CN104448243B - Solvent-free high-temperature-resistant modified epoxy system pultruded resin and preparation method thereof - Google Patents
Solvent-free high-temperature-resistant modified epoxy system pultruded resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a solvent-free high-temperature-resistant modified epoxy system pultruded resin and a preparation method thereof. The pultruded resin consists of carboxyl-containing imide oligomer, silane containing diamino, epoxy resin, a reactive diluent, a curing agent and an accelerant. The preparation method comprises the following steps: (1) carrying out a condensation reaction on carboxyl-containing aromatic diamine, aromatic dicarboxylic anhydrides and an end-capping reagent, and preparing the carboxyl-containing imide oligomer, (2) carrying out a chemical reaction on the carboxyl-containing imide oligomer, silane containing diamino and epoxy resin, thus obtaining a homogeneous phase sticky resin; adding the reactive diluent, uniformly stirring and mixing, thus obtaining a component A; (3) uniformly mixing the silane containing diamino and the accelerant, thereby obtaining a component B; and (4) taking the curing agent as a component C, uniformly mixing and stirring the three components, thereby obtaining the product. The manufacturing process is simple, and the product is excellent in comprehensive performance and wide in market prospects and is suitable for manufacturing production of carbon fiber, glass fiber and organic high-performance fiber reinforced pultruded composite materials.
Description
Technical field
The invention belongs to polymeric material field, more particularly to a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin
And preparation method thereof.
Background technology
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, have even more than by the viscous material intensity of itself, 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 selecting appropriate filler that shrinkage factor can be made to 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.
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
The solvent-free volatilization in the manufacturing, application process, environmental friendliness.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, its main spy
Levy and be：TGDDM epoxy resin, toughener, hydrogenated bisphenol A, curing agent, accelerator are well mixed, and high temperature resistant has been obtained without molten
Agent epoxy adhesive.But its resistance to elevated temperatures still has larger limitation, the reality for failing to meet under many hot environments should
With.
Yu Xinhai et al.【The development of high-strength epoxy-acid imide adhesive, insulating materials, 2014,47 (1)：73-76】It is public
Open BMI (BMI) to be modified epoxy resin, development has obtained the ET of high-strength epoxy-acid imide system
Adhesive.And a series of performance studies have been carried out to obtained ET adhesives.As a result show：The tensile shear strength of ET adhesives
Up to 28.4MPa, water absorption rate is less than 1%, and with good electric property and processing performance.
Chinese patent CN101397486A discloses a kind of preparation method 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
XNBR；B component is double (2,4- diamino phenoxies) the benzene aromatic polyvalent amine hardeners 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% of novolac epoxy resin and 12% (mass percent).1,4-
The addition of double (2,4- diamino phenoxies) benzene aromatic polyvalent amine hardeners is the 15-20% (quality of novolac epoxy resin
Percentage), 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 Xinhai et al.【The development [J] of high-temperature resistant single-component epoxy adhesive. bonding, 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：With maleic anhydride (MA) as end-blocking
Agent, with double (3- amino-4-hydroxylphenyls) HFC-236fas (BAHPFP) of 2,2-, double [4- (4- amino-benzene oxygens) phenyl] third of 2,2-
Material synthesis are obtained based on double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydrides (BPADA) of alkane (BAPOPP), 2,2-
Phenolic hydroxy group polyetherimide resin (HPEI)；With the synthesized HPEI for obtaining 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 preparation has obtained the high-temperature resistant single-component epoxy adhesive of excellent combination property.
Although the method is by polyetherimide resin of the synthesis 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 low.Because maleic anhydride is as end-blocking
Agent is come what is used, and the consumption of maleic anhydride is little.
The monomers such as (2) 2,2- double (3- amino-4-hydroxylphenyls) HFC-236fa (BAHPFP) 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.
Li En, Yu Xinhai et al.【Preparation containing the polyimide modified adhesive of carboxyl, insulating materials, 2012,45 (3)：
13-15,21】Disclose a kind of containing polyimide modified adhesive of carboxyl and preparation method thereof, be primarily characterized in that：Using 3,
5- double (4- amino-benzene oxygens) benzoic acid (35BAPBA) and diphenyl ether tetracarboxylic dianhydride (ODPA) are condensed, and thermoplasticity polyamides is obtained
Imines powder, obtained polyimide powder carries out compatibility with epoxyn system, and a kind of neo-epoxy resin is obtained
Adhesive, the adhesive has excellent mechanical property (shear strength is 32MPa), and (decomposition temperature is 390.3 to heat resistance
DEG C), hydrophobic performance (surface energy 49.02mJ/m2), bin stability (apparent activation energy is 176.3kJ/mol) etc..
Yu Xinhai et al.【The development of end carboxyl imines/epoxy adhesive, insulating materials, 2013,46 (1)：8-11】It is open
A kind of end carboxyl imines/epoxy adhesive and preparation method thereof, is characterized mainly in that：Using 4,4 '-diaminourea -4 "-hydroxyl
Triphenylmenthane (DAHTM) and trimellitic anhydride (TMA), are reacted by condensation reaction and hot imidization, and synthesis has obtained end carboxyl
Imines (CI-DAHTM) solution, then compound with epoxy resin-CTBN nbr carboxyl terminals copolymer and its curing agent, it is obtained
End carboxyl imines-the epoxy adhesive systems of excellent combination property, its tensile shear strength is up to more than 15MPa.
The content of the invention
The technical problem to be solved be to provide a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin and
Its preparation method, the pultrusion resin excellent combination property, environmental friendliness, raw material sources are convenient, preparation process is simple, low cost,
Manufacture suitable for carbon fiber, glass fibre, the enhanced molded through pultrusion of composite material of organic high-performance fiber is produced, and is particularly suitable for
Prepare in the pultrusion of the products such as carbon fiber reinforced cable core composite, have broad application prospects.
A kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin of the present invention, is 1-10 by mass ratio:5-10:100:
50-200:100-300:The imide oligomer containing carboxyl of 1-5, organosilicon diamines, epoxy resin, reactive diluent, curing agent and
Accelerator constitutes；Wherein, it is 2 by mol ratio in organic solvent that imide oligomer containing carboxyl is:1:2 aromatic series containing carboxyl two
Amine, aromatic dianhydride and end-capping reagent are made by by condensation and cyclodehydration reaction；The molecular structural formula of organosilicon diamines is such as
Under：
Wherein n is 1～30 natural number.
The aromatic diamine containing carboxyl is in 3,5- diaminobenzoic acids, double (4- amino-benzene oxygens) benzoic acid of 3,5-
One or two.
The aromatic dianhydride is selected from pyromellitic acid anhydride, 3,3', 4,4'- tetracarboxylic biphenyl dianhydrides, 3,3', 4,4'--
Tetracarboxylic benzophenone dianhydride, 3,3', 4,4'-- tetracarboxylic diphenyl ether dianhydrides, 3,3', 4,4'-- tetracarboxylic diphenyl sulfone dianhydrides, 2,
Double (3,4- dicarboxyphenyis) hexafluoropropane dianhydrides of 2-, double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 1,4-, the double (3,4- bis- of 1,3-
Carboxyphenoxy) benzene dianhydride, double (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides of 4,4'-, double (the 3,4- dicarboxyl benzene oxygen of 4,4'-
Base) diphenyl sulfone dianhydride, double (3,4- di carboxyl phenyloxies) the benzophenone dianhydrides of 4,4'-, 4,4'- be double (3,4- di carboxyl phenyloxies)
Double (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides of biphenyl dianhydride, 4,4'-, double [4- (3,4- di carboxyl phenyloxies) benzene of 2,2-
Base] propane dianhydride, one or more in double [4- (3,4- di carboxyl phenyloxies) phenyl] hexafluoropropane dianhydrides of 2,2-.
The one kind of the end-capping reagent in maleic anhydride, carbic anhydride, methylnadic anhydride, phthalic anhydride
Or it is several.
The organic solvent selected from N,N-dimethylformamide, toluene, dimethylbenzene, chlorobenzene, DMAC N,N' dimethyl acetamide,
One or more in METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
The epoxy resin is selected from ES216 epoxy resin, ECC202 epoxy resin, bisphenol A type epoxy resin, bisphenol-f type
Epoxy resin, bisphenol-s epoxy resin, glycidyl amine type epoxy resin, diglycidyl ether type epoxy resin, ethylene oxidic ester
Type epoxy resin, resorcinolformaldehyde resin epoxy resin, hydroquinones diglycidyl ether epoxy resin, phenol aldehyde type ring
Oxygen tree fat, N, N, N', N'- four glycidyl group -4,4'- MDA epoxy resin, N, N, N', N'- tetra- shrinks sweet
Oil base p-phenylenediamine epoxy resin, N, N, N', N'- four glycidyl group m-phenylene diamine (MPD) epoxy resin, N, N, N', N'- tetra- shrinks
Glyceryl -4,4'- MDA epoxy resin, N, N, N', N'- four glycidyl group -4,4'- benzidine epoxies
Resin, N, N, N', N'- four glycidyl group -3,3'- dimethyl -4,4'- diaminodiphenyl ether epoxy resin, N, N, N', N'-
The chloro- 4,4'- diaminodiphenyl ethers epoxy resin of four glycidyl group -3,3'- two, N, N, N', N'- four glycidyl group -4,4'-
Diaminodiphenyl ether epoxy resin, N, N, N', N'- four glycidyl group -4,4' diaminodiphenyl sulfone epoxy resin, N, N, N',
N'- four glycidyl group -3,4'- diaminodiphenyl ether asphalt mixtures modified by epoxy resin, N, N, N', N'- four glycidyl group -3,3'- diaminourea two
Benzene sulfone 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 group -1,3- double (2- trifluoromethyl-4-aminophenoxyls) benzene epoxy resin, N, the glycidol of N, N', N'- tetra-
Base -1,4- double (4- amino-benzene oxygens) benzene epoxy resin, N, the double (2- trifluoromethyl -4- of N, N', N'- four glycidyl group -1,4-
Amino-benzene oxygen) benzene epoxy resin, N, double (3- amino-benzene oxygens) the benzene epoxy resin of N, N', N'- four glycidyl group -1,4-,
N, N, N', N'- four glycidyl group -1,3- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N', N'- four glycidyl group -
4,4'- double (4- amino-benzene oxygens) diphenyl ether epoxy resin, N, double (the 2- fluoroforms of N, N', N'- four glycidyl group -4,4'-
Base -4- amino-benzene oxygens) diphenyl ether epoxy resin, N, double (the 4- amino-benzene oxygens) two of N, N', N'- four glycidyl group -4,4'-
Phenylmethane epoxy resin, N, double (2- trifluoromethyl-4-aminophenoxyls) the hexichol first of N, N', N'- four glycidyl group -4,4'-
Alkane epoxy resin, N, N, N', N'- four glycidyl group -4,4'- double (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N, N, N',
N'- four glycidyl groups -4,4'- double (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N', N'- tetra- contracts
Water glyceryl -4,4'- double (4- amino-benzene oxygens) biphenyl epoxy resin, N, the double (2- of N, N', N'- four glycidyl group -4,4'-
Trifluoromethyl-4-aminophenoxyl) biphenyl epoxy resin, N, double (the 4- aminobenzene oxygen of N, N', N'- four glycidyl group -4,4'-
Base) diphenyl sulfide epoxy resin, N, double (the 2- trifluoromethyl-4-aminophenoxyls) two of N, N', N'- four glycidyl group -4,4'-
Diphenyl sulfide epoxy resin, N, double (4- amino-benzene oxygens) the benzophenone epoxy resin of N, N', N'- four glycidyl group -4,4'-,
N, N, N', N'- four glycidyl group -4,4'- double (2- trifluoromethyl-4-aminophenoxyls) benzophenone 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'- tetra- shrinks
Glyceryl -2,2- double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane epoxy resin, N, N, N', N'- tetra- shrinks sweet
Oil base -2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N', N'- four glycidyl group -2,2-
Double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] HFC-236fa epoxy resin, N, the glycidyl of N, N', N', O- five-
4,4'- diaminourea -4 "-triphenylmenthane epoxy resin, N, the double (3- amino -4- of N, N', N', O, the O glycidyl of '-six -2,2-
Hydroxy phenyl) HFC-236fa epoxy resin, N, N, O- triglycidyl group para-aminophenol epoxy resin, N, N, O- tri- shrink sweet
Oil base m-aminophenol epoxy resin, terephthalic acid diglycidyl ester epoxy resin, Diglycidyl M-phthalate
Epoxy resin, o-phthalic acid diglycidyl ester epoxy resin, interior methine tetrahydrophthalic acid 2-glycidyl ester ring
Oxygen tree fat, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester epoxy resin, the sad diglycidyl ether epoxy of adjacent benzene two
One or more in resin.
The reactive diluent is selected from hydrogenated bisphenol A epoxy resin, CE793,3,4- epoxycyclohexyethylSiOi acid -3 ', 4 '-epoxy
The own methyl esters of basic ring, 3,4- epoxy radicals -6- methyl cyclohexanes acid -3 ', 4 '-epoxy radicals -6 '-methyl cyclohexane methyl esters, Dipentenedioxide
In one or more.
The curing agent is selected from HHPA, THPA, methyl tetrahydro phthalic anhydride, dodecenylsuccinic anhydride, methyl six
Hydrogen phthalic anhydride, tung oil acid anhydride, with 80 acid anhydrides of dicyclopentadiene and maleic acid anhydride reactant, with limonene and maleic two
Anhydride reaction and made by acid anhydrides, with one or more in the liquid acid anhydrides of turpentine oil and maleic acid anhydride reactant.
The accelerator is selected from aluminium acetylacetonate, 2-ethyl-4-methylimidazole, N, N- dimethyl open-chain crown ethers, DMP-
30th, in benzyl dimethylamine, 2,4,6- tri- (dimethylamino methyl) phenol, DBU, 1,8- diazabicyclo [5.4.0] hendecene -7
One or more.
A kind of preparation method of the solvent-free and high temperature-resistant modified epoxy system pultrusion resin of the present invention, including：
(1) carboxyl aromatic diamine, organic solvent will be contained to be put in reactor, under room temperature after stirring and dissolving, will add fragrance
Race's dibasic acid anhydride, stirring reaction adds end-capping reagent after -3 hours 1 hour in 1 DEG C -5 DEG C of the ice-water bath, continues stirring reaction 1
Hours -3 hours, acetic anhydride and pyridine are added, be heated to 80-100 DEG C of stirring reaction -5 hours 1 hour, add ethanol, stirred
Precipitation solids is mixed, is filtered, acetone soak drip washing, 80-100 DEG C of vacuum drying obtains imide oligomer containing carboxyl；Wherein, acetic acid
Acid anhydride is 2-8 with the mol ratio containing carboxyl aromatic diamine:1, pyridine is 0.1-1 with the mol ratio containing carboxyl aromatic diamine:1；
(2) carboxyl imide oligomer, organosilicon diamines, epoxy resin will be contained to add in reactor, 100 DEG C -120 will be heated to
DEG C, stirring reaction -1.5 hours 0.5 hour is cooled to 70 DEG C, adds reactive diluent, is uniformly mixed, and is homogeneously glued
Thick resin, i.e. component A；
(3) organosilicon diamines is well mixed with accelerator, obtains B component；
(4) component C is curing agent, and the component of A, B, C tri- is well mixed, and obtains the drawing of solvent-free and high temperature-resistant modified epoxy system
Crowded resin.
Beneficial effect
(1) solvent-free and high temperature-resistant modified epoxy system pultrusion resin of the invention has good combination property, solvent-free,
Environmental friendliness；
(2) solvent-free and high temperature-resistant modified epoxy system pultrusion resin of the invention has low viscosity, high reactivity,
With good pultrusion；
(3) solvent-free and high temperature-resistant modified epoxy system pultrusion resin of the invention can be applicable to carbon fiber reinforced plastic
Material, glass fibre reinforced composion, the pultrusion of organic high-performance fiber enhancing composite, high temperature resistant, high intensity, with
Carbon fiber has good wellability, and 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
In complete preparation process, be advantageously implemented industrialized production.
Description of the drawings
Fig. 1 is the gelation time-temperature of solvent-free and high temperature-resistant modified epoxy system pultrusion resin FPR-1 of embodiment 3
Curve；
Fig. 2 is the temperature-viscosity curve of solvent-free and high temperature-resistant modified epoxy system pultrusion resin FPR-1 of embodiment 3.
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 restriction 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
Double (4- amino-benzene oxygens) benzoic acid of 67.2 grams of (0.2 mole) 3,5-, 560 grams of DMAC N,N' dimethyl acetamides are put into
In reactor, under room temperature after stirring and dissolving, add 52.0 grams of (0.1 mole) 2,2- double [4- (3,4- di carboxyl phenyloxy) phenyl]
Propane dianhydride, stirring reaction adds 19.6 grams of (0.2 mole) maleic anhydrides after 1 hour in 1 DEG C of the ice-water bath, continues to stir
Reaction 3 hours, adds 40.8 grams of (0.4 mole) acetic anhydrides and 1.6 grams of (0.02 mole) pyridines, is heated to 80 stirring reactions
5 hours, add 5000 grams of ethanol, high-speed stirred to separate out solids, filter, it is common 2-3 time every time with 150 grams of acetone soak drip washing,
80 DEG C of vacuum drying, obtain 130.2 grams of imide oligomers containing carboxyl, are denoted as BBM-1.
Embodiment 2
Double (4- amino-benzene oxygens) benzoic acid of 67.2 grams of (0.2 mole) 3,5-, 1200 grams of DMAC N,N' dimethyl acetamides are put
In entering reactor, under room temperature after stirring and dissolving, double [4- (3, the 4- di carboxyl phenyloxy) benzene of 5.2 grams of (0.01 mole) 2,2- are added
Base] propane dianhydride and 27.9 grams of (0.09 mole) 3,3', 4,4'-- tetracarboxylic diphenyl ether dianhydrides, stir in 5 DEG C of ice-water bath
After reaction 3 hours, 19.6 grams of (0.2 mole) maleic anhydrides are added, continue stirring reaction 1 hour, (1.6 rub to add 163.2 grams
You) acetic anhydride and 15.8 grams of (0.2 mole) pyridines, it is heated to 100 DEG C of stirring reactions 1 hour, 8000 grams of ethanol are added, it is high
Speed stirring separates out solids, filters, common 2-3 time every time with 100 grams of acetone soak drip washing, 100 DEG C of vacuum drying, obtains 110.8 grams
Imide oligomer containing carboxyl, is denoted as BBM-2.
Embodiment 3
By 1.0 grams of BBM-1 imide oligomers containing carboxyl, 1.0 grams of organosilicon diamines, 80.0 grams of ES216 epoxy resin and
20.0 grams of N, N, N', N'- four glycidyl group -4,4'- MDAs epoxy resin is added in reactor, is heated to
100 DEG C, stirring reaction 1.5 hours is cooled to 70 DEG C, adds 50.0 grams of CE793, is uniformly mixed, and obtains 152.0 grams homogeneously
Viscous resin, i.e. component A, are denoted as A1.
4.0 grams of organosilicon diamines are well mixed with 1.0 grams of 2-ethyl-4-methylimidazoles, 5.0 grams of B components are obtained, are denoted as
B1。
Component C is curing agent, i.e., be made up of 80.0 grams of dodecenylsuccinic anhydrides and 20.0 grams of tung oil acid anhydrides (TOA), note
Make C1.The component of A1, B1, C1 tri- is well mixed, 257.0 grams of solvent-free and high temperature-resistant modified epoxy system pultrusion resins are obtained, is remembered
Make FPR-1.Its gelation time-temperature curve is as shown in Figure 1；Its viscosity-temperature dependency curve is as shown in Figure 2.
Embodiment 4
By the imide oligomer containing carboxyl of 4.0 grams of BBM-1 and 6.0 gram of BBM-2,3.0 grams of organosilicon diamines, 30.0 grams
ES216 epoxy resin, 30.0 grams of ECC202 epoxy resin and 40.0 grams of N, N, N', N'- four glycidyl group -4,4'- diaminourea
Diphenyl ether epoxy resin is added in reactor, is heated to 120 DEG C, and stirring reaction 0.5 hour is cooled to 70 DEG C, adds 150.0 grams
CE793 and 50.0 gram of hydrogenated bisphenol A epoxy resin, is uniformly mixed, and obtains 313.0 grams of homogeneous viscous resins, i.e. component A,
It is denoted as A2.
By 7.0 grams of organosilicon diamines, 3.0 grams of (dimethylamino methyl) phenol of 2,4,6- tri- and 2.0 grams of 2- ethyl -4- methyl
Imidazoles, is well mixed, and obtains 12.0 grams of B components, is denoted as B2.
Component C is curing agent, i.e., be made up of 180.0 grams of methyl tetrahydro phthalic anhydrides and 120.0 grams of tung oil acid anhydrides (TOA), is denoted as
C2.The component of A2, B2, C2 tri- is well mixed, 625.0 grams of solvent-free and high temperature-resistant modified epoxy system pultrusion resins are obtained, is denoted as
FPR-2。
Embodiment 5
Take appropriate embodiment 3, the solvent-free and high temperature-resistant modified epoxy system pultrusion resin of embodiment 4 respectively, i.e. FPR-1,
FPR-2, 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 into air blast
Solidified in baking oven：Start to warm up to 100 DEG C from room temperature, insulation reaction 1 hour is continuously heating to 160 DEG C, insulation reaction
1.5 hours, 180 DEG C are continuously heating to, insulation reaction 1 hour naturally cools to room temperature.Room is carried out to it using electronic tensile machine
Warm (25 DEG C) are tested with the tensile shear strength (σ) under high temperature (240 DEG C) state, as a result as shown in table 1.
Take appropriate embodiment 3, the solvent-free and high temperature-resistant modified epoxy system pultrusion resin of embodiment 4 respectively, i.e. FPR-1,
FPR-2, in polytetrafluoroethylene film film is above pushed away, and in being placed in vacuum drying chamber, is made into the side that size is 5mm × 5mm × 1mm
Shape sample, curing process is：Start to warm up to 100 DEG C from room temperature, insulation reaction 1 hour is continuously heating to 160 DEG C, and insulation is anti-
Answer 1.5 hours, be continuously heating to 180 DEG C, insulation reaction 1 hour naturally cools to room temperature.Using Guilin Electro Scientific research institute
The megger of production tests its specific insulation ρ v (1MHz, 25 DEG C), the results are shown in Table 1.
Using the TH2828S testers of Changzhou Tong Hui Electron equipment Co., Ltd test its dielectric loss (D) (1MHz, 25
DEG C), the results are shown in Table 1.
Using precision electronic balance, the square coupons of above-mentioned drying are weighed after (W1), be soaked in deionized water (25 DEG C)
In, after 72 hours, take out, surface is dried with filter paper, weigh (W2), is calculated water absorption rateData it is as shown in table 1.
The solvent-free and high temperature-resistant modified epoxy system pultrusion resin of table 1, the i.e. performance data of FPR-1, FPR-2
Claims (8)
1. a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin, it is characterised in that：It is 1-10 by mass ratio:5-10:
100:50-200:100-300:The imide oligomer containing carboxyl of 1-5, organosilicon diamines, epoxy resin, reactive diluent, solidification
Agent and accelerator constitute；Wherein, it is 2 by mol ratio in organic solvent that imide oligomer containing carboxyl is:1:2 containing carboxyl fragrance
Race's diamines, aromatic dianhydride and end-capping reagent are made by by condensation and cyclodehydration reaction；The molecular structure of organosilicon diamines
Formula is as follows：
Wherein n is 1～30 natural number；Containing carboxyl
Aromatic diamine is selected from one or two in double (4- amino-benzene oxygens) benzoic acid of 3,5- diaminobenzoic acids, 3,5-；End-blocking
One or more of agent in maleic anhydride, carbic anhydride, methylnadic anhydride, phthalic anhydride.
2. a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin according to claim 1, it is characterised in that：It is described
Aromatic dianhydride is selected from pyromellitic acid anhydride, 3,3', 4,4'- tetracarboxylic biphenyl dianhydrides, 3,3', 4,4'- tetracarboxylic hexichol first
Ketone dianhydride, 3,3', 4,4'- tetracarboxylic diphenyl ether dianhydrides, 3,3', double (the 3,4- dicarboxyls of 4,4'- tetracarboxylic diphenyl sulfone dianhydrides, 2,2-
Base phenyl) hexafluoropropane dianhydride, double (3,4- di carboxyl phenyloxies) benzene dianhydrides of 1,4-, double (3,4- di carboxyl phenyloxies) benzene of 1,3-
Double (3,4- di carboxyl phenyloxies) diphenyl sulfone dianhydrides of double (3,4- di carboxyl phenyloxies) diphenyl ether dianhydride of dianhydride, 4,4'-, 4,4'-,
Double (3,4- di carboxyl phenyloxies) the benzophenone dianhydrides of 4,4'-, 4,4'- double (3,4- di carboxyl phenyloxies) biphenyl dianhydride, 4,4'-
Double [4- (3,4- di carboxyl phenyloxies) phenyl] propane dianhydride of double (3,4- di carboxyl phenyloxies) diphenyl ether dianhydrides, 2,2-, 2,
One or more in double [4- (3,4- di carboxyl phenyloxies) phenyl] hexafluoropropane dianhydrides of 2-.
3. a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin according to claim 1, it is characterised in that：It is described
Organic solvent is selected from N,N-dimethylformamide, toluene, dimethylbenzene, chlorobenzene, DMAC N,N' dimethyl acetamide, N- methyl -2- pyrroles
One or more in pyrrolidone, dimethyl sulfoxide (DMSO).
4. a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin according to claim 1, it is characterised in that：It is described
Epoxy resin is selected from ES216 epoxy resin, ECC202 epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bis-phenol
S type epoxy resin, resorcinolformaldehyde resin epoxy resin, hydroquinones diglycidyl ether epoxy resin, phenol aldehyde type
Epoxy resin, N, N, N', N'- four glycidyl group -4,4'- MDA epoxy resin, N, N, N', N'- tetra- shrinks
Glyceryl p-phenylenediamine epoxy resin, N, N, N', N'- four glycidyl group m-phenylene diamine (MPD) epoxy resin, N, N, N', N'- tetra- contracts
Water glyceryl -4,4'- MDA epoxy resin, N, N, N', N'- four glycidyl group -4,4'- benzidine rings
Oxygen tree fat, N, N, N', N'- four glycidyl group -3,3'- dimethyl -4,4'- diaminodiphenyl ether epoxy resin, N, N, N',
The chloro- 4,4'- diaminodiphenyl ethers epoxy resin of N'- four glycidyl groups -3,3'- two, N, N, N', N'- four glycidyl group -4,
4'- diaminodiphenyl ether epoxy resin, N, N, N', N'- four glycidyl group -4,4' diaminodiphenyl sulfone epoxy resin, N, N,
N', N'- four glycidyl group -3,4'- diaminodiphenyl ether epoxy resin, N, N, N', N'- four glycidyl group -3,3'- diaminos
Base diphenyl sulphone (DPS) 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 group -1,3- double (2- trifluoromethyl-4-aminophenoxyls) benzene epoxy resin, N, N, N', N'- tetra- shrinks
Glyceryl -1,4- double (4- amino-benzene oxygens) benzene epoxy resin, N, double (the 2- fluoroforms of N, N', N'- four glycidyl group -1,4-
Base -4- amino-benzene oxygens) benzene epoxy resin, N, double (3- amino-benzene oxygens) the phenyl ring oxygen of N, N', N'- four glycidyl group -1,4-
Resin, N, N, N', N'- four glycidyl group -1,3- double (3- amino-benzene oxygens) benzene epoxy resin, N, N, N', N'- tetra- shrinks sweet
Oil base -4,4'- double (4- amino-benzene oxygens) diphenyl ether epoxy resin, N, the double (2- tri- of N, N', N'- four glycidyl group -4,4'-
Methyl fluoride -4- amino-benzene oxygens) diphenyl ether epoxy resin, N, double (the 4- aminobenzene oxygen of N, N', N'- four glycidyl group -4,4'-
Base) diphenyl-methane epoxy resin, N, double (the 2- trifluoromethyl-4-aminophenoxyls) two of N, N', N'- four glycidyl group -4,4'-
Phenylmethane epoxy resin, N, N, N', N'- four glycidyl group -4,4'- double (4- amino-benzene oxygens) diphenyl sulphone (DPS) epoxy resin, N,
N, N', N'- four glycidyl group -4,4'- double (2- trifluoromethyl-4-aminophenoxyls) diphenyl sulphone (DPS) epoxy resin, N, N, N',
N'- four glycidyl groups -4,4'- double (4- amino-benzene oxygens) biphenyl epoxy resin, N, N, N', N'- four glycidyl group -4,
4'- double (2- trifluoromethyl-4-aminophenoxyls) biphenyl epoxy resin, N, the double (4- of N, N', N'- four glycidyl group -4,4'-
Amino-benzene oxygen) diphenyl sulfide epoxy resin, N, the double (2- trifluoromethyl -4- amino of N, N', N'- four glycidyl group -4,4'-
Phenoxy group) diphenyl sulfide epoxy resin, N, double (4- amino-benzene oxygens) benzophenone of N, N', N'- four glycidyl group -4,4'-
Epoxy resin, N, double (2- trifluoromethyl-4-aminophenoxyls) the benzophenone epoxies of N, N', N'- four glycidyl group -4,4'-
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 groups -2,2- double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] propane epoxy resin, N, N, N',
N'- four glycidyl groups -2,2- double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa epoxy resin, N, N, N', N'- tetra- shrinks
Glyceryl -2,2- double [4- (2- trifluoromethyl-4-aminophenoxyls) phenyl] HFC-236fa epoxy resin, N, N, N', N', O- five
Glycidyl -4,4'- diaminourea -4 "-triphenylmenthane epoxy resin, N, N, N', N', O, the O glycidyl of '-six -2,2- is double
(3- amino-4-hydroxylphenyls) HFC-236fa epoxy resin, N, N, O- triglycidyl group para-aminophenol epoxy resin, N, N,
O- triglycidyl meta-aminophenol epoxy resin, terephthalic acid diglycidyl ester epoxy resin, M-phthalic acid two
Ethylene oxidic ester epoxy resin, o-phthalic acid diglycidyl ester epoxy resin, interior methine tetrahydrophthalic acid two contract
Water glycerine ester epoxy resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester epoxy resin, sad two ring of adjacent benzene two
One or more in oxygen propyl ester epoxy resin.
5. a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin according to claim 1, it is characterised in that：It is described
Reactive diluent is selected from CE793,3,4- epoxycyclohexyethylSiOi acid -3 ', 4 '-epoxycyclohexyethylSiOi methyl esters, 3,4- epoxy radicals -6- methyl rings
One or more in caproic acid -3 ', 4 '-epoxy radicals -6 '-methyl cyclohexane methyl esters, Dipentenedioxide.
6. a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin according to claim 1, it is characterised in that：It is described
Curing agent is selected from HHPA, THPA, methyl tetrahydro phthalic anhydride, dodecenylsuccinic anhydride, methyl hexahydrophthalic anhydride, eleostearic acid
Acid anhydride, make with 80 acid anhydrides of dicyclopentadiene and maleic acid anhydride reactant, with limonene and maleic acid anhydride reactant
Into acid anhydrides, with one or more in the liquid acid anhydrides of turpentine oil and maleic acid anhydride reactant.
7. a kind of solvent-free and high temperature-resistant modified epoxy system pultrusion resin according to claim 1, it is characterised in that：It is described
Accelerator is selected from aluminium acetylacetonate, 2-ethyl-4-methylimidazole, N, N- dimethyl open-chain crown ethers, benzyl dimethylamine, 2,4,6-
One or more in three (dimethylamino methyl) phenol, 1,8- diazabicyclos [5.4.0] hendecene -7.
8. a kind of preparation method of solvent-free and high temperature-resistant modified epoxy system pultrusion resin as claimed in claim 1, including：
(1) carboxyl aromatic diamine, organic solvent will be contained to be put in reactor, under room temperature after stirring and dissolving, will add aromatic series two
First acid anhydrides, stirring reaction adds end-capping reagent after -3 hours 1 hour in 1 DEG C -5 DEG C of the ice-water bath, continue stirring reaction 1 hour -
3 hours, acetic anhydride and pyridine are added, be heated to 80-100 DEG C of stirring reaction -5 hours 1 hour, add ethanol, stirring analysis
Go out solids, filter, acetone soak drip washing, 80-100 DEG C of vacuum drying obtains imide oligomer containing carboxyl；Wherein, acetic anhydride with
Mol ratio containing carboxyl aromatic diamine is 2-8:1, pyridine is 0.1-1 with the mol ratio containing carboxyl aromatic diamine:1；
(2) carboxyl imide oligomer, organosilicon diamines, epoxy resin will be contained to add in reactor, 100 DEG C -120 DEG C will be heated to,
Stirring reaction -1.5 hours 0.5 hour, is cooled to 70 DEG C, adds reactive diluent, is uniformly mixed, and obtains homogeneous sticky tree
Fat, i.e. component A；
(3) organosilicon diamines is well mixed with accelerator, obtains B component；
(4) component C is curing agent, and the component of A, B, C tri- is well mixed, and obtains solvent-free and high temperature-resistant modified epoxy system pultrusion tree
Fat.
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| CN104892903B (en) * | 2015-05-12 | 2017-10-24 | 东华大学 | A kind of high-temperature resistance carbon fiber cable core MHPI type epoxy pultrusion resins and preparation method thereof |
| CN106146844B (en) * | 2016-07-29 | 2018-08-14 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of BDAPFP types and preparation method thereof |
| CN106146848B (en) * | 2016-07-29 | 2018-08-03 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of 14BDAPB types and preparation method thereof |
| CN106146843B (en) * | 2016-07-29 | 2018-08-14 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of BDAPP types and preparation method thereof |
| CN106146846B (en) * | 2016-07-29 | 2018-08-03 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of BAHPP types and preparation method thereof |
| CN106220850B (en) * | 2016-07-29 | 2018-09-25 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of DADHBP types and preparation method thereof |
| CN106220851B (en) * | 2016-07-29 | 2018-10-23 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of YASI types and preparation method thereof |
| CN106146847B (en) * | 2016-07-29 | 2018-08-03 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of BAHPFP types and preparation method thereof |
| CN106243353B (en) * | 2016-07-29 | 2018-09-25 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of BDATHQ types and preparation method thereof |
| CN106146845B (en) * | 2016-07-29 | 2018-08-14 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of BDADDE types and preparation method thereof |
| CN106146842B (en) * | 2016-07-29 | 2018-08-14 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of 13BDAPB types and preparation method thereof |
| CN106220852B (en) * | 2016-07-29 | 2018-09-25 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of BDABP types and preparation method thereof |
| CN111138657B (en) * | 2019-12-30 | 2022-09-09 | 温州大学 | Terpolymer resin |
| CN111876116A (en) * | 2020-06-24 | 2020-11-03 | 南北兄弟药业投资有限公司 | Polyimide modified epoxy resin composite conductive adhesive and preparation method thereof |
| WO2024006101A2 (en) * | 2022-06-28 | 2024-01-04 | Huntsman Advanced Materials Americas Llc | Curable epoxy resin compositions with high glass transition temperature |
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| CN102618200B (en) * | 2012-03-21 | 2013-11-13 | 东华大学 | Organosilicone-epoxy-polyimide adhesive and preparation method thereof |
| CN102786775B (en) * | 2012-07-25 | 2014-07-02 | 东华大学 | RTM epoxy resin matrix and its preparation method |
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