CN104479299B - A kind of carbon fiber cable core high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin and preparation method thereof - Google Patents
A kind of carbon fiber cable core high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin and preparation method thereof Download PDFInfo
- Publication number
- CN104479299B CN104479299B CN201410854288.9A CN201410854288A CN104479299B CN 104479299 B CN104479299 B CN 104479299B CN 201410854288 A CN201410854288 A CN 201410854288A CN 104479299 B CN104479299 B CN 104479299B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- cable core
- fiber cable
- temperature resistant
- high temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to a kind of carbon fiber cable core high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin and preparation method thereof, this matrix resin is made up of ES216 epoxy resin, tetrabromo bisphenol-a epoxy resin, DOPO, PHT4, four maleimide resins, firming agent, accelerator and reactive diluent.Preparation method includes: (1) mixing ES216 epoxy resin and four maleimide resins, heat temperature raising, and stirring reaction adds reactive diluent, and stirring obtains component A；(2) mixing tetrabromo bisphenol-a epoxy resin and DOPO, PHT4, heat temperature raising, stirring reaction, add reactive diluent, and stirring obtains B component；(3) C component is firming agent and accelerator；By A, B, C tri-component be uniformly mixed.The present invention is suitable for the manufacture of the fibre-reinforced advanced composite materials such as carbon fiber, glass fibre, aramid fiber, is especially suitable for the pultrusion manufacture of carbon fiber cable core.
Description
Technical field
The invention belongs to matrix resin field, particularly to a kind of carbon fiber cable core with the high temperature resistant phosphorus solvent-free ring of bromine type
Oxygen matrix resin and preparation method thereof.
Background technology
It is known that epoxy resin has many excellent performances: the adhesive property that (1) is good: adhesive strength is high, bonding
Wide, it and many metals (such as ferrum, steel, copper, aluminum, metal alloy etc.) or nonmetallic materials are (such as glass, pottery, timber, plastics
Deng) adhesive strength the highest, have even more than by the intensity of viscous material itself, therefore can be used for many stress members
In, it is one of the main component of structural adhesive；(2) good processing characteristics: the motility of Formulaion of epoxy resin, processing work
The multiformity of skill and product properties is the most prominent in macromolecular material；(3) good stability: the solidification of epoxy resin
Mainly relying on the ring opening polyaddition of epoxy radicals, therefore do not produce low-molecular material in solidification process, its cure shrinkage is heat
One of kind minimum in thermosetting resin, generally 1%-2%, if selecting suitable filler that shrinkage factor can be made to be down to 0.2%
Left and right；Epoxy main chains after solidification is ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore has the resistance to acids and bases of excellence.
Therefore, epoxy resin is widely used in the every field of national economy: either high-technology field is still
Field of general technology, either all can see its trace in defence and military or civilian industry, or even daily life.
Entering 21 century, the application of macromolecular material is more and more extensive, and the development of human society and the life of people are the most not
The application of macromolecular material can be left.Meanwhile, people are the highest to the requirement of living environment, it is desirable to macromolecular material
Solvent-free volatilization in the manufacturing, application process, environmental friendliness.Therefore, solvent-free macromolecular material, the most 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 the preparation method of a kind of heat-resistant solvent-free epoxy adhesive, and it is the most special
Levy and be: TGDDM epoxy resin, toughener, hydrogenated bisphenol A, firming agent, accelerator mix homogeneously, prepared high temperature resistant without molten
Agent epoxy adhesive.But its resistance to elevated temperatures still has bigger limitation, failing to meet the reality under many hot environments should
With.
Chinese patent CN101397486A discloses the preparation method of a kind of bi-component solvent-free epoxy resin adhesive, its
It is characterized mainly in that: it includes component A and B component, and wherein component A contains novolac epoxy resin, alicyclic type epoxy resin and end
Carboxy terminated nitrile rubber；B component is double (2,4-diamino phenoxy) the benzene aromatic polyvalent amine hardener of 1,4-.Alicyclic ring type asphalt mixtures modified by epoxy resin
The addition of fat and nbr carboxyl terminal is respectively the 20-35% and 12% (mass percent) of novolac epoxy resin.1,4-
15-20% (the quality that addition is novolac epoxy resin of double (2,4-diamino phenoxy) benzene aromatic polyvalent amine hardener
Percent), gained adhesive system good manufacturability.But its heat resistance is the most preferable.
Chinese patent CN1927908A discloses the preparation method of a kind of phenolic hydroxyl group containing polyimide powder, due to phenolic hydroxyl group
Existence, 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 made further to reach good toughening effect.
Yu Xinhai et al. [development [J] of high-temperature resistant single-component epoxy adhesive. bonding, 2008,29 (12): 16-19] public
Open the preparation method of a kind of high-temperature resistant single-component epoxy adhesive, be primarily characterized in that: with maleic anhydride (MA) for end-blocking
Agent, with 2, double (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-, 2, double [4-(4-amino-benzene oxygen) phenyl] third of 2-
Double [4-(3,4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) of alkane (BAPOPP), 2,2-is that main material synthesis obtains
Phenolic hydroxy group polyetherimide resin (HPEI)；It it is resistant, toughened dose with the synthesized HPEI obtained, with N, N, N', N'-tetra-
Glycidyl-4,4'-MDA (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.
The method, although contained the polyetherimide resin of active reactive group (hydroxyl, unsaturated double-bond) by synthesis
(HPEI), epoxy resin has been carried out toughening modifying, and has achieved preferable technique effect.But, there is also some shortcomings:
(1) reactable group is limited, and the particularly content of unsaturated double-bond is on the low side.Because maleic anhydride is as end-blocking
Agent uses, and the consumption of maleic anhydride is little.
The monomers such as (2) 2,2-double (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) are expensive, cause polyethers acyl
The cost of imide resin (HPEI) and adhesive is the highest, is unfavorable for large-scale promotion application, can only be confined to some special dimension.
Maleimide resin have excellence resistance to elevated temperatures, particularly four maleimide resins, meanwhile, itself and ring
Epoxy resins has a good chemical reactivity, and therefore, four maleimide resins are that particularly excellent high temperature resistant of epoxy resin changes
Property agent.
The existing patent literature of development and application work about four maleimide resins:
Chinese invention patent CN101250152A discloses double (the 2,4-dimaleimide phenoxyl) benzene of a kind of 1,3-
Molecular structure of four maleimide resins and preparation method thereof.
Chinese invention patent CN101239940A discloses double (the 2,4-dimaleimide phenoxyl) benzene of a kind of 1,4-
Molecular structure of four maleimide resins and preparation method thereof.
Chinese invention patent CN101921482A discloses the double [4-(2,4-dimaleimide phenoxyl) of a kind of 2,2-
Phenyl] molecular structure of propane four maleimide resin, preparation method and applications.It is primarily characterized in that: the present invention relates to
And one thermoset polyimide resin and preparation method thereof, this resin is made up of component A and B component, and its weight ratio is 1:2-
6；Wherein component A is the dimaleoyl imino polyimide resin solution that homogeneous phase transparent is thick, solid content 10%-25%；B group
It is divided into four dimaleoyl imino bisphenol-A solution, solid content 30%-40%；Preparation method is: dimaleoyl imino polyimides tree
The preparation method of fat liquid (component A) includes following two steps: (1) is by double for 2,2-[4-(2,4-diamino phenoxy) phenyl] third
Alkane and highly polar aprotic organic solvent are put in reactor, under room temperature, after stirring and dissolving is complete, add maleic anhydride solid powder
End, stirs under room temperature to being completely dissolved, and after continuing stirring reaction 0.5 hour, adds aromatic dicarboxylic anhydride, and under room temperature, stirring is anti-
Answer 5-8 hour, it is thus achieved that the resin solution that homogeneous phase transparent is thick；(2) azeotropy dehydrant is added, the stirring reaction of azeotropic reflux water-dividing
After 6-8 hour, obtain the dimaleoyl imino polyimide resin liquid that homogeneous phase transparent is thick；Four dimaleoyl imino bisphenol-As
The preparation method of solution (B component) includes following two steps: (1) is by double for 2,2-[4-(2,4-diamino phenoxy) phenyl] third
Alkane and highly polar aprotic organic solvent are put in reactor, under room temperature, after stirring and dissolving is complete, add maleic anhydride solid powder
End, stirs under room temperature to being completely dissolved, after continuing stirring reaction 3 hours, it is thus achieved that homogeneous phase transparent solution；(2) azeotropic dehydration is added
Agent, after the stirring of azeotropic reflux water-dividing is reacted 5 hours, obtains four dimaleoyl imino bisphenol-A solution of homogeneous phase transparent.
The thermoset polyimide resin that this invention obtains can be applied not only to high-temperature resistance adhesive and glass fibre increases
The matrix resin of strong composite, and also apply be applicable to carbon fiber, the fibre-reinforced advanced person of the contour performance of aramid fiber again
The matrix resin of condensation material, is with a wide range of applications.
Chinese invention patent CN101973147A discloses double (the 2,4-dimaleimide phenoxyl) benzene of a kind of 1,4-
The molecular structure of four maleimide resins, application and preparation method thereof.It is primarily characterized in that: the present invention relates to a kind of resistance to height
The preparation method of temperature polyimides glass cloth laminated board, mainly comprises the steps: under (1) room temperature, is the 1 of 1:2 by mol ratio,
Double (2, the 4-diamino phenoxy) benzene of 4-and maleic anhydride add in highly polar aprotic organic solvent, stir reaction 1 under room temperature
After hour, adding aromatic diamine monomer, after stirring and dissolving is complete, add aromatic dicarboxylic anhydride, under room temperature, stirring reaction 3 is little
Time, add initiator, stirring and dissolving, obtain the thick resin solution of homogeneous phase transparent, i.e. component A；(2) it is 1:4 by mol ratio
Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene and maleic anhydride add in highly polar aprotic organic solvent, under room temperature, stirring is anti-
After answering 2 hours, obtain the resin solution of homogeneous phase transparent, i.e. B component；(3) when using, by A, B component mix homogeneously under room temperature,
Polyimide precursor resin solution, uses glass cloth impregnating resin solution, preliminary drying semi-solid preparation to obtain prepreg, enters height after stacking
Temperature and pressure machine heat cure, obtains high-temperature resistant polyimide glass fabric laminated board.
The method technique is simple, low cost, environmental friendliness, can complete preparation process in common apparatus, it is adaptable to work
Industry produces.
The high-temperature resistant polyimide glass fabric laminated board that this invention obtains, the thermal weight loss initial temperature of its resin cured matter
Tonset is 591.9 DEG C, has extremely excellent thermostability, can be applied not only to the high temperature resistant electric insulation material of high power motor
Material, and can be applicable to the high-temperature-resistant structure part material of the primary load bearing of aerospace flight vehicle, it is with a wide range of applications.
Chinese invention patent CN101962436A discloses a kind of heat resist modification multi-functional epoxy used for advanced composite material
Matrix resin and preparation method thereof, is primarily characterized in that: use Isosorbide-5-Nitrae-bis-(2,4-dimaleimide phenoxyl) benzene
Four maleimide resins and polyfunctional epoxy resin, nbr carboxyl terminal CTBN react the novel fire resistant obtaining high tenacity
Resin, adds organic solvent, and stirring and dissolving is uniform, obtains the viscous liquid of homogeneous phase transparent, i.e. component A；Firming agent is with organic
Solvent mixes, and stirring and dissolving is uniform, obtains B component；A, B component are mixed, stirs, obtain used for advanced composite material
Heat resist modification multi-functional epoxy's substrate resin solution.
Summary of the invention
The technical problem to be solved is to provide a kind of high temperature resistant phosphorus solvent-free ring of bromine type of carbon fiber cable core
Oxygen matrix resin and preparation method thereof, this matrix resin excellent combination property, environmental friendliness, raw material sources are convenient, preparation technology
Simply, low cost, it is suitable for the manufacture of the fibre-reinforced advanced composite materials such as carbon fiber, glass fibre, aramid fiber, it is possible to
It is applied to the pultrusion of the products such as carbon fiber reinforced cable core composite, has broad application prospects.
A kind of carbon fiber cable core of the present invention high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, described matrix resin
By the ES216 epoxy resin that mass ratio is 100:10-50:10-100:10-85:4-25:100-300:10-20:30-100, four
Bromine bisphenol A epoxide resin, DOPO, PHT4, four maleimide resins, firming agent, accelerator and reactive diluent composition.
Four described maleimide resins are double selected from double (the 2,4-dimaleimide phenoxyl) benzene of 1,4-, 1,3-
Double [4-(the 2,4-dimaleimide phenoxyl) phenyl] propane of (2,4-dimaleimide phenoxyl) benzene, 2,2-, 2,
2-double [4-(2,4-dimaleimide phenoxyl) phenyl] HFC-236fa, 4,4 '-bis-(2,4-dimaleimide base benzene oxygen
Base) diphenyl ether, 4,4 '-bis-(2,4-dimaleimide phenoxyl) diphenyl-methanes, 4,4 '-bis-(2,4-dimaleimides
Phenoxyl) benzophenone, 4,4 '-bis-(2,4-dimaleimide phenoxyl) diphenyl sulphone (DPS)s, 4,4 '-bis-(2,4-bis-Malaysias
Imide phenoxy group) one or more in biphenyl.
Described firming agent is selected from HHPA, THPA, methyl tetrahydro phthalic anhydride, dodecenylsuccinic anhydride, methyl
HHPA, tung oil acid anhydride, with dicyclopentadiene and 80 anhydride of maleic acid anhydride reactant, with limonene and maleic
Dicarboxylic anhydride reaction anhydride, with Oleum Terebinthinae and one or more in the liquid anhydride of maleic acid anhydride reactant.
Described accelerator be selected from aluminium acetylacetonate, 2-ethyl-4-methylimidazole, N, N-dimethyl open-chain crown ether,
DMP-30, benzyl dimethylamine, N, accelerine, 2,4,6-tri-(dimethylamino methyl) phenol, DBU, 1,8-diaza are double
One or more in ring [5.4.0] hendecene-7.
Described reactive diluent is selected from hydrogenated bisphenol A epoxy resin, CE793,3,4-epoxycyclohexyethylSiOi acid-3 ', 4 '-ring
Epoxide hexamethylene methyl ester, 3,4-epoxy radicals-6-methyl cyclohexane acid-3 ', 4 '-epoxy radicals-6 '-methyl cyclohexane methyl ester, titanium dioxide diamyl
One or more in alkene.
A kind of carbon fiber cable core of present invention preparation method of high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, bag
Include following steps:
(1) putting in reactor by ES216 epoxy resin and four maleimide resins, stirring mixing, in 100 DEG C-120
DEG C reaction 0.5 hour-1.5 hours after, be cooled to less than 80 DEG C, add reactive diluent, after being uniformly mixed, obtain A group
Part；(2) tetrabromo bisphenol-a epoxy resin is put in reactor with DOPO, react 0.5 hour-1.5 hours in 100 DEG C-120 DEG C
After, add PHT4, after continuing reaction 0.5 hour-1.5 hours, add reactive diluent, be uniformly mixed, obtain B group
Part；
(3) C component is firming agent and accelerator, puts in reactor by component A, B component, in 100 DEG C-110 DEG C stirrings
After mixing 10min-20min, it is cooled to less than 50 DEG C, adds C component, mix homogeneously, obtain carbon fiber cable core with high temperature resistant
Phosphorus bromine type non-solvent epoxy matrix resin.
Beneficial effect
(1) carbon fiber cable core of the present invention has good comprehensive with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin
Performance, solvent-free, environmental friendliness；
(2) carbon fiber cable core of the present invention is with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, has low viscosity,
High reactivity, has good pultrusion；
(3) carbon fiber cable core of the present invention is with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, can be applicable to carbon fine
The pultrusion of dimension composite, high temperature resistant, high intensity, with carbon fiber, there is good wellability, interface performance is good, has wide
Wealthy application prospect；
(4) preparation technology of the present invention is simple, low cost, easy to operate, reaction raw materials convenient sources, can be at common apparatus
In complete preparation process, be advantageously implemented industrialized production.
Accompanying drawing explanation
Fig. 1 is the viscous of the high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin CFPM-1 of carbon fiber cable core of embodiment 1
Degree-temperature curve；
Fig. 2 is the solidifying of the high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin CFPM-1 of carbon fiber cable core of embodiment 1
Gel time-temperature curve.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Embodiment 1
By 100.0 grams of ES216 epoxy resin and 25.0 grams of double [4-(2,4-dimaleimide phenoxyl) benzene of 2,2-
Base] propane puts in reactor, stirring mixing, and after 120 DEG C of reactions 0.5 hour, it is cooled to less than 80 DEG C, adds 70.0 grams of work
Property diluent CE793, after being uniformly mixed, obtains 195.0 grams of component A, is denoted as A1.
By 50.0 grams of tetrabromo bisphenol-a epoxy resins and 10.0 grams of DOPO (9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-
Oxide) put in reactor, after 120 DEG C of reactions 0.5 hour, add 10.0 grams of PHT4s, continue reaction 0.5 hour
After, add 30.0 grams of reactive diluent CE793, be uniformly mixed, obtain 100.0 grams of B component, be denoted as B1.
Component C, by 100.0 grams of dodecenylsuccinic anhydrides and 20.0 grams of N, N-dimethyl open-chain crown ether compositions, is denoted as
C1.A1 component, B1 component are put in reactor, after 110 DEG C of stirring mixing 10min, is cooled to less than 50 DEG C, adds C1 group
Point, mix homogeneously, obtain 415.0 grams of carbon fiber cable cores with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, be denoted as CFPM-
1.Use BROOKFIELD CAP2000+ viscosity tester that its variation relation carrying out viscosity with temperature is tested, result
As shown in Figure 1；Use gelation time tester that it is carried out gelation time variation with temperature relation test, result such as figure
Shown in 2.
Embodiment 2
By double to 100.0 grams of ES216 epoxy resin and 2.0 grams of 1,4-(2,4-dimaleimide phenoxyl) benzene, 2.0 grams
2,2-double [4-(2,4-dimaleimide phenoxyl) phenyl] propane are put in reactor, and stirring mixing, in 100 DEG C of reactions
After 1.5 hours, it is cooled to less than 80 DEG C, adds 10.0 grams of reactive diluent CE793, after being uniformly mixed, obtain 114.0 grams
Component A, is denoted as A2.
By 10.0 grams of tetrabromo bisphenol-a epoxy resins and 100.0 grams of DOPO (9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-
Oxide) put in reactor, after 100 DEG C of reactions 1.5 hours, add 85.0 grams of PHT4s, continue reaction 1.5 hours
After, add 20.0 grams of reactive diluent CE793, be uniformly mixed, obtain 215.0 grams of B component, be denoted as B2.
Component C is by 200.0 grams of methyl tetrahydro phthalic anhydrides, 100.0 grams of dodecenylsuccinic anhydrides and 5.0 grams of 2-ethyl-4-first
Base imidazoles, 5.0 grams of N, N-dimethyl open-chain crown ether compositions, be denoted as C2.A2 component, B2 component are put in reactor, in 100
DEG C stirring mixing 20min after, be cooled to less than 50 DEG C, add C2 component, mix homogeneously, obtain 639.0 grams of carbon fiber cable cores
With high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, it is denoted as CFPM-2.
Embodiment 3
Take respectively appropriate embodiment 1, embodiment 2 carbon fiber cable core with high temperature resistant phosphorus bromine type non-solvent epoxy matrix tree
Fat, i.e. CFPM-1, CFPM-2, and be uniformly applied to respectively in standard rustless steel test piece, after room temperature hangs 10min, overlapping, folder
Tightly, put in convection oven and solidify: start to warm up to 100 DEG C from room temperature, insulation reaction 1.5 hours, be continuously heating to 140
DEG C, insulation reaction 1.5 hours, it is continuously heating to 170 DEG C, insulation reaction 1.5 hours, naturally cool to room temperature.Electronics is utilized to draw
Power machine carries out room temperature (25 DEG C) and tensile shear strength (σ) test under high temperature (240 DEG C) state to it, and result is as shown in table 1.
Take respectively appropriate embodiment 1, embodiment 2 carbon fiber cable core with high temperature resistant phosphorus bromine type non-solvent epoxy matrix tree
Fat, i.e. CFPM-1, CFPM-2, push away film on polytetrafluoroethylene film, is placed in vacuum drying oven, is made into a size of 5mm
The square coupons of × 5mm × 1mm, curing process is: start to warm up to 100 DEG C from room temperature, insulation reaction 1.5 hours, continues to rise
Warm to 140 DEG C, insulation reaction 1.5 hours, it is continuously heating to 170 DEG C, insulation reaction 1.5 hours, naturally cool to room temperature.
The megger utilizing Guilin Electro Scientific institute to produce tests its specific insulation ρ v (1MHz, 25 DEG C), result
It is shown in Table 1.
The TH2828S tester utilizing Changzhou Tong Hui Electron equipment Co., Ltd test its dielectric loss (D) (1MHz, 25
DEG C), the results are shown in Table 1.
Utilize precision electronic balance, after weighed by above-mentioned dry square coupons (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 as shown in table 1.
Utilize precision electronic balance, above-mentioned dry square coupons is weighed after (G1), be positioned over climatic chamber (85
DEG C, RH85%) in, after 72 hours, take out, dry surface with filter paper, weigh (G2), is calculated the data of hydroscopicity (ψ) such as
Shown in table 1.
The table 1 carbon fiber cable core performance data of high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin
Claims (6)
1. a carbon fiber cable core is with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, it is characterised in that: described matrix tree
Fat by the ES216 epoxy resin that mass ratio is 100:10-50:10-100:10-85:4-25:100-300:10-20:30-100,
Tetrabromo bisphenol-a epoxy resin, DOPO, PHT4, four maleimide resins, firming agent, accelerator and reactive diluent group
Become.
A kind of carbon fiber cable core the most according to claim 1 with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, its
It is characterised by: four described maleimide resins are double selected from double (the 2,4-dimaleimide phenoxyl) benzene of 1,4-, 1,3-
Double [4-(the 2,4-dimaleimide phenoxyl) phenyl] propane of (2,4-dimaleimide phenoxyl) benzene, 2,2-, 2,
2-double [4-(2,4-dimaleimide phenoxyl) phenyl] HFC-236fa, 4,4 '-bis-(2,4-dimaleimide base benzene oxygen
Base) diphenyl ether, 4,4 '-bis-(2,4-dimaleimide phenoxyl) diphenyl-methanes, 4,4 '-bis-(2,4-dimaleimides
Phenoxyl) benzophenone, 4,4 '-bis-(2,4-dimaleimide phenoxyl) diphenyl sulphone (DPS)s, 4,4 '-bis-(2,4-bis-Malaysias
Imide phenoxy group) one or more in biphenyl.
A kind of carbon fiber cable core the most according to claim 1 with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, its
It is characterised by: described firming agent is selected from HHPA, THPA, methyl tetrahydro phthalic anhydride, dodecenylsuccinic anhydride, methyl
HHPA, tung oil acid anhydride, with dicyclopentadiene and 80 anhydride of maleic acid anhydride reactant, with limonene and maleic
Dicarboxylic anhydride reaction anhydride, with Oleum Terebinthinae and one or more in the liquid anhydride of maleic acid anhydride reactant.
A kind of carbon fiber cable core the most according to claim 1 with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, its
It is characterised by: described accelerator is selected from aluminium acetylacetonate, 2-ethyl-4-methylimidazole, N, N-dimethyl open-chain crown ether, benzyl
Base dimethylamine, N, accelerine, 2,4,6-tri-(dimethylamino methyl) phenol, 1,8-diazabicyclo [5.4.0] 11
One or more in alkene-7.
A kind of carbon fiber cable core the most according to claim 1 with high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin, its
It is characterised by: described reactive diluent is selected from hydrogenated bisphenol A epoxy resin, CE793,3,4-epoxycyclohexyethylSiOi acid-3 ', 4 '-
EpoxycyclohexyethylSiOi methyl ester, 3,4-epoxy radicals-6-methyl cyclohexane acid-3 ', 4 '-epoxy radicals-6 '-methyl cyclohexane methyl ester, titanium dioxide two
One or more in amylene.
6. the carbon fiber cable core as claimed in claim 1 preparation of high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin
Method, comprises the steps:
(1) ES216 epoxy resin and four maleimide resins are put in reactor, stirring mixing, anti-in 100 DEG C-120 DEG C
After answering 0.5 hour-1.5 hours, it is cooled to less than 80 DEG C, adds reactive diluent, after being uniformly mixed, obtain component A；
(2) tetrabromo bisphenol-a epoxy resin is put in reactor with DOPO, react 0.5 hour-1.5 hours in 100 DEG C-120 DEG C
After, add PHT4, after continuing reaction 0.5 hour-1.5 hours, add reactive diluent, be uniformly mixed, obtain B group
Part；
(3) C component is firming agent and accelerator, puts in reactor by component A, B component, in 100 DEG C-110 DEG C stirring mixing
After 10min-20min, it is cooled to less than 50 DEG C, adds C component, mix homogeneously, obtain the high temperature resistant phosphorus bromine of carbon fiber cable core
Type non-solvent epoxy matrix resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410854288.9A CN104479299B (en) | 2014-12-26 | 2014-12-26 | A kind of carbon fiber cable core high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410854288.9A CN104479299B (en) | 2014-12-26 | 2014-12-26 | A kind of carbon fiber cable core high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104479299A CN104479299A (en) | 2015-04-01 |
| CN104479299B true CN104479299B (en) | 2016-11-30 |
Family
ID=52753914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410854288.9A Expired - Fee Related CN104479299B (en) | 2014-12-26 | 2014-12-26 | A kind of carbon fiber cable core high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104479299B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI639639B (en) * | 2017-07-17 | 2018-11-01 | 台光電子材料股份有限公司 | Resin composition and articles made from it |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191004B (en) * | 2010-12-31 | 2014-02-05 | 莱芜金鼎电子材料有限公司 | Thermosetting adhesive for flexible basic material and preparation method thereof |
| CN102786775B (en) * | 2012-07-25 | 2014-07-02 | 东华大学 | RTM epoxy resin matrix and its preparation method |
| CN103396529B (en) * | 2013-07-11 | 2016-01-06 | 东华大学 | A kind of high temperature resistant electric insulation veneer sheet matrix resin and preparation method thereof |
| CN103483552B (en) * | 2013-09-29 | 2016-01-20 | 东华大学 | A kind of carbon-fibre composite matrix resin and preparation method thereof |
-
2014
- 2014-12-26 CN CN201410854288.9A patent/CN104479299B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104479299A (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448243B (en) | Solvent-free high-temperature-resistant modified epoxy system pultruded resin and preparation method thereof | |
| CN101629062A (en) | Polyimide-epoxy resin adhesive and preparation method and application thereof | |
| CN102260480B (en) | High-temperature-resistant modified epoxy resin adhesive and preparation method thereof | |
| CN101914357A (en) | Epoxy-organic silicon polyimide adhesive and preparation method thereof | |
| CN103146331B (en) | 4,4'-bis(2,4-diamidophenoxy)biphenyl high-temperature-resistant epoxy adhesive and preparation method thereof | |
| CN102181251B (en) | Epoxy resin adhesive modified by unsaturated polyimide and preparation method thereof | |
| CN103013414B (en) | Alpha-cyanogroup-beta-ethyl ethoxyacrylate modified epoxy resin adhesive and preparation method thereof | |
| CN104761874A (en) | Pultrusion resin for high temperature-resistant carbon fiber-reinforced cable core and preparation method of pultrusion resin | |
| CN103214793B (en) | Advanced composite material matrix resin and preparation method thereof | |
| CN103396529B (en) | A kind of high temperature resistant electric insulation veneer sheet matrix resin and preparation method thereof | |
| CN104497480B (en) | A kind of high temperature resistant phosphorus-nitrogen type non-solvent epoxy matrix resin and preparation method thereof | |
| CN101962436B (en) | High-temperature-resistant modified polyfunctional epoxy matrix resin for advanced composite material and preparation thereof | |
| CN103483552B (en) | A kind of carbon-fibre composite matrix resin and preparation method thereof | |
| CN102031082B (en) | Benzimidazole diamine curing type epoxy adhesive and preparation method thereof | |
| CN104479299B (en) | A kind of carbon fiber cable core high temperature resistant phosphorus bromine type non-solvent epoxy matrix resin and preparation method thereof | |
| CN106220851B (en) | A kind of siliceous epoxy acid imide matrix resin of YASI types and preparation method thereof | |
| CN104829844B (en) | A kind of carbon fiber cable core MHFPI type fire resistant epoxy matrix resins and preparation method thereof | |
| CN102627932B (en) | High temperature resistant epoxy-imine resin adhesive and preparation method thereof | |
| CN104497481A (en) | Solvent-free base resin for carbon fiber cable cores and preparation method thereof | |
| CN103030787A (en) | Benzimidazole-epoxy matrix resin and preparation method thereof | |
| CN103409092B (en) | Solvent-free epoxy-tetramaleimide resin adhesive and preparation method thereof | |
| CN104892903B (en) | A kind of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins and preparation method thereof | |
| CN106146843B (en) | A kind of siliceous epoxy acid imide matrix resin of BDAPP types and preparation method thereof | |
| CN106117517B (en) | A kind of siliceous epoxy acid imide matrix resin of BDADDM types and preparation method thereof | |
| CN106220850B (en) | A kind of siliceous epoxy acid imide matrix resin of DADHBP types and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161130 Termination date: 20191226 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |