CN104829844B - A kind of carbon fiber cable core MHFPI type fire resistant epoxy matrix resins and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of carbon fiber cable core MHFPI type fire resistant epoxy matrix resins and preparation method thereof, consisting of：Mass ratio is 100:1‑15:20‑200:100 300 polyfunctional epoxy resin, MHFPI polyimide resins, reactive diluent and curing agent.Preparation method comprises the following steps：(1) MHFPI polyimide resins are obtained by the reaction of 2,2 pairs of (hydroxy phenyl of 3 amino 4) HFC-236fas, aromatic diamine, aromatic dianhydride and maleic anhydride；(2) MHFPI polyimide resins and polyfunctional epoxy resin are carried out into copolyreaction, is subsequently added reactive diluent and continues to react, add curing agent to be uniformly mixed.Preparation process is simple of the present invention, environment-friendly, products obtained therefrom excellent combination property, is suitable for pultrusion molding process, the pultrusion manufacture of carbon fiber cable core composite is can be applied to, with wide market application foreground.

Description

A kind of carbon fiber cable core MHFPI type fire resistant epoxy matrix resins and its preparation Method

Technical field

The invention belongs to polymeric material field, more particularly to a kind of carbon fiber cable core MHFPI type fire resistant epoxies Matrix resin and preparation method thereof.

Background technology

Using steel-core-aluminium twisted wire, this material that important function has been played in power Transmission transmission line of electricity now more. However, developing rapidly with national economy, electricity needs rapid growth, convey and bring huge pressure on a large scale to electric power Power.The shortcomings of steel-core-aluminium twisted wire has big weight, high energy consumption, tower spacing is short, sag is big, for this reason, it may be necessary to study a kind of new Section bar material is to substitute steel core, so as to the advanced core that lightweight, intensity is big, energy consumption is low, tower spacing is big, sag is small is obtained.Carbon is fine Dimension is that a kind of proportion is small, intensity is high, modulus is big, high temperature resistant, corrosion resistant high-performance fiber, therefore, using fibre reinforced, resistance to The aluminium twisted wire that high-temperature resin base composite core is obtained instead of steel core, can bring huge leap to power transmission, and it is lightweight, strong Degree is big, rigidity high, high temperature resistant, anticorrosive, and power consumption is small, sag is small and has security higher, be novel energy-conserving, Environment-friendly type transmission pressure.

Epoxy resin has excellent caking property, moulding processability, electrical insulation properties and excellent mechanical property Deng being widely used in the fields such as Aero-Space, electronic apparatus, automobile, naval vessel.But epoxy resin there is also some and lack Point, such as heat resistance is relatively low, much not as good as aromatic heterocyclic polymer systems such as polyimides, polybenzimidazoles, polybenzoxazoles, Epoxy-resin systems mechanical property, electric property in high temperature environments etc. declines notable, it is difficult to meet practical application request.Cause This, the resistant, toughened focus for being modified, being current scientific and technical personnel both at home and abroad research is carried out to epoxy resin.

It is well known that epoxy resin has many excellent performances：(1) good adhesive property：Adhesive strength is high, bonding Wide, it is with many metals (such as iron, steel, copper, aluminium, metal alloy) or nonmetallic materials (such as glass, ceramics, timber, plastics Deng) adhesive strength it is very high, the even more than intensity by viscous material in itself having, therefore can be used for many stress members In, it is one of main component of structural adhesive；(2) good processing characteristics：The flexibility of Formulaion of epoxy resin, processing work The diversity of skill and product properties is the most prominent in macromolecular material；(3) good stability：The solidification of epoxy resin Mainly by the ring opening polyaddition of epoxy radicals, therefore low-molecular material is not produced in solidification process, its cure shrinkage is heat One of minimum kind, generally 1%-2% in thermosetting resin, if the appropriate filler of selection can make shrinkage factor be down to 0.2% Left and right；Epoxy main chains after solidification are ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore with excellent resistance to acids and bases.

Therefore, epoxy resin is widely used in the every field of national economy：Either high-technology field is still Field of general technology, either can see its trace in defence and military or civilian industry, or even daily life.

Chinese invention patent CN103146330A discloses a kind of double [4- (2,4- diamino phenoxies) phenyl] six of 2,2- Fluoro-propane type high temperature resistant epoxy adhesive and preparation method thereof, is 1 by mass ratio:Component A and the B component composition of 1-2, wherein, A Component is the copolymer reacted with epoxy resin by double [4- (2,4- diamino phenoxies) phenyl] HFC-236fas of 2,2-；B Component is in highly polar non-matter by double [4- (2,4- diamino phenoxies) phenyl] HFC-236fas of 2,2- with aromatic dicarboxylic anhydride The solid content reacted in sub- organic solvent and toluene is the homogeneous phase transparent solution of 15%-30%.Preparation method includes：Room temperature Under, by A, B component in mass ratio 1:1-2 is uniformly mixed.

It is resistance to that Chinese invention patent CN103131369A discloses a kind of double (2,4- diamino phenoxies) the diphenyl sulphone (DPS) types of 4,4'- High-temp epoxy adhesive and preparation method thereof, is 1 by mass ratio:1-2 component A and B component composition, wherein component A be by 4, The copolymer that 4 '-bis- (2,4- diamino phenoxies) diphenyl sulphone (DPS)s react with epoxy resin；B component is by 4,4 '-bis- (2,4- Diamino phenoxy) diphenyl sulphone (DPS) and consolidating that aromatic dicarboxylic anhydride reacts in highly polar aprotic organic solvent and toluene Content is the homogeneous phase transparent solution of 15%-30%.Preparation method includes：At room temperature, by A, B component in mass ratio 1:1-2 is stirred It is well mixed.

Chinese invention patent CN103146331A discloses a kind of double (2,4- diamino phenoxies) the resistance to height of biphenyl type of 4,4'- Temperature epoxy adhesive and preparation method thereof, is 1 by mass ratio:Component A and the B component composition of 1-2, wherein component A be by 4,4 '- The copolymer that double (2,4- diamino phenoxies) biphenyl react with epoxy resin；B component is by 4,4 '-bis- (2,4- diaminos Phenoxyl) solid content that is reacted in highly polar aprotic organic solvent and toluene with aromatic dicarboxylic anhydride of biphenyl is The homogeneous phase transparent solution of 15%-30%.Preparation method includes：At room temperature, by A, B component in mass ratio 1:1-2 stirring mixing is equal It is even.

Chinese invention patent CN103030787A discloses a kind of benzimidazole-epoxy matrix resin and preparation method thereof, Resin is made up of the component of A, B two.Preparation method, comprises the following steps：(1) by N, N, N ', N '-four glycidyl group -2,2- is double [4- (4- amino-benzene oxygens) phenyl] propane is put into reactor with 2- (4- aminophenyls) -5- aminobenzimidazoles, and heating rises It is warm to add reactive diluent and organic solvent to 70-80 DEG C of stirring reaction 15min-30min, stir, obtain component A； (2) curing agent and organic solvent are mixed, stirring and dissolving is uniform, that is, obtain B component；(3) when using, A, B component are mixed, is stirred Mix uniform.

Chinese invention patent CN103013414A discloses a kind of alpha-cyano-β-ethoxy ethyl acrylate modified epoxy tree Fat adhesive and preparation method thereof, the composition of adhesive is：Mass ratio is 100:100~50:60~30:5~20:30~80 Epoxy resin, epoxy ester resin, endurable active toughener, alpha-cyano-β-ethoxy ethyl acrylate and curing agent.Preparation method, bag Include following steps：Epoxy resin is mixed with endurable active toughener, in after 60 DEG C of -80 DEG C of reaction 15-20min, epoxy-ester tree is added Fat and alpha-cyano-β-ethoxy ethyl acrylate, are uniformly mixed, and obtain component A；Curing agent is B component；When using, will A, B component are well mixed, and obtain final product.

Into 21 century, the application of macromolecular material is more and more extensive, and the development of human society and the life of people are not The application of macromolecular material can be left.At the same time, requirement of the people to living environment is also more and more high, it is desirable to macromolecular material Solvent-free volatilization, environment-friendly in the manufacturing, application process.Therefore, solvent-free macromolecular material, particularly solvent-free ring Oxygen basic resin system is one of direction of the current research and development of emphasis in the world.

Chinese patent CN101148656A discloses a kind of preparation method of heat-resistant solvent-free epoxy adhesive, TGDDM rings Oxygen tree fat, toughener, hydrogenated bisphenol A, curing agent, accelerator are well mixed, and heat-resistant solvent-free epoxy adhesive has been obtained.But Its resistance to elevated temperatures still has larger limitation, fails to meet the practical application under many hot environments.

Chinese patent CN101397486A discloses a kind of preparation method of bi-component solvent-free epoxy resin adhesive, it Including component A and B component, wherein component A contains novolac epoxy resin, alicyclic type epoxy resin and nbr carboxyl terminal；B groups It is double (2,4- diamino phenoxies) the benzene aromatic polyvalent amine hardeners of 1,4- to divide.Alicyclic type epoxy resin and end carboxyl butyronitrile rubber The addition of glue is respectively the 20-35% and 12% (mass percent) of novolac epoxy resin.Double (the 2,4- diaminobenzene oxygen of 1,4- Base) benzene aromatic polyvalent amine hardener addition for novolac epoxy resin 15-20% (mass percent), gained adhesive System good manufacturability.But its heat resistance is preferable not enough.

Chinese patent CN1927908A discloses a kind of preparation method of phenolic hydroxyl group containing polyimide powder, due to phenolic hydroxyl group Presence, its polyimide powder can with epoxy reaction, formed covalent bond, such that it is able to improve thermoplastic polyimide resin With the compatibility of epoxy resin, and epoxy-resin systems can be further made to reach good toughening effect.

Yu Xin seas et al.【Development [J] bondings of high-temperature resistant single-component epoxy adhesive, 2008,29 (12)：16-19】It is public A kind of preparation method of high-temperature resistant single-component epoxy adhesive is opened, has been primarily characterized in that：It is end-blocking with maleic anhydride (MA) Agent, with double (3- amino-4-hydroxylphenyls) HFC-236fas (BAHPFP) of 2,2-, double [4- (4- amino-benzene oxygens) phenyl] third of 2,2- Double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides (BPADA) of alkane (BAPOPP), 2,2- are obtained for main Material synthesis Phenolic hydroxy group polyetherimide resin (HPEI)；It it is resistant, toughened dose with the synthesized HPEI for obtaining, with N, N, N', N'- tetra- Glycidyl -4,4'- MDAs (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent Deng preparation has obtained the high-temperature resistant single-component epoxy adhesive of excellent combination property.

Chinese invention patent CN103483552A discloses a kind of carbon fibre composite matrix resin and its preparation side Method, the carbon fibre composite matrix resin is by N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether (TGDADPE) double [4- (2- trifluoromethyl-4-maleimide phenoxyls) benzene of epoxy resin, ES216 epoxy resin, 2,2- Base] propane, 3,3 '-dimethyl -4,4 '-bis- (4- carboxyl phthalimide groups) diphenyl-methanes, curing agent and organic solvent composition；Its Preparation method, comprises the following steps：(1) by N, N, N ', N '-four glycidyl group -4,4 ' diaminodiphenyl ether (TGDADPE) ring Oxygen tree fat and 3,3 '-dimethyl -4,4 '-bis- (4- carboxyl phthalimide groups) diphenyl-methanes are put into reactor, in 80 DEG C -100 Stirring reaction is after -1 hour 0.5 hour in DEG C temperature range, add ES216 epoxy resin and 2,2- it is double [4- (2- trifluoromethyls - 4- maleimide phenoxyls) phenyl] propane, continue stirring reaction -1 hour 0.5 hour, organic solvent is added, stirring is equal It is even, obtain component A；(2) curing agent and organic solvent are mixed, stirring and dissolving obtains B component in homogeneous；(3) when using, by A groups Part, B component are well mixed.

Chinese invention patent CN103408727A disclose a kind of TGBAPOPP mold bases resin used for advanced composite material and Its preparation method, the matrix resin is by N, N, N ', double [4- (4- amino-benzene oxygens) phenyl] third of N '-four glycidyl group -2,2- Alkane (TGBAPOPP), o-cresol formaldehyde epoxy resin, N- isopropyls-N '-diphenyl-para-phenylene diamine, 2,2,4- trimethyl -1,2- diaminos Double [4- (4- maleimide phenoxyls) phenyl] propane of base quinoline, 2,2-, curing agent and organic solvent composition；Preparation method Comprise the following steps：By N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] propane, orthoresols Double [4- (4- maleimide phenoxyls) phenyl] propane of formaldehyde epoxy resin, 2,2- are put into reactor, in 90 DEG C -100 DEG C Within the temperature range of react certain hour after, N- isopropyls-N '-diphenyl-para-phenylene diamine solution, 2,2,4- front threes are added at room temperature Base -1,2- dihyaroquinoline solution, is uniformly mixed, and adds curing agent solution, is uniformly mixed.

Chinese invention patent CN103483553A discloses a kind of TGDADPE types epoxy matrix resin used for advanced composite material And preparation method thereof, the matrix resin is 100 by mass ratio:5-10:10-20:1-5:The N of 80-200, N, N ', N '-four shrinks Glyceryl -4,4 '-diaminodiphenyl ether epoxy resin (TGDADPE), aromatic diamine, aromatic dicarboxylic anhydride, curing agent Constituted with organic solvent；Its preparation method comprises the following steps：By N, N, N ', N '-four glycidyl group -4,4 '-diaminourea two Phenylate epoxy resin (TGDADPE) and aromatic diamine are put into reactor, are reacted within the temperature range of 50 DEG C -90 DEG C After 30min-40min, room temperature is cooled to, adds the homogeneous phase solution of aromatic dicarboxylic anhydride, curing agent and organic solvent, stirring is mixed Close uniform.

The content of the invention

The technical problems to be solved by the invention are to provide a kind of carbon fiber cable core MHFPI types fire resistant epoxy matrix Resin and preparation method thereof, the matrix resin excellent combination property is environment-friendly, and raw material sources are convenient, preparation process is simple, into This is low, can also be applied to the pultrusion of the products such as multiple fiber enhancing high temperature resistant composite, has broad application prospects

A kind of carbon fiber cable core of the invention MHFPI type fire resistant epoxy matrix resins, consisting of：Mass ratio is 100:1-15:20-200:The polyfunctional epoxy resin of 100-300, MHFPI polyimide resins, reactive diluent and curing agent； Wherein, MHFPI polyimide resins are by mol ratio 1:1-5:1-3:Double (3- amino-4-hydroxylphenyls) hexafluoros of the 2,2- of 2-6 The reaction of propane, aromatic diamine, aromatic dianhydride and maleic anhydride is formed.

Described polyfunctional epoxy resin is selected from N, N, N ', N '-four glycidyl group p-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-phenylene diamine (MPD) epoxy resin, N, N, O- triglycidyl group para-aminophenol epoxy resin, N, N, O- triglycidyl meta-aminophenols epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-MDA ring Oxygen tree fat, N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-diethyl -4,4 '-MDA epoxy resin, 3,3 '-two chloro- N, N, N ', N ' - Four glycidyl group -4,4 '-MDA epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-diaminourea two Phenylate epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-DADPS epoxy resin, N, N, N ', N '-four contracts Water -3,4 '-diaminodiphenyl ether of glyceryl epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-DADPS ring Oxygen tree fat, N, N, N ', N '-four glycidyl group -4,4 '-benzidine epoxy resin, N, N, N ', N '-four glycidyl group P-phenylenediamine epoxy resin, N, N, N ', N '-four glycidyl group m-phenylene diamine (MPD) epoxy resin, N, N, N ', the glycidols of N '-four Base -1,4- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,4- is double (3- amino-benzene oxygens) Benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,3- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four Glycidyl -1,3- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', the double (2- tri- of N '-four glycidyl group -1,4- Methyl fluoride -4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', the double (2- trifluoromethyl -4- ammonia of N '-four glycidyl group -1,3- Phenoxyl) benzene epoxy resin, N, N, N ', the glycidyl -4,4 of N ', O- five '-diaminourea -4 "-hydroxyl triphenylmenthane epoxy Resin, N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four shrinks Glyceryl -2,2- double [4- (3- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- is double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- is double [4- (3- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', the double [4- (2- tri- of N '-four glycidyl group -2,2- Methyl fluoride -4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- ammonia Phenoxyl) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl -4- aminobenzene oxygen Base) diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group - 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 ' - Double (4- amino-benzene oxygens) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyls -4- Amino-benzene oxygen) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) hexichol Ketone epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone Epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ', N ' - Four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resins, N, N, N ', N ', O, O '-six contracting One or more in double (3- amino-4-hydroxylphenyls) the HFC-236fa epoxy resin of water glyceryl -2,2-.

Described reactive diluent is selected from hydrogenated bisphenol A epoxy resin, CE-793 epoxy resin, ES216 epoxy resin, 1, 3- diglycidyls resorcinol type epoxy, 3,4- epoxycyclohexyethylSiOis acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4- epoxies Base -6- methyl cyclohexanes acid -3 ', 4 '-epoxy radicals -6 '-methyl cyclohexane methyl esters, ECC202 epoxy resin, in Dipentenedioxide One or more.

Described curing agent is selected from aluminium acetylacetonate, 2-methylimidazole, 2-ethyl-4-methylimidazole, N, N- dimethyl benzenes Amine, N, N- dimethyl open-chain crown ether, DMP-30, benzyl dimethylamine, 2,4,6- tri- (dimethylamino methyl) phenol, DBU, 1,8- Diazabicyclo [5.4.0] hendecene -7, HHPA, K-12 curing agent, THPA, methyl tetrahydro phthalic anhydride, laurylene base Succinyl oxide, methyl hexahydrophthalic anhydride, tung oil acid anhydride, with 80 acid anhydrides of dicyclopentadiene and maleic acid anhydride reactant, with The acid anhydrides of limonene and maleic acid anhydride reactant, with the liquid acid anhydrides of turpentine oil and maleic acid anhydride reactant One or more.

Described aromatic diamine is selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 4,4 '-MDA, 3, 3 '-dimethyl -4,4 ' MDA, 4,4 '-diaminodiphenyl ether, 4,4 '-benzidine, 3,3 '-dimethyl -4, 4 ' benzidines, 2,2 '-dimethyl -4,4 ' benzidine, 3,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, Double (3- amino-benzene oxygens) benzene of 4,4 '-DADPS, 3,3 '-DADPS, 1,3-, double (the 3- aminobenzene oxygen of 1,4- Base) benzene, double (4- amino-benzene oxygens) benzene of 1,3-, double (4- amino-benzene oxygens) benzene of 1,4-, the double (2- trifluoromethyl -4- amino of 1,3- Phenoxy group) benzene, double (2- trifluoromethyl-4-aminophenoxyls) benzene of 1,4-, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '- Double (3- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS)s, 4,4 '-bis- (4- amino Phenoxy group) diphenyl ether, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) two Phenylate, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfides, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulfides, 4,4 '-bis- (2- tri- Methyl fluoride -4- amino-benzene oxygens) diphenyl sulfide, 4,4 '-bis- (4- amino-benzene oxygens) benzophenone, 4,4 '-bis- (3- aminobenzene oxygen Base) benzophenone, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone, 4,4 '-bis- (4- amino-benzene oxygens) connection Benzene, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl, 4,4 '-bis- (4- Amino-benzene oxygen) diphenyl-methane, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyl -4- aminobenzenes Epoxide) diphenyl-methane, double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2-, double [4- (3- amino-benzene oxygens) benzene of 2,2- Base] HFC-236fa, double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] HFC-236fas of 2,2-, double [4- (the 4- amino of 2,2- Phenoxy group) phenyl] propane, double [4- (3- amino-benzene oxygens) phenyl] propane of 2,2-, the double [4- (2- trifluoromethyl -4- amino of 2,2- Phenoxy group) phenyl] propane, one or more in double (4- aminophenyls) HFC-236fas of 2,2-.

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-, 4,4 '-bis- (3,4- di carboxyl phenyloxies) biphenyl dianhydrides, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides, 4, 4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl sulfone dianhydrides, 4,4 '-bis- (3,4- di carboxyl phenyloxies) benzophenone dianhydrides, 1,4- One or more in double (3,4- di carboxyl phenyloxies) benzene dianhydrides of double (3,4- di carboxyl phenyloxies) benzene dianhydrides, 1,3-.

A kind of carbon fiber cable core of the invention preparation method of MHFPI type fire resistant epoxy matrix resins, including such as Lower step：

(1) by double (3- amino-4-hydroxylphenyls) HFC-236fas of 2,2-, aromatic diamine and highly polar non-proton organic molten Agent is added in reactor, at room temperature stirring and dissolving, adds aromatic dianhydride, and stirring reaction adds maleic acid after 0.5 hour Acid anhydride, continues stirring reaction 0.5 hour, adds aliphatic anhydride and catalyst, small in stirring reaction at 60 DEG C -100 DEG C 1 hour -2 Shi Hou, adds precipitating agent, high-speed stirred, filtering to reclaim mother liquor, filter cake is washed with acetone, 5 is vacuum dried at 70 DEG C -90 DEG C small When -8 hours, obtain MHFPI polyimide resins；

(2) by polyfunctional epoxy resin addition reactor, stirring after heating to 80 DEG C, adds MHFPI polyamides sub- Polyimide resin, in after 80 DEG C of -120 DEG C of stirring reactions -2 hours 1 hour, is cooled to less than 90 DEG C, adds reactive diluent to continue to stir Reaction -1 hour 0.5 hour is mixed, less than 60 DEG C are cooled to, curing agent is added, is uniformly mixed.

Highly polar aprotic organic solvent in the step (1) is selected from N,N-dimethylformamide, N, N- dimethyl second One or more in acid amides, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, dimethyl sulfoxide (DMSO)；Highly polar non-matter Sub- organic solvent is 4-6 with the mass ratio of reactant:1；The quality of reactant refers to double (the 3- amino-4-hydroxylphenyls) six of 2,2- The quality sum of fluoro-propane, aromatic diamine, aromatic dianhydride and maleic anhydride.

Aliphatic anhydride in the step (1) is selected from acetic anhydride, propionic andydride, chloracetic acid acid anhydride, trifluoroacetic anhydride (TFAA) Plant or several；Aliphatic anhydride is 3-6 with the mass ratio of reactant:1；The quality of reactant refers to the double (3- amino -4- hydroxyls of 2,2- Base phenyl) HFC-236fa, aromatic diamine, aromatic dianhydride and maleic anhydride quality sum.

Catalyst in the step (1) is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine, picoline, dimethyl pyrazole One or more in pyridine；Catalyst is 0.01-0.1 with the mass ratio of aromatic dianhydride：1.

Precipitating agent in the step (1) is selected from methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propane diols, tetrahydrofuran, methyl four One or more in hydrogen furans, glycol monoethyl ether, ethylene glycol monoethyl ether；Precipitating agent and highly polar aprotic organic solvent Mass ratio is 2-5:1.

Acetone and the mass ratio of highly polar aprotic organic solvent in the step (1) are 1-2:1.

Beneficial effect

(1) carbon fiber cable core of the invention has good combination property with MHFPI type fire resistant epoxy matrix resins, It is solvent-free, it is environment-friendly；

(2) carbon fiber cable core of the invention MHFPI type fire resistant epoxy matrix resins, high with low viscosity Reactivity, with good pultrusion；

(3) carbon fiber cable core of the invention MHFPI type fire resistant epoxy matrix resins, can be applied to carbon fiber etc. many The pultrusion of kind of fibre reinforced composites product, high temperature resistant, high intensity have good leaching with the multiple fiber such as carbon fiber Lubricant nature, interface performance is good, has broad application prospects；

(4) preparation process is simple of the present invention, low cost, easy to operate, reaction raw materials convenient sources, can be in common apparatus Middle completion preparation process, is advantageously implemented industrialized production.

Brief description of the drawings

Fig. 1 is that the carbon fiber cable core of embodiment 3 is bent with the viscosity versus temperature of MHFPI type fire resistant epoxy matrix resins M-1 Line；

Fig. 2 be embodiment 3 the carbon fiber cable core gelation time of MHFPI type fire resistant epoxy matrix resins M-1- Temperature curve.

Specific 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 for having read instruction of the present invention, 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 36.6 grams of (0.1 mole) 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa, 41.0 grams of (0.1 moles) 2, Double [4- (3- amino-benzene oxygens) phenyl] propane of 2- and 520 grams of DMAs are added in reactor, are stirred at room temperature After mixing dissolving, 31.0 grams of (0.1 moles) 3,3 ', 4 are added, 4 '-tetracarboxylic diphenyl ether dianhydride, stirring reaction is added after 0.5 hour 19.6 grams of (0.2 mole) maleic anhydrides, continue stirring reaction 0.5 hour, 385 grams of acetic anhydrides and 0.3 gram of pyridine are added, in 100 Stirring reaction adds 520 grams of methyl alcohol and 520 grams of ethanol after 1 hour at DEG C, and high-speed stirred, filtering reclaims mother liquor, with 520 gram third Ketone washs filter cake, is vacuum dried 8 hours at 70 DEG C, obtains 115.4 grams of MHFPI polyimide resins, is denoted as MHFPI-1.

Embodiment 2

By 3.66 grams of (0.01 mole) 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa, 4.1 grams of (0.01 moles) 2, 2- double [4- (4- amino-benzene oxygens) phenyl] propane, 8.0 grams of (0.04 mole) 3,4 '-diaminodiphenyl ethers, 100 grams of N, N- diformazans Yl acetamide and 100 grams of METHYLPYRROLIDONEs are added in reactor, at room temperature after stirring and dissolving, add 3.2 grams (0.01 mole) 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride and 10.4 grams of double [4- (3,4- dicarboxyls of (0.02 mole) 2,2- Phenoxy group) phenyl] propane dianhydride, after 0.5 hour, 5.9 grams of (0.06 mole) maleic anhydrides of addition continue to stir anti-stirring reaction Answer 0.5 hour, add 200 grams of acetic anhydrides and 1.3 grams of triethylamines, in after stirring reaction at 60 DEG C 2 hours, add 175 grams of methyl alcohol, Mother liquor is reclaimed in high-speed stirred, filtering, and filter cake is washed with 400 grams of acetone, is vacuum dried 5 hours at 90 DEG C, obtains 32.8 grams MHFPI polyimide resins, are denoted as MHFPI-2.

Embodiment 3

By 100.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether epoxy resin adds reactor In, stirring after heating to 80 DEG C, adds 1.0 grams of MHFPI-1 polyimide resins, in after 80 DEG C of stirring reactions 1 hour, It is cooled to less than 90 DEG C, adds 20.0 grams of hydrogenated bisphenol A epoxy resins to continue stirring reaction 1 hour, is cooled to less than 60 DEG C, plus Enter 100.0 grams of methyl tetrahydro phthalic anhydrides and 1.0 grams of aluminium acetylacetonates, be uniformly mixed, obtain 322.0 grams of carbon fiber cable cores and use MHFPI type fire resistant epoxy matrix resins, are denoted as M-1, and its temperature-viscosity curve is as shown in figure 1, gelation time-temperature is bent Line is as shown in Figure 2.

Embodiment 4

By 50.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-MDA epoxy resin and 50.0 grams of N, N, O- triglycidyl group para-aminophenol epoxy resin are added in reactor, stirring, after heating to 80 DEG C, add 5.0 Gram MHFPI-2 polyimide resins, in after 120 DEG C of stirring reactions 2 hours, are cooled to less than 90 DEG C, add 20.0 grams of hydrogenations double Phenol A epoxy resin and 80.0 grams of 1,3- diglycidyls resorcinol type epoxies continue stirring reaction 0.5 hour, are cooled to Less than 60 DEG C, add 100.0 grams of tung oil acid anhydrides, 10.0 grams of 2-ethyl-4-methylimidazoles and 100.0 grams of dodecenyl-succinic acids Acid anhydride, is uniformly mixed, and obtains 415.0 grams of carbon fiber cable core MHFPI type fire resistant epoxy matrix resins, is denoted as M-2.

Embodiment 5

By 100.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-MDA epoxy resin adds reactor In, stirring after heating to 80 DEG C, adds 10.0 grams of MHFPI-1 and 5.0 gram of polyimide resins of MHFPI-2, in 100 DEG C stirring reaction is cooled to less than 90 DEG C after 1.5 hours, adds 200.0 grams of 1,3- diglycidyl resorcinol asphalt mixtures modified by epoxy resin Fat continues stirring reaction 0.5 hour, is cooled to less than 60 DEG C, adds 100.0 grams of methyl tetrahydro phthalic anhydrides, 10.0 grams of 2- ethyls -4- Methylimidazole and 190.0 grams of dodecenylsuccinic anhydrides, are uniformly mixed, and obtain 615.0 grams of carbon fiber cable core MHFPI Type fire resistant epoxy matrix resin, is denoted as M-3.

Embodiment 6

The carbon fiber cable core MHFPI type fire resistant epoxy matrix resins of appropriate 3~embodiment of embodiment 5 are taken respectively, That is M-1~M-3, and be uniformly applied to respectively in standard stainless steel test piece, after room temperature hangs 0.5 hour, overlapping is clamped, and is put To enter solidified in convection oven：Started to warm up to 90 DEG C from room temperature, insulation reaction 1 hour is continuously heating to 150 DEG C, insulation Reaction 1 hour, is continuously heating to 180 DEG C, and insulation reaction 2 hours naturally cools to room temperature.It is carried out using electronic tensile machine Room temperature (25 DEG C) is tested with the tensile shear strength (σ) under high temperature (240 DEG C) state, as a result as shown in table 1.

The carbon fiber cable core MHFPI type fire resistant epoxy matrix resins of appropriate 3~embodiment of embodiment 5 are taken respectively, That is M-1~M-3, film is above pushed away in polytetrafluoroethylene film, is placed in vacuum drying chamber, be made into size for 5mm × 5mm × The square coupons of 1mm, curing process is：Started to warm up to 90 DEG C from room temperature, insulation reaction 1 hour is continuously heating to 150 DEG C, Insulation reaction 1 hour, is continuously heating to 180 DEG C, and insulation reaction 2 hours naturally cools to room temperature.

The megger produced using Guilin Electro Scientific research institute tests its specific insulation ρ v (1MHz, 25 DEG C), as a result It is shown in Table 1.

Its dielectric loss (D) (1MHz, 25 is tested using the TH2828S testers of Changzhou Tong Hui Electron equipment Co., Ltd DEG C), the results are shown in Table 1.

Using precision electronic balance, above-mentioned dry square coupons are weighed after (W1), be soaked in deionized water (25 DEG C) In, after 72 hours, take out, dry surface with filter paper, weigh (W2), be calculated water absorption rate () data it is as shown in table 1.Profit With precision electronic balance, above-mentioned dry square coupons are weighed after (G1), be positioned over climatic chamber (85 DEG C, RH85%) In, after 72 hours, take out, surface is dried with filter paper, weigh (G2), and the data for being calculated hydroscopicity (ψ) are as shown in table 1.

The carbon fiber cable core of table 1 performance data of MHFPI type fire resistant epoxies matrix resin (M-1~M-3)

Claims (12)

1. a kind of carbon fiber cable core MHFPI type fire resistant epoxy matrix resins, it is characterised in that：Consisting of：Mass ratio It is 100:1-15:20-200:The polyfunctional epoxy resin of 100-300, MHFPI polyimide resins, reactive diluent and solidification Agent；Wherein, the preparation method of MHFPI polyimide resins includes：

Double (3- amino-4-hydroxylphenyls) HFC-236fas of 2,2-, aromatic diamine and highly polar aprotic organic solvent are added In reactor, stirring and dissolving, adds aromatic dianhydride at room temperature, and stirring reaction adds maleic anhydride after 0.5 hour, continues Stirring reaction 0.5 hour, adds aliphatic anhydride and catalyst, in after stirring reaction at 60 DEG C -100 DEG C -2 hours 1 hour, plus Enter precipitating agent, mother liquor is reclaimed in high-speed stirred, filtering, and filter cake wash with acetone, vacuum drying 5 hours -8 is small at 70 DEG C -90 DEG C When, obtain MHFPI polyimide resins；Wherein, 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa, aromatic diamine, virtues The mol ratio of fragrant race's dianhydride and maleic anhydride is 1:1-5:1-3:2-6.

2. a kind of carbon fiber cable core according to claim 1 MHFPI type fire resistant epoxy matrix resins, its feature exists In：Described polyfunctional epoxy resin is selected from N, N, N ', N '-four glycidyl group p-phenylenediamine epoxy resin, N, N, N ', N '- Four glycidyl group m-phenylene diamine (MPD) epoxy resin, N, N, O- triglycidyl group para-aminophenol epoxy resin, N, N, O- tri- contract Water glyceryl m-aminophenol epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-MDA asphalt mixtures modified by epoxy resin Fat, N, N, N ', N '-four glycidyl group -3,3 '-dimethyl -4,4 '-MDA epoxy resin, N, N, N ', N ' - Four glycidyl group -3,3 '-diethyl -4,4 '-MDA epoxy resin, 3,3 '-two chloro- N, N, N ', N '-four contracts Water -4,4 '-MDA of glyceryl epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether Epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-DADPS epoxy resin, N, N, N ', N '-four shrinks sweet Oil base -3,4 '-diaminodiphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -3,3 '-DADPS asphalt mixtures modified by epoxy resin Fat, N, N, N ', N '-four glycidyl group -4,4 '-benzidine epoxy resin, N, N, N ', N '-four glycidyl group -1,4- Double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', double (3- amino-benzene oxygens) the phenyl ring oxygen of N '-four glycidyl group -1,4- Resin, N, N, N ', N '-four glycidyl group -1,3- double (4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four shrinks sweet Oil base -1,3- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N ', N '-four glycidyl group -1,4- pairs (2- trifluoromethyls - 4- amino-benzene oxygens) benzene epoxy resin, N, N, N ', the double (2- trifluoromethyl -4- aminobenzene oxygen of N '-four glycidyl group -1,3- Base) benzene epoxy resin, N, N, N ', the glycidyl -4,4 of N ', O- five '-diaminourea -4 "-hydroxyl triphenylmenthane epoxy resin, N, N, N ', N '-four glycidyl group -2,2- double [4- (4- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', N '-four contracts Water glyceryl -2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four glycidyl group - 2,2- double [4- (3- amino-benzene oxygens) phenyl] propane epoxy resin, N, N, N ', the double [4- (2- of N '-four glycidyl group -2,2- Trifluoromethyl-4-aminophenoxyl) phenyl] propane epoxy resin, N, N, N ', double [4- (the 3- ammonia of N '-four glycidyl group -2,2- Phenoxyl) phenyl] HFC-236fa epoxy resin, N, N, N ', the double [4- (2- trifluoromethyls -4- of N '-four glycidyl group -2,2- Amino-benzene oxygen) phenyl] HFC-236fa epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) Diphenyl ether epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether Epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N ', N '-four contracts Water glyceryl -4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulfide epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- ammonia Phenoxyl) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl -4- aminobenzenes Epoxide) diphenyl-methane epoxy resin, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) benzophenone ring Oxygen tree fat, N, N, N ', N '-four glycidyl group -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone asphalt mixtures modified by epoxy resin Fat, N, N, N ', N '-four glycidyl group -4,4 '-bis- (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N ', N '-four shrinks Glyceryl -4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resins, N, N, N ', N ', O, the O glycidol of '-six One or more in double (3- amino-4-hydroxylphenyls) the HFC-236fa epoxy resin of base -2,2-.

3. a kind of carbon fiber cable core according to claim 1 MHFPI type fire resistant epoxy matrix resins, its feature exists In：Described reactive diluent is selected from hydrogenated bisphenol A epoxy resin, CE-793 epoxy resin, ES216 epoxy resin, 1,3- bis- Glycidyl resorcinol type epoxy, 3,4- epoxycyclohexyethylSiOis acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4- epoxy radicals - 6- methyl cyclohexanes acid -3 ', 4 '-epoxy radicals -6 '-methyl cyclohexane methyl esters, ECC202 epoxy resin, the one kind in Dipentenedioxide Or it is several.

4. a kind of carbon fiber cable core according to claim 1 MHFPI type fire resistant epoxy matrix resins, its feature exists In：Described curing agent be selected from aluminium acetylacetonate, 2-methylimidazole, 2-ethyl-4-methylimidazole, N, accelerine, N, N- dimethyl open-chain crown ether, DMP-30, benzyl dimethylamine, 2,4,6- tri- (dimethylamino methyl) phenol, DBU, 1,8- phenodiazine Miscellaneous bicyclic [5.4.0] hendecene -7, HHPA, K-12 curing agent, THPA, methyl tetrahydro phthalic anhydride, dodecenyl succinate Acid anhydrides, methyl hexahydrophthalic anhydride, tung oil acid anhydride, with 80 acid anhydrides of dicyclopentadiene and maleic acid anhydride reactant, with terpene two The acid anhydrides of alkene and maleic acid anhydride reactant, with the liquid acid anhydrides of turpentine oil and maleic acid anhydride reactant Plant or several.

5. a kind of carbon fiber cable core according to claim 1 MHFPI type fire resistant epoxy matrix resins, its feature exists In：Described aromatic diamine is selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 4,4 '-MDA, 3,3 '-two Methyl -4,4 ' MDA, 4,4 '-diaminodiphenyl ether, 4,4 '-benzidine, ' two of 3,3 '-dimethyl -4,4 Aminobphenyl, 2,2 '-dimethyl -4,4 ' benzidine, 3,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 4,4 ' - Double (3- amino-benzene oxygens) benzene of double (3- amino-benzene oxygens) benzene of DADPS, 3,3 '-DADPS, 1,3-, 1,4-, Double (4- amino-benzene oxygens) benzene of 1,3-, double (4- amino-benzene oxygens) benzene of 1,4-, 1,3- are double (2- trifluoromethyl-4-aminophenoxyls) Benzene, 1,4- double (2- trifluoromethyl-4-aminophenoxyls) benzene, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s, 4,4 '-bis- (3- ammonia Phenoxyl) diphenyl sulphone (DPS), 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS)s, 4,4 '-bis- (4- amino-benzene oxygens) Diphenyl ether, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl ether, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) diphenyl ether, 4, 4 '-bis- (4- amino-benzene oxygens) diphenyl sulfides, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl sulfides, 4,4 '-it is bis- (2- trifluoromethyls- 4- amino-benzene oxygens) diphenyl sulfide, 4,4 '-bis- (4- amino-benzene oxygens) benzophenone, 4,4 '-bis- (3- amino-benzene oxygens) hexichol Ketone, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) benzophenone, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, 4,4 '- Double (3- amino-benzene oxygens) biphenyl, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) biphenyl, 4,4 '-bis- (4- aminobenzene oxygen Base) diphenyl-methane, 4,4 '-bis- (3- amino-benzene oxygens) diphenyl-methanes, 4,4 '-bis- (2- trifluoromethyl-4-aminophenoxyls) two Double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of phenylmethane, 2,2-, double [4- (3- amino-benzene oxygens) phenyl] hexafluoros of 2,2- Double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] HFC-236fas of propane, 2,2-, the double [4- (4- amino-benzene oxygens) of 2,2- Phenyl] propane, double [4- (3- amino-benzene oxygens) phenyl] propane of 2,2-, the double [4- (2- trifluoromethyl-4-aminophenoxyls) of 2,2- Phenyl] propane, one or more in double (4- aminophenyls) HFC-236fas of 2,2-.

6. a kind of carbon fiber cable core according to claim 1 MHFPI type fire resistant epoxy matrix resins, its feature exists In：Described aromatic dianhydride is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, 3,3 ', 4,4 '-four Carboxyl biphenyl dianhydride, 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, 3,3 ', 4,4 '-tetracarboxylic diphenyl sulfone dianhydride, 2,2- are double Double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides of (3,4- dicarboxyphenyis) hexafluoropropane dianhydride, 2,2-, 2,2- are double [4- (3,4- di carboxyl phenyloxies) phenyl] hexafluoropropane dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxies) biphenyl dianhydrides, 4, 4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides, 4,4 '-bis- (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides, 4,4 '- Double (3,4- di carboxyl phenyloxies) diphenyl sulfone dianhydrides, 4,4 '-bis- (3,4- di carboxyl phenyloxies) benzophenone dianhydrides, 1,4- are double One or more in double (3,4- di carboxyl phenyloxies) benzene dianhydrides of (3,4- di carboxyl phenyloxies) benzene dianhydride, 1,3-.

7. a kind of carbon fiber cable core as claimed in claim 1 preparation method of MHFPI type fire resistant epoxy matrix resins, Comprise the following steps：

(1) 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa, aromatic diamine and highly polar aprotic organic solvents are added Enter in reactor, stirring and dissolving, adds aromatic dianhydride at room temperature, stirring reaction adds maleic anhydride after 0.5 hour, after Continuous stirring reaction 0.5 hour, adds aliphatic anhydride and catalyst, in after stirring reaction at 60 DEG C -100 DEG C -2 hours 1 hour, Precipitating agent, high-speed stirred, filtering is added to reclaim mother liquor, filter cake wash with acetone, vacuum drying 5 hours is -8 small at 70 DEG C -90 DEG C When, obtain MHFPI polyimide resins；

(2) by polyfunctional epoxy resin addition reactor, stirring after heating to 80 DEG C, adds MHFPI polyimides trees Fat, in after 80 DEG C of -120 DEG C of stirring reactions -2 hours 1 hour, is cooled to less than 90 DEG C, adds reactive diluent to continue to stir anti- Answer -1 hour 0.5 hour, be cooled to less than 60 DEG C, add curing agent, be uniformly mixed.

8. a kind of carbon fiber cable core according to claim 7 preparation side of MHFPI type fire resistant epoxy matrix resins Method, it is characterised in that：Highly polar aprotic organic solvent in the step (1) is selected from N,N-dimethylformamide, N, N- bis- One or more in methylacetamide, METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, dimethyl sulfoxide (DMSO)；Qiang Ji Property aprotic organic solvent and reactant mass ratio be 4-6:1；The quality of reactant refers to double (the 3- amino-4-hydroxies of 2,2- Phenyl) HFC-236fa, aromatic diamine, aromatic dianhydride and maleic anhydride quality sum.

9. a kind of carbon fiber cable core according to claim 7 preparation side of MHFPI type fire resistant epoxy matrix resins Method, it is characterised in that：Aliphatic anhydride in the step (1) is selected from acetic anhydride, propionic andydride, chloracetic acid acid anhydride, trifluoroacetic anhydride (TFAA) In one or more；Aliphatic anhydride is 3-6 with the mass ratio of reactant:1；The quality of reactant refers to double (the 3- ammonia of 2,2- Base -4- hydroxy phenyls) HFC-236fa, aromatic diamine, aromatic dianhydride and maleic anhydride quality sum.

10. a kind of carbon fiber cable core according to claim 7 preparation side of MHFPI type fire resistant epoxy matrix resins Method, it is characterised in that：Catalyst in the step (1) is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, pyridine, picoline, two One or more in picoline；Catalyst is 0.01-0.1 with the mass ratio of aromatic dianhydride：1.

A kind of 11. carbon fiber cable cores according to claim 7 preparation side of MHFPI type fire resistant epoxy matrix resins Method, it is characterised in that：Precipitating agent in the step (1) be selected from methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propane diols, tetrahydrofuran, One or more in methyltetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether；Precipitating agent is non-proton organic with highly polar The mass ratio of solvent is 2-5:1.

A kind of 12. carbon fiber cable cores according to claim 7 preparation side of MHFPI type fire resistant epoxy matrix resins Method, it is characterised in that：Acetone and the mass ratio of highly polar aprotic organic solvent in the step (1) are 1-2:1.