CN104892903B - A kind of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins and preparation method thereof, consisting of：Mass ratio is 100:1‑12:50‑100:150 200 polyfunctional epoxy resin, MHPI polyimide resins, reactive diluent and curing agent.Preparation method comprises the following steps：(1) reacted by the dihydroxybiphenyl of 3,3 ' diaminourea 4,4 ', aromatic diamine, aromatic dianhydride and maleic anhydride and MHPI polyimide resins are made；(2) polyfunctional epoxy resin and MHPI polyimide resins are carried out after copolyreaction, adds after reactive diluent, stirring hybrid reaction, add curing agent, be uniformly mixed.The present invention is easy to operate, environment-friendly, can complete to prepare on common apparatus, products obtained therefrom excellent combination property, viscosity is low, and good manufacturability can be applied to the pultrusion of carbon fiber cable core, with good market application foreground.

Description

A kind of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins and its preparation Method

Technical field

The invention belongs to polymeric material field, more particularly to a kind of high-temperature resistance carbon fiber cable core is drawn with MHPI types epoxy Squeeze resin and preparation method thereof.

Background technology

Steel-core-aluminium twisted wire being used transmission line of electricity now, this material has played important function in power Transmission 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 that the advanced core that lightweight, intensity is big, energy consumption is low, tower spacing is big, sag is small is made.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 High-temperature resin base composite core replaces the aluminium twisted wire that steel core is obtained, and huge leap can be brought to power transmission, it is lightweight, strong Degree is big, rigidity height, high temperature resistant, anticorrosive, and power consumption is small, sag is small and has higher security, 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 lacks there is also some Point, such as heat resistance is relatively low, much not as good as aromatic heterocyclic polymer systems such as polyimides, polybenzimidazoles, polybenzoxazoles, Mechanical property, the electric property of epoxy-resin systems in high temperature environments etc. declines notable, it is difficult to meet practical application request.Cause This, resistant, toughened modification is carried out to epoxy resin, is the focus of the current research of scientific and technical personnel both at home and abroad.

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 available 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 high polymer material；(3) good stability：The solidification of epoxy resin The ring opening polyaddition of epoxy radicals is mainly relied on, 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:1-2 component A and B component composition, wherein, A Component is the copolymer reacted by double [4- (2,4- diamino phenoxies) phenyl] HFC-236fas of 2,2- with epoxy resin；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 15%-30% homogeneous phase transparent solution.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 be 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 15%-30% homogeneous phase transparent solution.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 resistance to height of double (2,4- diamino phenoxies) biphenyl types of 4,4'- Temperature epoxy adhesive and preparation method thereof, is 1 by mass ratio:1-2 component A and B component composition, wherein component A be by 4,4 '- The copolymer that double (2,4- diamino phenoxies) biphenyl react with epoxy resin；B component be by 4,4 '-bis- (2,4- diaminos Phenoxyl) solid content that is reacted with aromatic dicarboxylic anhydride in highly polar aprotic organic solvent and toluene of biphenyl is 15%-30% homogeneous phase transparent solution.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 Temperature adds reactive diluent and organic solvent, stirs, obtain component A to after 70-80 DEG C of stirring reaction 15min-30min； (2) curing agent and organic solvent are mixed, stirring and dissolving is uniform, that is, obtains B component；(3) in use, A, B component are mixed, stir 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, obtain component A；Curing agent is B component；In use, will A, B component are well mixed, and are produced.

Into 21 century, the application of high polymer material is more and more extensive, and the development of human society and the life of people are not The application of high polymer 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 high polymer material Solvent-free volatilization, environment-friendly in the manufacturing, application process.Therefore, solvent-free high polymer 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 made.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 be 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, so as 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 has been 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 that main Material synthesis is obtained Phenolic hydroxy group polyetherimide resin (HPEI)；Using synthesized obtained HPEI as resistant, toughened dose, with N, N, N', N'- tetra- Glycidyl -4,4'- MDAs (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent Deng preparing and obtained the high-temperature resistant single-component epoxy adhesive of excellent combination property.

This method, although by synthesizing the polyetherimide resin containing active reactive group (hydroxyl, unsaturated double-bond) (HPEI) toughening modifying, has been carried out to epoxy resin, and has achieved preferable technique effect.But, there is also some shortcomings：

(1) reactable group is limited, and the content of particularly unsaturated double-bond is relatively low.Because maleic anhydride is as end-blocking Agent is come what is used, and the consumption of maleic anhydride is seldom.

The monomers such as double (3- amino-4-hydroxylphenyls) HFC-236fas (BAHPFP) of (2) 2,2- are expensive, cause polyethers acyl The cost of imide resin (HPEI) and adhesive is very high, is unfavorable for large-scale promotion application, can only be confined to some special dimensions.

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 ethers (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, continues stirring reaction -1 hour 0.5 hour, adds organic solvent, 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) in use, 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 after reaction certain time, 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:5-10:10-20:1-5:80-200 N, N, N ', N '-four shrinks Glyceryl -4,4 '-diaminodiphenyl ether epoxy resin (TGDADPE), aromatic diamine, aromatic dicarboxylic anhydride, curing agent With organic solvent composition；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, the homogeneous phase solution of aromatic dicarboxylic anhydride, curing agent and organic solvent is added, 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 high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusions Resin and preparation method thereof, the matrix resin excellent combination property is environment-friendly, and raw material sources are convenient, and preparation technology 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 high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins of the present invention, consisting of：Mass ratio is 100:1-12:50-100:150-200 polyfunctional epoxy resin, MHPI polyimide resins, reactive diluent and curing agent； Wherein, MHPI polyimide resins are by mol ratio 1:1-3:1-2:The 3,3 ' of 2-4-diaminourea-4,4 '-dihydroxybiphenyl, virtue Fragrant race's diamines, aromatic dianhydride and maleic anhydride reaction are 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 '-diaminodiphenylsulfone 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 '-diaminodiphenylsulfone 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 ', N ', the glycidyls -4,4 of 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 It is one or more of.

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 Succinic anhydride, methyl hexahydrophthalic anhydride, tung oil acid anhydride, with 80 acid anhydrides of dicyclopentadiene and maleic acid anhydride reactant, with Limonene is with the acid anhydrides of 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 '-diaminodiphenylsulfone, 3,3 '-diaminodiphenylsulfone, 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, the 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 preparation method of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins of the present invention, including it is as follows Step：(1) by 3,3 '-diaminourea -4,4 '-dihydroxybiphenyl, aromatic diamine and the addition of highly polar aprotic organic solvent are instead Answer in kettle, at room temperature after stirring and dissolving, add aromatic dianhydride, stirring reaction adds maleic anhydride, continue to stir after 1 hour Reaction 1.5 hours is mixed, aliphatic anhydride and catalyst is added, in after stirring reaction at 60 DEG C -100 DEG C -2 hours 1 hour, added Mother liquor is reclaimed in precipitating agent, high-speed stirred, filtering, is washed and is dried in vacuo -8 hours 5 hours at filter cake, 70 DEG C -90 DEG C with acetone, Obtain MHPI polyimide resins；

(2) polyfunctional epoxy resin is added in reactor, stirring is heated to after 100 DEG C, adds MHPI polyamides sub- Polyimide resin, in after 100 DEG C of -120 DEG C of stirring reactions -2 hours 1 hour, is cooled to less than 90 DEG C, adds reactive diluent and continues 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 The mass ratio of sub- organic solvent and reactant is 4-6:1；The quality of reactant refers to 3,3 '-diaminourea -4,4 '-dihydroxy connection Benzene, aromatic diamine, the quality sum of aromatic dianhydride and maleic anhydride.

Aliphatic anhydride in the step (1) in acetic anhydride, propionic andydride, chloracetic acid acid anhydride, trifluoroacetic anhydride (TFAA) one Plant or several；The mass ratio of aliphatic anhydride and reactant is 3-6:1；The quality of reactant refers to 3,3 '-diaminourea -4,4 ' - Dihydroxybiphenyl, aromatic diamine, the quality sum of aromatic dianhydride and maleic anhydride.

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 and the mass ratio of aromatic dianhydride are 0.01-0.1：1.

Precipitating agent in the step (1) is selected from methanol, 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.

The mass ratio of acetone and highly polar aprotic organic solvent in the step (1) is 1-2:1.

Beneficial effect

(1) high-temperature resistance carbon fiber cable core of the invention has good combination property with MHPI type epoxy pultrusion resins, It is solvent-free, it is environment-friendly；

(2) high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins of the invention, with low viscosity, high is anti- Should be active, with good pultrusion；

(3) high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins of the invention, 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 technology of the present invention is simple, cost is low, 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 the carbon fiber cable core MHPI type fire resistant epoxy matrix resins PTM-1 of embodiment 3 viscosity versus temperature Curve.

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 21.6 grams of (0.1 mole) 3,3 '-diaminourea -4,4 '-dihydroxybiphenyl (DADHBP), 51.8 grams (0.1 mole) 2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas and 870 grams of DMFs are added in reactor, in room After the lower stirring and dissolving of temperature, 52.0 grams of (0.1 moles) 2 are added, double [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydrides of 2- are stirred After mixing reaction 1 hour, 19.6 grams of (0.2 mole) maleic anhydrides are added, continue stirring reaction 1.5 hours, 440 grams of acetic anhydrides are added With 0.6 gram of pyridine, in after stirring reaction at 90 DEG C 1 hour, adding 800 grams of methanol and 940 grams of ethanol, high-speed stirred is filtered, returned Mother liquor is received, is washed and is dried in vacuo 8 hours at filter cake, 70 DEG C with 870 grams of acetone, obtain 135.2 grams of MHPI polyimide resins, remembered Make MHPI-1.

Embodiment 2

By 21.6 grams of (0.1 mole) 3,3 '-diaminourea -4,4 '-dihydroxybiphenyl (DADHBP), 51.8 grams (0.1 mole) Double [4- (4- amino-benzene oxygens) phenyl] HFC-236fas of 2,2- and 40.0 grams of (0.2 mole) 3,4 '-diaminodiphenyl ethers, 300 grams DMF and 700 grams of METHYLPYRROLIDONEs are added in reactor, at room temperature after stirring and dissolving, are added 52.0 grams of double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides of (0.1 mole) 2,2- and 31.0 grams of (0.1 moles) 3,3 ', 4,4 '-tetracarboxylic diphenyl ether dianhydride, stirring reaction adds 39.2 grams of (0.4 mole) maleic anhydrides after 1 hour, continues to stir anti- Answer 1.5 hours, add 1410.0 grams of acetic anhydrides, 2.3 grams of triethylamines and 6.0 grams of pyridines, in after stirring reaction at 80 DEG C 2 hours, 5000 grams of methanol are added, mother liquor is reclaimed in high-speed stirred, filtering, vacuum drying 5 at filter cake, 90 DEG C is washed with 2000 grams of acetone small When, 215.3 grams of MHPI polyimide resins are obtained, MHPI-2 is denoted as.

Embodiment 3

By 30.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenyl ether epoxy resin and 70.0 grams of N, N, N ', N ' double [4- (4- amino-benzene oxygens) phenyl] the propane epoxy resin of-four glycidyl group -2,2- are added in reactors, stirring, Heat to after 100 DEG C, add 8.0 grams of MHPI-1 polyimide resins, in after 100 DEG C of stirring reactions 1 hour, be cooled to 90 Below DEG C, add 50.0 grams of hydrogenated bisphenol A epoxy resins and continue stirring reaction 1 hour, be cooled to less than 60 DEG C, add 140.0 Gram methyl tetrahydro phthalic anhydride and 10.0 grams of 2-ethyl-4-methylimidazoles, are uniformly mixed, obtain 308.0 grams of high-temperature resistance carbon fibers Cable core MHPI type epoxy pultrusion resins, are denoted as PTM-1, its temperature-viscosity curve is as shown in figure 1, gelation time-temperature Relation is as shown in table 1.

Embodiment 4

By 40.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-diaminodiphenylsulfone epoxy resin and 60.0 grams of N, N, O- triglycidyl group para-aminophenol epoxy resin is added in reactor, stirring, is heated to after 100 DEG C, adds 5.0 grams MHPI-1 and 7.0 gram of MHPI-2 polyimide resin, in after 120 DEG C of stirring reactions 2 hours, being cooled to less than 90 DEG C, addition 75.0 grams of 1,3- diglycidyls resorcinol type epoxies continue stirring reaction 0.5 hour, are cooled to less than 60 DEG C, addition 50.0 grams of tung oil acid anhydrides, 15.0 grams of 2-ethyl-4-methylimidazoles and 135.0 grams of dodecenylsuccinic anhydrides, are uniformly mixed, 387.0 grams of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins are obtained, PTM-2 is denoted as.

Embodiment 5

By 100.0 grams of N, N, N ', N '-four glycidyl group -4,4 '-MDA epoxy resin adds reactor In, stirring is heated to after 100 DEG C, adds 1.0 grams of MHPI-2 polyimide resin, small in 110 DEG C of stirring reactions 1.5 Shi Hou, is cooled to less than 90 DEG C, adds 80.0 grams of 1,3- diglycidyls resorcinol type epoxies and 20.0 grams of CE-793 Epoxy resin continues stirring reaction 0.5 hour, is cooled to less than 60 DEG C, adds 70.0 grams of methyl tetrahydro phthalic anhydrides, 15.0 grams of 2- second Base -4-methylimidazole and 85.0 grams of dodecenylsuccinic anhydrides, are uniformly mixed, and obtain 371.0 grams of high-temperature resistance carbon fiber electricity Cable core MHPI type epoxy pultrusion resins, are denoted as PTM-3.

Embodiment 6

The high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins of appropriate 3~embodiment of embodiment 5 are taken respectively, i.e., PTM-1~PTM-3, and be uniformly applied to respectively in standard stainless steel test piece, room temperature was hung after 0.5 hour, was overlapped, and was clamped, It is put into convection oven and is solidified：Started to warm up from room temperature to 95 DEG C, insulation reaction 2 hours is continuously heating to 145 DEG C, guarantor Temperature reaction 1 hour, is continuously heating to 170 DEG C, insulation reaction 2 hours naturally cools to room temperature.It is entered using electronic tensile machine Row 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 high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins of appropriate 3~embodiment of embodiment 5 are taken respectively, i.e., PTM-1~PTM-3, film is above pushed away in polytetrafluoroethylene film, is placed in vacuum drying chamber, be made into size for 5mm × 5mm × 1mm square coupons, curing process is：Started to warm up from room temperature to 95 DEG C, insulation reaction 2 hours is continuously heating to 145 DEG C, Insulation reaction 1 hour, is continuously heating to 170 DEG C, 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 2.

Its dielectric loss (D) (1MHz, 25 is tested using the TH2828S testers of Changzhou Tong Hui Electron equipment Co., Ltd DEG C), it the results are shown in Table 2.

Using precision electronic balance, the square coupons of above-mentioned drying are weighed after (W1), deionized water (25 DEG C) is soaked in In, after 72 hours, take out, dry surface with filter paper, weigh (W2), calculating obtains water absorption rateData it is as shown in table 1.Profit With precision electronic balance, the square coupons of above-mentioned drying are weighed after (G1), climatic chamber (85 DEG C, RH85%) is positioned over In, after 72 hours, take out, dry surface with filter paper, weigh (G2), the data that calculating obtains hydroscopicity (ψ) are as shown in table 2.

The high-temperature resistance carbon fiber cable core of table 1 MHPI type epoxy pultrusion resins PTM-1 gelation time t_gel

Temperature (DEG C)	120	140	150	160	170	180	190	200
									tgel(s)	631	232	151	101	65	40	27	20

The performance data of the high-temperature resistance carbon fiber cable core of table 2 MHPI type epoxy pultrusion resins

Claims (12)

1. a kind of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins, it is characterised in that：Consisting of：Mass ratio is 100:1-12:50-100:150-200 polyfunctional epoxy resin, MHPI polyimide resins, reactive diluent and curing agent； Wherein, MHPI polyimide resins are by mol ratio 1:1-3:1-2:The 3,3 ' of 2-4-diaminourea-4,4 '-dihydroxybiphenyl, virtue Fragrant race's diamines, aromatic dianhydride and maleic anhydride reaction are formed.

2. a kind of high-temperature resistance carbon fiber cable core according to claim 1 MHPI type epoxy pultrusion 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 '-diaminodiphenylsulfone 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 '-diaminodiphenylsulfone 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 ', N ', the glycidyls -4,4 of 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 high-temperature resistance carbon fiber cable core according to claim 1 MHPI type epoxy pultrusion 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, one kind in Dipentenedioxide Or it is several.

4. a kind of high-temperature resistance carbon fiber cable core according to claim 1 MHPI type epoxy pultrusion 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, benzyl dimethylamine, 2,4,6- tri- (dimethylamino methyl) phenol, 1,8- diazabicyclos [5.4.0] hendecene -7, HHPA, K-12 curing agent, THPA, methyl tetrahydro phthalic anhydride, dodecenylsuccinic anhydride, first Base HHPA, tung oil acid anhydride, with 80 acid anhydrides of dicyclopentadiene and maleic acid anhydride reactant, with limonene with along fourth The acid anhydrides of enedioic acid anhydride reactant, with one kind or several in the liquid acid anhydrides of turpentine oil and maleic acid anhydride reactant Kind.

5. a kind of high-temperature resistance carbon fiber cable core according to claim 1 MHPI type epoxy pultrusion 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 diaminodiphenylsulfone, 3,3 '-diaminodiphenylsulfone, 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) Double (2- trifluoromethyl-4-aminophenoxyls) benzene of benzene, 1,4-, 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, the one or more in double (4- aminophenyls) HFC-236fas of 2,2-.

6. a kind of high-temperature resistance carbon fiber cable core according to claim 1 MHPI type epoxy pultrusion 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 high-temperature resistance carbon fiber cable core preparation method of MHPI type epoxy pultrusion resins, comprises the following steps：

(1) by 3,3 '-diaminourea -4,4 '-dihydroxybiphenyl, aromatic diamine and the addition reaction of highly polar aprotic organic solvent In kettle, at room temperature after stirring and dissolving, aromatic dianhydride is added, stirring reaction adds maleic anhydride after 1 hour, continue to stir Reaction 1.5 hours, adds aliphatic anhydride and catalyst, heavy in after stirring reaction at 60 DEG C -100 DEG C -2 hours 1 hour, adding Agent is analysed, mother liquor is reclaimed in high-speed stirred, filtering, is washed and is dried in vacuo -8 hours 5 hours at filter cake, 70 DEG C -90 DEG C with acetone, obtained To MHPI polyimide resins；

(2) polyfunctional epoxy resin is added in reactor, stirring is heated to after 100 DEG C, adds MHPI polyimides trees Fat, in after 100 DEG C of -120 DEG C of stirring reactions -2 hours 1 hour, is cooled to less than 90 DEG C, adds reactive diluent and continues 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 preparation side of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins according to claim 7 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 3,3 '-diaminourea -4,4 '-dihydroxy Base biphenyl, aromatic diamine, the quality sum of aromatic dianhydride and maleic anhydride.

9. a kind of preparation side of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins according to claim 7 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；The mass ratio of aliphatic anhydride and reactant is 3-6:1；The quality of reactant refer to 3,3 '-diaminourea- 4,4 '-dihydroxybiphenyl, aromatic diamine, the quality sum of aromatic dianhydride and maleic anhydride.

10. a kind of preparation side of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins according to claim 7 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 and the mass ratio of aromatic dianhydride are 0.01-0.1：1.

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

12. a kind of preparation side of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins according to claim 7 Method, it is characterised in that：The mass ratio of acetone and highly polar aprotic organic solvent in the step (1) is 1-2:1.