter, in being dried 2 hours at 100 DEG C, that is, obtains the conductive filler of 1000.0 grams of coupling agent treatments, is denoted as ECF-3.

By 8000 gram mass percent concentrations for 10% the glycidoxypropyl group triethoxysilane aqueous solution, 300.0 Gram graphene powder and 700.0 grams of silver-plated copper powders are put into reactor, in after 80 DEG C of stirrings 1 hour, are cooled to room temperature, are filtered, In being dried 1 hour at 100 DEG C, that is, the conductive filler of 1000.0 grams of coupling agent treatments is obtained, ECF-4 is denoted as.

Embodiment 4

By 1000 grams of PA66 resins, 300 grams of PPO resins, 50 grams of FMPI-1 resins, 100 grams of ECF-1 conductive fillers, 25 grams Maleic anhydride is grafted polyhexamethylene adipamide resin and 75 grams of maleic anhydride grafted polypheylene ether resins, the 3 gram of four [β-(uncles of 3,5- bis- Butyl -4- hydroxy phenyls) propionic acid] pentaerythritol ester and 7 grams of 2- (2 '-hydroxyl -5 '-aminomethyl phenyl) BTA mixing, use Double screw extruder, high-temperature fusion mixing is carried out at 270 DEG C, and granulation obtains 1560 grams of electrodepositable fluorinated polyimide modifications Engineering plastic alloy, is denoted as PPFMA-1.Its performance data is as shown in table 1.

By 1000 grams of PA66 resins, 500 grams of PPO resins, 35 grams of FMPI-1 resins, 65 grams of FMPI-2 resins, 80 grams of ECF-2 Conductive filler, 110 grams of ECF-3 conductive fillers, 110 grams of ECF-4 conductive fillers, 75 grams of maleic anhydride grafting polyhexamethylene adipamide Resin and 125 grams of maleic anhydride grafted polypheylene ether resins, 13 gram of three (2,4- di-tert-butyl-phenyls) phosphite ester and 17 grams of 2- (2 '-hydroxyl -5 '-t-octyl phenyl) BTA mixing, using double screw extruder, high-temperature fusion mixing is carried out at 290 DEG C, Granulation, obtains 2130 grams of electrodepositable fluorinated polyimide modified engineered plastic alloys, is denoted as PPFMA-2.Its performance data is such as Shown in table 1.

By 1000 grams of PA66 resins, 1000 grams of PPO resins, 65 grams of FMPI-1 resins, 85 grams of FMPI-2 resins, 250 grams ECF-1 conductive fillers, 250 grams of ECF-3 conductive fillers, 160 grams of maleic anhydride grafting polyhexamethylene adipamide resins and 140 grams of horses Maleic anhydride grafted polyphenylene oxide resin, 15 gram of four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, 15 gram 1, Double (3,5- di-tert-butyl-hydroxy phenyl) the propionic acid hydrazines of 2- and 20 grams of 2- (2 '-hydroxyl -5 '-aminomethyl phenyl) BTA mixing, Using double screw extruder, high-temperature fusion mixing is carried out at 280 DEG C, granulation obtains 3000 grams of electrodepositable fluorinated polyimides Modified engineered plastic alloy, is denoted as PPFMA-3.Its performance data is as shown in table 1.

The performance data of the electrodepositable fluorinated polyimide modified engineered plastic alloy of table 1

Claims (16)

1. a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy, it is characterised in that：By mass ratio 100:30-100: 5-15:10-50:10-30:1-5 PA66 resins, PPO resins, FMPI resins, conductive filler, compatilizer and auxiliary agent composition；Its In, FMPI resins be by mol ratio be 1:2:7-12:Double [4- (2,4- diamino phenoxies) phenyl] hexafluoros third of 5-10 2,2- Alkane, maleic anhydride, aromatic dianhydride, the obtained dimaleoyl imino polyimide resin of aromatic diamine reaction.

2. a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 1, it is characterised in that： Described PA66 resins are the polyhexamethylene adipamide resins as obtained by 1,6- hexamethylene diamines and 1,6- adipic acids by polycondensation reaction.

3. a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 1, it is characterised in that： Described PPO resins are the polyphenylene oxide resin by itself polycondensation reaction by 2,6- xylenols.

4. a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 1, it is characterised in that： Described conductive filler is selected from graphene, conductive black, copper powder, aluminium powder, silver powder, nickel powder, silver-plated copper powder, silver-plated nickel powder, silver-plated One or more in glass microballoon.

5. a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 1, it is characterised in that： Described compatilizer is selected from maleic anhydride grafting polyhexamethylene adipamide resin, maleic anhydride grafted polypheylene ether resin, maleic acid One or more in acid anhydride graft phenylethene-ethylene-butadiene-styrene copolymer resin.

6. a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 1, it is characterised in that： Described auxiliary agent be selected from four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, β-(3,5- di-t-butyls- 4- hydroxy phenyls) the positive octadecanol ester of propionic acid, three (2,4- di-tert-butyl-phenyls) phosphite esters, 2,6- di-t-butyl -4- methyl Phenol, N, N '-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propiono] hexamethylene diamine, the two (2- hydroxyl -3- tert-butyl group -5- first Base phenyl) methane, 4,4 '-thiobis (6- tert-butyl-m-cresols), double (3,5- di-tert-butyl-hydroxy phenyls) propionic acid of 1,2- Hydrazine, dilauryl thiodipropionate, the polymer of succinic acid and 4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine alcohols, it is double (2,2, 6,6- tetramethyl -4- piperidyls) sebacate, double (3,5- di-tert-butyl-4-hydroxyl benzyls monoethyl phosphate) nickel, 2,4- dihydroxies Base benzophenone, 2-hydroxy-4-n-octoxybenzophenone, ESCALOL 567,2- (2 '-hydroxyl -5 '-first Base phenyl) BTA, 2- (2 '-hydroxyl -3 '-the tert-butyl group -5 '-aminomethyl phenyl) -5- chlorinated benzotriazoles, 2- (2 '-hydroxyl - 3 ', 5 '-diamyl phenyl) BTA, 2- (2 '-hydroxyl -5 '-t-octyl phenyl) BTA, 2-Phenylbenzimidazole -5- Sulfonic acid, 2- [2 '-hydroxyl -3 ', 5 '-bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl] BTA, 2- (2H- BTAs -2-) -6- One or more in (dodecyl) -4- methylphenols.

7. a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 1, it is characterised in that： Described aromatic dianhydride is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic acid Base biphenyl dianhydride, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl sulfone dianhydride, 2,2- pairs (3, 4- dicarboxyphenyis) hexafluoropropane dianhydride, double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides of 2,2-, the double [4- of 2,2- (3,4- di carboxyl phenyloxies) phenyl] hexafluoropropane dianhydride, double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 1,4-, 1,3- it is double (3, 4- di carboxyl phenyloxies) benzene dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl sulfone dianhydrides, 4,4 '-bis- (3,4- dicarboxyls Phenoxy group) benzophenone dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) biphenyl dianhydrides, 4,4 '-bis- (3,4- dicarboxyl benzene oxygen Base) one or more in diphenyl ether dianhydride.

8. a kind of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 1, it is characterised in that： Described aromatic diamine is selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, methylresorcinol diamines, trimethyl m-phenylene diamine (MPD), first Base p-phenylenediamine, 4,4 '-MDA, 3,3 '-dimethyl -4,4 '-MDA, 4,4 '-diaminourea two Phenylate, 3,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 4,4 '-diaminodiphenylsulfone, 3,3 '-diaminodiphenylsulfone, Double (4- amino-benzene oxygens) benzene of 4,4 '-benzidine, 1,3-, double (4- amino-benzene oxygens) benzene of 1,4-, double (the 3- aminobenzenes of 1,3- Epoxide) benzene, double (3- amino-benzene oxygens) benzene of 1,4-, double [4- (4- amino-benzene oxygens) phenyl] propane of 2,2-, the double [4- (3- of 2,2- Amino-benzene oxygen) phenyl] propane, double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2-, double [4- (the 3- aminobenzenes of 2,2- Epoxide) phenyl] HFC-236fa, 4,4 '-bis- (4- amino-benzene oxygens) -3,3 ', 5,5 '-tetramethyl biphenyl, 4,4 '-bis- (4- amino Phenoxy group) biphenyl, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl ether, 4,4 '-bis- (3- Amino-benzene oxygen) diphenyl ether, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl-methanes, 4,4 '-bis- (3- amino-benzene oxygens) hexichol first Alkane, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulphone (DPS)s, 2,2 '-two (trifluoromethyls)- Double (2- trifluoromethyl-4-aminophenoxyls) benzene of 4,4 '-benzidine, 1,4-, the double (3- trifluoromethyl -4- aminobenzenes of 1,4- Epoxide) benzene, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,3-, double (3- trifluoromethyl-4-aminophenoxyls) benzene of 1,3-, Double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane of 2,2-, the double [4- (3- trifluoromethyl -4- aminobenzene oxygen of 2,2- Base) phenyl] propane, double [4- (2- the trifluoromethyl-4-aminophenoxyls) -2,6- 3,5-dimethylphenyls] propane of 2,2-, the double [4- of 2,2- (3- trifluoromethyl-4-aminophenoxyls) -2,6- 3,5-dimethylphenyls] propane, the double [4- (2- trifluoromethyl -4- aminobenzene oxygen of 2,2- Base) phenyl] HFC-236fa, double [4- (3- trifluoromethyl-4-aminophenoxyls) phenyl] HFC-236fas of 2,2-, 4,4 '-bis- (2- tri- Methyl fluoride -4- amino-benzene oxygens) diphenyl-methane, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) diphenyl-methanes, 4,4 '-it is bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) -3,3 ', 5,5 '-tetramethyl Base biphenyl, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether, 4,4 '-bis- (3- trifluoromethyl -4- aminobenzene oxygen Base) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- trifluoromethyl -4- aminobenzenes Epoxide) diphenyl sulphone (DPS), 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) -3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) -3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-bis- (2- trifluoromethyl -4- aminobenzenes Epoxide) diphenyl sulfide, 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) diphenyl sulfides, 4,4 '-bis- (2- trifluoromethyls -4- Amino-benzene oxygen) benzophenone, the one or more of 4,4 '-bis- (3- trifluoromethyl-4-aminophenoxyls) benzophenone.

9. a kind of preparation method of electrodepositable fluorinated polyimide modified engineered plastic alloy as claimed in claim 1, bag Include following steps：

(1) double [4- (2,4- diamino phenoxies) phenyl] HFC-236fas of 2,2- and highly polar aprotic organic solvent are added anti- Answer in kettle, at room temperature after stirring and dissolving, ice-water bath is cooled to less than 5 DEG C, adds maleic anhydride and aromatic dianhydride, stirring reaction After -2 hours 1 hour, aromatic diamine is added, continues stirring reaction -4 hours 2.5 hours, dehydrating agent and catalysis is subsequently added Agent, removes ice-water bath, is heated to 90 DEG C -100 DEG C, stirring reaction -8 hours 4 hours adds precipitating agent, stirs 1 hour, Filtering, is washed 2 times -3 times with acetone, and 90 DEG C of vacuum drying obtain FMPI resins；

(2) conductive filler is handled with coupling agent aqueous solution, its concrete technology is：Coupling agent aqueous solution and conductive filler are put into instead Answer in kettle, after 60 DEG C -80 DEG C are stirred -2 hours 1 hour, be cooled to room temperature, filter, in drying -2 hours 1 hour at 100 DEG C, Obtain the conductive filler of coupling agent treatment；Wherein, the mass ratio of coupling agent aqueous solution and conductive filler is 4-8:1；

(3) PA66 resins, PPO resins, FMPI resins, conductive filler, compatilizer and auxiliary agent are mixed, using twin-screw extrusion Machine, in 270 DEG C of -290 DEG C of progress high-temperature fusion mixing, granulation obtains the conjunction of electrodepositable fluorinated polyimide modified engineered plastic Gold.

10. a kind of preparation method of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 9, It is characterized in that：Highly polar aprotic organic solvent in the step (1) is selected from N,N-dimethylformamide, N, N- dimethyl One or more in acetamide, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, dimethyl sulfoxide (DMSO)；Wherein, Qiang Ji Property aprotic organic solvent and total reactant mass ratio be 3-5：1；The quality of total reactant refers to the double [4- (2,4- bis- of 2,2- Amino-benzene oxygen) phenyl] HFC-236fa, maleic anhydride, the quality sum of aromatic dianhydride and aromatic diamine.

11. a kind of preparation method of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 9, It is characterized in that：Dehydrating agent in the step (1) be selected from acetic anhydride, propionic andydride, butyric anhydride, trifluoroacetic anhydride (TFAA), chloracetic acid acid anhydride, One or more in dicyclohexylcarbodiimide；Wherein, the mol ratio of dehydrating agent and aromatic dianhydride is 2.5-3.5:1.

12. a kind of preparation method of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 9, It is characterized in that：Catalyst in the step (1) is selected from triethylamine, tri-n-butylamine, pyridine, picoline, lutidines, connection One or more in pyridine, methyl bipyridyl；Wherein, the mol ratio of catalyst and aromatic dianhydride is 0.01-0.1:1.

13. a kind of preparation method of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 9, It is characterized in that：Precipitating agent in the step (1) is selected from methanol, ethanol, propyl alcohol, isopropanol, ethylene glycol, ethylene glycol list first One or more in ether, glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, MEK；Wherein, precipitating agent with The mass ratio of highly polar aprotic organic solvent is 2-5：1.

14. a kind of preparation method of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 9, It is characterized in that：The mass ratio of acetone and highly polar aprotic organic solvent in the step (1) is 0.5-1:1.

15. a kind of preparation method of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 9, It is characterized in that：The mass percent concentration of coupling agent aqueous solution in the step (2) is 1%~10%.

16. a kind of preparation side of electrodepositable fluorinated polyimide modified engineered plastic alloy according to claim 15 Method, it is characterised in that：Described coupling agent is selected from 3- aminopropyl triethoxysilanes, 3- aminopropyl trimethoxysilanes, epoxy One or more in propoxypropyl triethoxysilane, glycidoxy trimethoxy silane.