CN108485202A - A kind of carbon fiber prepreg composition epoxy resin - Google Patents
A kind of carbon fiber prepreg composition epoxy resin Download PDFInfo
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- CN108485202A CN108485202A CN201810362796.3A CN201810362796A CN108485202A CN 108485202 A CN108485202 A CN 108485202A CN 201810362796 A CN201810362796 A CN 201810362796A CN 108485202 A CN108485202 A CN 108485202A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention belongs to Material Fields, and in particular to a kind of carbon fiber prepreg composition epoxy resin, including following components：100 parts by weight of bisphenol A epoxide resin；10 ~ 30 parts by weight of unsaturated polyester (UP)；10 ~ 50 parts by weight of carbochain polymer；5 ~ 50 parts by weight of filler；0.2 ~ 2 parts by weight of organic peroxide.The composition epoxy resin of the present invention is strong in carbon fiber interface binding power, and the composite materials property that fibre reinforced obtains is excellent, and cure shrinkage is low, and product size precision is high, and with sterilization antibacterial effect.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of carbon fiber prepreg composition epoxy resin.
Technical background
Epoxy resin is to refer to the organic compound containing two or more epoxy groups in molecule.Due to molecule knot
Contain active epoxy group in structure, makes them that can be crosslinked with a plurality of types of curing agent and react and being formed insoluble has
The high polymer of three-dimensional reticular structure.Epoxy resin after solidification has good physics, chemical property, it is to metal and nonmetallic
The surface of material has excellent adhesive strength, and dielectric properties are good, and deformation retract rate is small, and product size stability is good, hardness
Height, flexibility is preferable, to alkali and most of solvent-stable, thus is widely used in the every field of people's production and living, can be with
It pours into a mould, impregnate, the purposes such as lamination material, bonding agent, coating.
Carbon fiber is the inorganic fibers 90% or more containing carbon mass fraction, has low-density, high specific strength, high ratio
The advantages that modulus, high-temperature corrosion resistance, high chemical stability.It, can be significantly with carbon fiber as reinforcing material come reinforced plastics
The mechanical property of plastics is improved, the especially raising of tensile strength is widely used in the fields such as aerospace and communications and transportation.
But since carbon fiber is mainly made of graphite-based carbon, there is natural chemical inertness, surface energy is higher, with resin
The associativity of (especially epoxy resin) is poor, and interface binding power is weak, leads to the compression, bending and interlaminar shear strength of composite material
It is all relatively low, further increasing for material property is influenced, its application range is limited.
By research, the people have found that the interface of epoxy resin and carbon fiber can be improved by the modification to epoxy resin
Binding force, to improve the mechanical property of composite material.
Chinese patent CN107057283A discloses a kind of method improving carbon fiber epoxy interface binding power, is logical
It crosses and adds graphene oxide, carbon nanotube and isocyanates in the epoxy to improve the interface knot of epoxy resin and carbon fiber
Resultant force and effect of impregnation, to improve the bending strength and interlaminar shear strength of composite material.But graphene oxide, carbon nanometer
The bad dispersibility of pipe in the epoxy, needs by being ultrasonically treated, and stability is inadequate, is unable to long-term preservation.
Chinese patent CN106046682A discloses a kind of method improving epoxy resin fiber composite property, is logical
It crosses and adds galapectite/carbon nano-composite material in the epoxy to improve the interface binding power of epoxy resin and fiber, improve
Performance.This method has that galapectite/carbon nano-composite material is not easy to disperse in the epoxy, leads to asphalt mixtures modified by epoxy resin
The storage of fat and practicability Shortcomings.
Invention content
In order to improve epoxy resin and carbon fiber associativity, the bending strength and interlaminar shear strength of composite material are improved,
The present invention provides a kind of carbon fiber prepreg composition epoxy resins, include following components：
100 parts by weight of bisphenol A epoxide resin；
10~30 parts by weight of unsaturated polyester (UP)；
10~50 parts by weight of carbochain polymer；
5~50 parts by weight of filler；
0.2~2 parts by weight of organic peroxide.
Further, the unsaturated polyester (UP) by unsaturated dibasic acid, monounsaturated dicarboxylic acid, ternary acid, dihydric alcohol polycondensation and
At, and weight ratio is unsaturated dibasic acid:Monounsaturated dicarboxylic acid:Ternary acid:Dihydric alcohol=10:(5~10):(0.1~1):(10
~20).
Preferably, unsaturated polyester (UP) is prepared in raw material, the unsaturated dibasic acid in mesaconic acid, the itaconic acid one
Kind is a variety of, and the monounsaturated dicarboxylic acid is one or more in ethanedioic acid or 3- phenyl glutaric acids, and the ternary acid is selected from
One or more in citric acid or tricarballylic acid, the dihydric alcohol is selected from 1,6- hexylene glycols or one kind or more in dipropylene glycol
Kind.
Further, the unsaturated polyester (UP) is 1000~3000mPas in 25 DEG C of viscosity.
Further, the carbochain polymer is selected from polystyrene and its copolymer, polyvinyl acetate and its copolymer
In it is one or more.
Further, the carbochain polymer is polyethylene, polystyrene, the copolymerization of polystyrene-poly butadienestyrene block
It is one or more in object or polystyrene-poly (Ethylene/Butylene) block copolymer.
Further, the filler includes one or more in silicon carbide, pps powder, polystyrene microsphere,
Wherein, the polystyrene microsphere is the crosslinked polystyrene microsphere of surface carboxylation.
Preferably, the grain size of the filler is preferably 10~1000nm, and particle diameter distribution is less than 1.3.
Further, the organic peroxide includes one or more in cyclohexanone peroxide, diacetyl peroxide.
Further, the carbon fiber prepreg composition epoxy resin also contains free radical inhibitors 2- methoxies
Base phenol.
Also include to cure made of above-mentioned carbon fiber prepreg epoxy resin composition meanwhile in the present invention
Object and carbon fibre reinforced composite, by above-mentioned composition epoxy resin be impregnated into the prepreg obtained in carbon fiber and
The carbon fibre reinforcement that prepreg is formed by curing.
Advantageous effect：The composition epoxy resin of the present invention is strong in carbon fiber interface binding power, what fibre reinforced obtained
Composite materials property is excellent, and cure shrinkage is low, and product size precision is high, and with sterilization antibacterial effect.
Specific implementation mode
Hereinafter, being carried out to the composition epoxy resin, carbon fiber prepreg and carbon fibre reinforced composite of the present invention detailed
Thin explanation.
In composition epoxy resin of the present invention bisphenol A epoxide resin be by bisphenol-A and epoxychloropropane under alkaline condition
High-molecular compound made of condensation, is the main component of resin, has good physical and mechanical property, high temperature resistant, chemically-resistant
Drug, electrical insulation properties.
Unsaturated polyester (UP) is the polyester containing unsaturated double-bond made of polyacid and polyhydric alcohol.It can be by any
Unsaturated polyacid or unsaturated polyol are generated by polycondensation reaction known in one kind, unsaturated polyacid specific example such as Malaysia
Acid, fumaric acid, citraconic acid, mesaconic acid, 2- methylmaleic acids, 2,4- dimethyl -2- glutaconates, 2,5- dimethyl -2- oneself
Enedioic acid, 2- heptylene diacids, 3- heptylene diacids, itaconic acid etc., unsaturated polyol specific example such as trimethylolpropane diene
Propyl ether.Unsaturated polyester (UP) has excellent processing performance and corrosion resistance, and price is cheap compared with epoxy resin, derives from a wealth of sources.
But unsaturated polyester (UP) mechanical property is poor compared with epoxy resin, cure shrinkage is larger, therefore the additive amount of unsaturated polyester (UP) is unsuitable
Too much, preferably 15~20 parts by weight.
Unsaturated polyester (UP) of the present invention is formed by unsaturated dibasic acid, monounsaturated dicarboxylic acid, ternary acid, dihydric alcohol polycondensation,
And weight ratio is unsaturated dibasic acid:Monounsaturated dicarboxylic acid:Ternary acid:Dihydric alcohol=10:(5~10):(0.1~1):(10~
20)。
Wherein, unsaturated dibasic acid can be enumerated as maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2,4- dimethyl -2-
Glutaconate, 2,5- dimethyl -2- hexene diacids, 2- heptylene diacids, 3- heptylene diacids, itaconic acid etc..Preferably 2,4- diformazans
Base -2- glutaconates, 2,5- dimethyl -2- hexene diacids, 2- heptylene diacids, 3- heptylene diacids, citraconic acid, mesaconic acid, clothing health
Acid；More preferably itaconic acid.
Monounsaturated dicarboxylic acid can control the degree of unsaturation of unsaturated polyester resin, control the performance of epoxy resin.The present invention
Monounsaturated dicarboxylic acid used is well known monounsaturated dicarboxylic acid, can enumerate phthalic acid, M-phthalic acid, terephthalic acid (TPA), chlorine bridge
Acid, succinic acid, adipic acid, decanedioic acid, tetrachlorophthalic acid, tetrabromophthalate, methylene tetrahydrophthalic acid,
3- phenyl glutaric acids etc. can also be their one or more mixtures.Preferably ethanedioic acid, adipic acid, O-phthalic
It is one or more in acid, HET acid, succinic acid, 3- phenyl glutaric acids, more preferably 3- phenyl glutaric acid.Preferably, two are saturated
First acid is (6~8) with unsaturated dibasic acid weight ratio：10.
Ternary acid can be ternary acid well known in the art, can be with multiple dihydric alcohols, organic peroxide, epoxy resin
It reacts and improves crosslinking curing rate, improve the performance after epoxy resin composition.Specific such as trimellitic acid, equal benzene three
Acid, tricarballylic acid, citric acid, nitrilotriacetic acid etc. integrate in order to obtain from the angle of excellent in performance, preferably tricarballylic acid
The composition epoxy resin haveing excellent performance, it is preferable that ternary acid is (0.3~0.7) with unsaturated dibasic acid weight ratio：10.
Dihydric alcohol can use dihydric alcohol well known in the art, can be exemplified as ethylene glycol, propylene glycol, neopentyl glycol, fourth
Glycol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexylene glycol etc., from the angle of excellent in performance, preferably the third two
It is one or more in alcohol, hexylene glycol, neopentyl glycol, pentanediol, dipropylene glycol.The asphalt mixtures modified by epoxy resin of excellent combination property in order to obtain
Oil/fat composition, it is preferable that dihydric alcohol is (13~18) with unsaturated dibasic acid weight ratio：10.
Unsaturated polyester (UP) can use the type and dosage of above-mentioned raw materials, be synthesized by well known method.In the synthesis
Various conditions are set according to the type and dosage of raw material.Usually, in the atmosphere of inert gases such as nitrogen, with organic gold
Belong to salt to do under catalyst, with 140~230 DEG C at a temperature of be esterified under pressure or decompression and obtain.Specific catalyst can enumerate second
It is one or more in sour manganese, stannous oxalate, zinc acetate, cobalt acetate etc..
Further, in order to ensure that unsaturated polyester (UP) has better compatibility and a processing performance, preferably unsaturated polyester (UP)
25 DEG C of viscosity is 1000~3000mPas, more preferably 25 DEG C of 1500~2500mPas of viscosity, and viscosity, which can be used, revolves
Turn rheometer measurement.
Wherein, carbochain polymer is the polymer that macromolecular main chain is made of carbon atom completely, can be used for improving epoxy
The processing performance of resin combination reduces solidification cubical contraction.Carbochain polymer can be carbon chain polymerization well known in the art
Object is exemplified as homopolymer, one kind in copolymer or more of olefin and its derivatives polymer, alkynes and its derivative polymer
Kind.One kind of specific such as polyethylene, polypropylene, polyvinyl alcohol, acid polyethylene, poly, polystyrene and its copolymer
Or it is a variety of.From the angle of excellent in performance, preferably polystyrene-poly butadienestyrene block copolymer, polystyrene-poly (ethylene-fourth
Alkene) one or more in block copolymer, mixture both more preferably, weight part ratio 4:1~1:1, preferably 2:1
~1:2.In order to ensure to have outstanding processing performance and low solidification cubical contraction and outstanding mechanical property, carbochain polymer
Content is 20~40 parts by weight.
Wherein, as the filler in composition epoxy resin, the heat resistance for improving composition and composite material.It is preferred that
For calcium carbonate, graphite, silica, silicon carbide, boron nitride, aluminium oxide, pps powder, polyaniline powder, polystyrene
One or more in microballoon, the grain size of filler is preferably 10~1000nm, and more preferably 100~500nm, particle diameter distribution is less than
1.3, it is more preferably less than 1.2.For better compatibility and heat resistance, more preferably pps powder, polystyrene is micro-
Ball.In order to improve the excellent comprehensive performance of composition epoxy resin, filer content preferably 15~40 parts by weight.The polyphenylene sulfide
Ether powder refer to polyphenylene sulfide crush at low temperature be made.The polystyrene microsphere is to pass through microemulsion by styrene monomer
The synthesis of the methods of polymerization, emulsion polymerization, dispersion copolymerization method, suspension polymerization and seeded polymerization is made.
Further, the polystyrene microsphere is the crosslinked polystyrene microsphere of surface carboxylation.Make filler and ring
The compatibility of epoxy resin composition, dispersion are more uniform.The crosslinked polystyrene microsphere of the surface carboxylation can pass through
It is prepared by following methods：Using styrene, acrylic acid as monomer, divinylbenzene is crosslinking agent, and azodiisobutyronitrile is initiator, is adopted
It is synthesized with dispersin polymerization and crosslinking agent post-addition method.Grain size is preferably 10~1000nm, and particle diameter distribution is less than 1.2.
In the present invention, the grain size of filler is its number average bead diameter, and particle diameter distribution is the weight average particle diameter and number average bead diameter of filler
Ratio can be measured with laser particle analyzer.
Wherein, as the organic peroxide in composition epoxy resin, the solidification of composition epoxy resin can be promoted
Rate and effect can be well known any type organic peroxide, such as peroxycarbonates, peroxyester, diacyl
It is one or more in peroxide, dialkyl peroxide.The content of organic peroxide is less than 0.2 parts by weight, to epoxy
The solidification of resin combination promotes unobvious；When organic peroxide content be more than 2 parts by weight, be further added by organic peroxide
Content can not promote the solidification of composition epoxy resin, preferably 0.5~1.5 parts by weight.
Further, also contain free radical inhibitors in the composition epoxy resin, organic peroxy can be controlled
The reaction rate of object ensures that composite material has excellent comprehensive performance.Preferably phenolic compounds, benzoquinones, quinhydrones, catechol,
The composition of stable free radical and/or phenthazine.The amount for the free radical inhibitors that can be added can be in comparatively wide range
Interior variation, and can be selected as reaching the primary index of desired gel time.It can be according to composition epoxy resin
Type selects suitable free radical inhibitors, specific choice, 2- metoxyphenols, 4- metoxyphenols, 2,6- di-t-butyls-
4- methylphenols, 2,6 di t butyl phenol, 2,4,6- pseudocuminols, 2,4,6- tri- (dimethylamino methyl) phenol, 4,
4 '-thio-two (3- methyl -6- tert-butyl phenols), 4,4 '-isopropylidenediphenols, 2,4- di-t-butyls phenol, 6,6 ' -
Two-paracresol of di-t-butyl -2,2 '-methylene, quinhydrones, 2- methylnaphthohydroquinones, 2-tert-butyl hydroquinone, 2,5- di-t-butyl hydrogen
Quinone, 2,6- di-tert-butyl hydroquinones, 2,6- dimethyl hydroquinones, 2,3,5- trimethylhydroquinone, catechol, 4- tert-butyl catechols, 4,
6- di-t-butyls catechol, benzoquinones, tetra- chloro- 1,4- benzoquinones of 2,3,5,6-, methylbenzoquinone, 2,6- phlorones, naphthoquinones, l-
Oxygroup -2,2,6,6- tetramethyl piperidines, 1- oxygroup -2,2,6,6- tetramethyl piperidine -4- alcohol (the also referred to as chemical combination of TEMPOL
Object), l- oxygroups -2,2,6, the 6- tetramethyl piperidine -4- ketone compound of TEMPON (also referred to as), 1- oxygroups -2,2,6,6- tetra-
Methyl -4- Carboxy-piperidins the compound of 4- carboxyls-TEMPO (also referred to as), l- oxygroups -2,2,5,5- tetramethyls-pyrrolidines,
L- oxygroup -2,2,5,5- tetramethyl -3- carboxy pyrroles alkane (also referred to as 3- carboxyls-PROXYL), ten thousand oxygroup free radical of jar (unit of capacitance)
(galvinoxyl), aluminium-N- nitroso phenyl hydroxylamines, diethyl hydroxylamine, phenthazine and/or these arbitrary compounds derivative
Or combination.
The epoxy resin composition for carbon-fiber-reinforced composite material of the present invention can coordinate curing agent to use.Here illustrate
Curing agent be the present invention composition epoxy resin contained in epoxy resin curing agent, can be anti-with epoxy group to have
The compound for the active group answered.As curing agent, such as dicyandiamide, aromatic polyamine, aminobenzoic acid can be specifically enumerated
Esters, various acid anhydrides, linear phenol-aldehyde resin, o-cresol-formaldehyde resin, polyphenyl phenolic compounds, imdazole derivatives, aliphatic amine, tetramethyl
Carboxylic acid anhydrides, carboxylic acid hydrazine, amine carboxylic acid, the polymercaptan and three of base guanidine, thiocarbamide addition amine, methyl hexahydro phthalic anhydride etc
The Lewis acid complexes etc. of boron fluoride ethylamine complex etc.
The preparation method of composition epoxy resin of the present invention is to mix the raw material of composition epoxy resin according to its proportioning
Uniformly.
The prepreg of the present invention can manufacture by the following method：The composition epoxy resin of the present invention is dissolved into organic
In solvent, then make it containing being dipped into reinforcing fiber, takes out, make evaporation of the solvent using baking oven etc.；Or by by epoxy resin group
Object heating is closed, makes it containing being dipped into reinforcing fiber, is taken out cooling.
The carbon-fibre reinforced epoxy resin composite material of the present invention can be molded with above-mentioned carbon fiber prepreg hot-press solidifying
It is made.
The composition epoxy resin and its carbon fiber prepreg, carbon fibre composite of the present invention can apply to industrial life
The various aspects of production and people's lives are specific as aerospace field, outdoor sports equipment, the accessory of communications and transportation, industry are raw
The mold of production and the common tool of daily life etc..
Mode by the following examples to the present invention composition epoxy resin, used the composition epoxy resin
Prepreg and carbon fibre reinforced composite are further illustrated.It is the carbon fiber that is used in embodiment, resin raw material, pre-
The evaluation with the production method of carbon fibre reinforced composite, the evaluation method and tensile strength that have hole compressive strength is expected in leaching
Method is as follows.
Unsaturated polyester (UP) synthesis material is as follows：
【Unsaturated dibasic acid】
A1：Mesaconic acid, the production of Shanghai Hao Hua Chemical Co., Ltd.s；
A2：Itaconic acid, the production of Henan De Wang chemical industry Industrial Co., Ltd.；
【Monounsaturated dicarboxylic acid】
B1：Adipic acid, the production of Shanghai Yuan Ji Co., Ltds；
B2：3- phenyl glutaric acids, the production of Hubei Wan get Chemical Co., Ltd.s；
【Ternary acid】
C1：Bio tech ltd's production is ground in citric acid, Shanghai one；
C2：Tricarballylic acid, the production of one base Industrial Co., Ltd. of Shanghai；
【Dihydric alcohol】
D1：1,6- hexylene glycol, the production of Hubei Wan get Chemical Co., Ltd.s；
D2：Dipropylene glycol, the production of Hubei Ju Sheng Science and Technology Ltd.s；
Unsaturated polyester (UP) is obtained according to raw material and formula, the method for being prepared by the following procedure shown in table 1：
1, it will be passed through nitrogen in reaction kettle to drain air, unsaturated dibasic acid, monounsaturated dicarboxylic acid, ternary acid is then added
It is uniformly mixed with polyalcohol；
2, heating mixture makes it fully melt to 130 DEG C or more, and decompression excludes the moisture of reaction generation, and constantly monitors
Viscosity of the system at 25 DEG C reduces the temperature to 105 DEG C when viscosity reaches analog value shown in table 1；
3, the 2- metoxyphenols of 1 parts by weight are added into reaction kettle, continue to stir 5min, cooling obtained unsaturated polyester (UP)
Resin.
1 unsaturated polyester (UP) of table
Composition epoxy resin synthesis material is as follows：
【Bisphenol A epoxide resin】
E：Hubei Chu Shengwei Chemical Co., Ltd.s produce, and molecular weight is 3100~7000；
【Carbochain polymer】
F1：Polyethylene, China Shenhua Coal to Liquid and Chemical Co., Ltd.'s production, the trade mark 8007, density 0.963g/cm3,190 DEG C
Lower melt index is 8.2g/10min；
F2：Polystyrene, the production of Dow group, the trade mark 1200, density 1.05g/cm3, melt index at 200 DEG C
For 5.0g/10min；
F3：Polystyrene-poly butadienestyrene block copolymer：Aldrich chemical reagents corporations produce, average molecular weight
1700, styrene 68wt%, acid value 335-375mg KOH/g.
F4：Polystyrene-poly (Ethylene/Butylene) block copolymer：Aldrich chemical reagents corporations produce, average molecular weight
89000, the dynamic viscosity of 20% toluene solution is 550Cp.
【Filler】
G1：Silicon carbide powder：Shanghai Nai Ou nanosecond science and technology Co., Ltd produces NO-C-001-1, grain size 50nm；
G2：Pps powder, toray Co., Ltd. produce A360M, grain size 200nm.
G3：Mass ratio is 15 by the crosslinked polystyrene microsphere of surface carboxylation:1:1:1 styrene, acrylic acid, two
Vinyl benzene and azodiisobutyronitrile are dissolved in the mixed solution of water and ethyl alcohol, under the atmosphere of nitrogen, are heated to 70 DEG C of reactions 8
Hour is made, grain size 500nm；
【Organic peroxide】
H1：Cyclohexanone peroxide, the production of Hubei Xin Mingtai Chemical Co., Ltd.s；
H2：Diacetyl peroxide, the production of Shanghai Hao Hua Chemical Co., Ltd.s；
【Free radical inhibitors】
I1：2- metoxyphenols, the production of Shanghai Nuo Tai Chemical Co., Ltd.s
【Carbon fiber】
Toray Co., Ltd. produces CO6142, thickness 0.15mm, surface density, 119g/m2.
Embodiment 1~17
The composition epoxy resin of embodiment 1~17 is added to mixer together according to raw material and proportioning shown in table 2
In, it is kneaded 20min at 160 DEG C, is cooled to room temperature and is made.
2 composition epoxy resin of table
Wherein "-" indicates not containing free radical inhibitors.
Comparative example 1
Bisphenol A epoxide resin is contained only in the composition epoxy resin of this comparative example.
Comparative example 2
In the composition epoxy resin of this comparative example only by the bisphenol A epoxide resin of 100 parts by weight and 10 parts by weight not
Saturated resin a is mixed.
Comparative example 3
In the composition epoxy resin of this comparative example only by the bisphenol A epoxide resin of 100 parts by weight and 10 parts by weight not
Saturated resin a, 10 parts by weight carbon chain compound F1 mix.
Comparative example 4
In the composition epoxy resin of this comparative example only by the bisphenol A epoxide resin of 100 parts by weight and 10 parts by weight not
Saturated resin a, the carbon chain compound F1 of 10 parts by weight, 5 parts by weight filler G1 mix.
Comparative example 5
In the composition epoxy resin of this comparative example only by the bisphenol A epoxide resin of 100 parts by weight and 10 parts by weight not
Saturated resin a, the filler G1 of 5 parts by weight, 0.2 parts by weight organic peroxide H1 mix.
Comparative example 6
Only by the filler of the bisphenol A epoxide resin and 5 parts by weight of 100 parts by weight in the composition epoxy resin of this comparative example
G1, the carbon chain compound F1 of 10 parts by weight, 0.2 parts by weight organic peroxide H1 mix.
By composition epoxy resin that embodiment and comparative example is prepared, (quality is asphalt mixtures modified by epoxy resin with curing agent ethylene diamine
The 10% of oil/fat composition) it is uniformly mixed to obtain uncured epoxy resin mixed liquor.Composition epoxy resin is molded
Shrinking percentage is tested.Test result is as described in Table 3.
Obtained uncured epoxy resin mixed liquor is applied with resin weight per unit area 50g/m2 using knife type coater
On cloth to processing release paper, resin film is made.The resin film is overlapped to carbon fiber (the toray Co., Ltd. production unidirectionally gathered
CO6142, thickness 0.15mm, surface density, 119g/m2) both sides, heated under 100 DEG C, 1 atmospheric pressure of temperature using hot-rolling plus
It is pressed onto 1MPa, makes composition epoxy resin containing being dipped into carbon fiber, obtains prepreg.The multilayer prepreg is set fitly to overlay
Together, in 100 DEG C of temperature, hot-press solidifying obtains carbon fibre reinforced composite sample in 10 hours under the conditions of 1MPa.To composite wood
Material carries out tensile strength, bending strength and interlaminar shear strength test.Test result is as described in Table 3.
The present invention needs the performance measured and its assay method.
Tensile strength：Prepreg is cut into defined size, on unidirectionally after laminated 6, is vacuum-packed, uses height
Kettle is pressed, cures 2 hours at 180 DEG C of temperature, pressure 6kg/cm2, obtains carbon fibre reinforced composite.By the unidirectional strengthening material
Material is cut into wide 12.7mm, long 230mm, and the thin slice of the fiberglass reinforced plastics of 1.2mm, long 50mm is bonded at both ends, is obtained
Test film.Using Instron universal testing machines, according to the specification of JISK7073-1988, tension test is carried out to the test film.
Bending strength：The prepreg multilayer of preparation is fitly stacked together, it is hot under the conditions of 1MPa in 100 DEG C of temperature
Carbon fibre reinforced composite is obtained within cured 10 hours, the bending that processing growth × width x thickness is 100mm × 15mm × 4mm is strong
Test specimen is spent, is tested by GB/T 1449-2005.
Interlaminar shear strength：The prepreg multilayer of preparation is fitly stacked together, in 100 DEG C of temperature, 1MPa conditions
Lower hot-press solidifying obtains carbon fibre reinforced composite in 10 hours, the interlaminar shear strength test specimen of standard is processed into, with GB/
It is measured on the basis of T 1450.1-2005.
Molding shrinkage：(toray Co., Ltd. produces CO6142, thickness to the carbon cloth that 10 layers are cut
0.15mm, surface density, 119g/m2) fitly overlay in the closed mold that length × width x thickness is 100mm × 100mm × 4mm,
(quality is epoxy composite to the composition epoxy resin of filling embodiment and comparative example with curing agent ethylene diamine in a mold again
The 10% of object) mixed liquor, be heated to seal to 100 DEG C of curing moldings, obtain carbon fibre reinforced composite and measure composite wood
The volume of material.Then：
Molding shrinkage=(volume of carbon fibre reinforced composite volume/mold) × 100%.
3 the performance test results of table
As shown in table 3, compared with comparative example 1~6, the composition epoxy resin of embodiment and its carbon fibre initial rinse of preparation
The mechanical property and molding shrinkage of material and carbon fibre reinforced composite all improve a lot.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto.
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of carbon fiber prepreg composition epoxy resin, which is characterized in that include following components：
100 parts by weight of bisphenol A epoxide resin；
10 ~ 30 parts by weight of unsaturated polyester (UP)；
10 ~ 50 parts by weight of carbochain polymer；
5 ~ 50 parts by weight of filler；
0.2 ~ 2 parts by weight of organic peroxide.
2. carbon fiber prepreg composition epoxy resin according to claim 1, which is characterized in that described unsaturated poly-
Ester is formed by unsaturated dibasic acid, monounsaturated dicarboxylic acid, ternary acid, dihydric alcohol polycondensation, and weight ratio is unsaturated dibasic acid:Saturation
Binary acid:Ternary acid:Dihydric alcohol=10:（5~10）:（0.1~1）:（10~20）.
3. carbon fiber prepreg composition epoxy resin according to claim 2, which is characterized in that unsaturated polyester (UP)
It prepares in raw material, the unsaturated dibasic acid is one or more in mesaconic acid or itaconic acid, the monounsaturated dicarboxylic acid choosing
From one or more in ethanedioic acid or 3- phenyl glutaric acids, one kind in citric acid or tricarballylic acid of the ternary acid or
A variety of, the dihydric alcohol is one or more in 1,6- hexylene glycols or dipropylene glycol.
4. carbon fiber prepreg composition epoxy resin according to claim 3, which is characterized in that described unsaturated poly-
Ester is 1000 ~ 3000mPas in 25 DEG C of viscosity.
5. carbon fiber prepreg composition epoxy resin according to claim 1, which is characterized in that the carbon chain polymerization
Object is one or more in polystyrene and its copolymer, polyvinyl acetate and its copolymer.
6. carbon fiber prepreg composition epoxy resin according to claim 5, which is characterized in that the carbon chain polymerization
Object is polyethylene, polystyrene, polystyrene-poly butadienestyrene block copolymer or polystyrene-poly（Ethylene/Butylene）Block
It is one or more in copolymer.
7. carbon fiber prepreg composition epoxy resin according to claim 1, which is characterized in that the filler includes
It is one or more in silicon carbide, pps powder, polystyrene microsphere, wherein the polystyrene microsphere is surface carboxylic
The crosslinked polystyrene microsphere of base.
8. according to claim 7 carbon fiber prepreg composition epoxy resin, which is characterized in that the grain size of the filler is preferred
For 10 ~ 1000nm, particle diameter distribution is less than 1.3.
9. carbon fiber prepreg composition epoxy resin according to claim 1, which is characterized in that the organic peroxy
Compound includes one or more in cyclohexanone peroxide, diacetyl peroxide.
10. according to claim 1-9 any one of them carbon fiber prepreg composition epoxy resins, which is characterized in that also
Contain free radical inhibitors 2- metoxyphenols.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109677562A (en) * | 2018-12-06 | 2019-04-26 | 江苏越科新材料有限公司 | A kind of anchor chain and preparation method thereof based on composite material |
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|---|---|---|---|---|
| JP2005060644A (en) * | 2003-08-11 | 2005-03-10 | Biruken Kk | Epoxy/unsaturated polyester/methyl trisilane containing silicone dispersion composite resin composition |
| CN104262903A (en) * | 2014-09-09 | 2015-01-07 | 丹阳丹金汽车部件有限公司 | Modified carbon fiber composite material with strong bond force and preparation method thereof |
| US20170267808A1 (en) * | 2014-12-23 | 2017-09-21 | Hexcel Composites Limited | Resin composition |
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2018
- 2018-04-20 CN CN201810362796.3A patent/CN108485202B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060644A (en) * | 2003-08-11 | 2005-03-10 | Biruken Kk | Epoxy/unsaturated polyester/methyl trisilane containing silicone dispersion composite resin composition |
| CN104262903A (en) * | 2014-09-09 | 2015-01-07 | 丹阳丹金汽车部件有限公司 | Modified carbon fiber composite material with strong bond force and preparation method thereof |
| US20170267808A1 (en) * | 2014-12-23 | 2017-09-21 | Hexcel Composites Limited | Resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109677562A (en) * | 2018-12-06 | 2019-04-26 | 江苏越科新材料有限公司 | A kind of anchor chain and preparation method thereof based on composite material |
| CN109677562B (en) * | 2018-12-06 | 2024-01-30 | 江苏越科新材料有限公司 | Anchor chain based on composite material and preparation method thereof |
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