CN106633659A - Segmented copolymer-epoxy resin pre-mixture and preparation method thereof, resin compound for carbon fiber prepreg and preparation method thereof - Google Patents
Segmented copolymer-epoxy resin pre-mixture and preparation method thereof, resin compound for carbon fiber prepreg and preparation method thereof Download PDFInfo
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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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a segmented copolymer-epoxy resin pre-mixture and a preparation method thereof, a resin compound for a carbon fiber prepreg and the preparation method thereof. The segmented copolymer-epoxy resin pre-mixture contains a liquid epoxy resin, a segmented copolymer and a compatilizer, wherein the weight ratio of the liquid epoxy resin to the segmented copolymer to the compatilizer is (50-95):(5-50):(0.5-5). The segmented copolymer-epoxy resin pre-mixture has excellent toughness, so that the impact strength of the resin compound for the carbon fiber prepreg is increased. The two preparation methods both have the characteristics that the raw materials are easily available and the operation is simple.
Description
Technical field
The present invention relates to block copolymer-epoxy resin, in particular it relates to block copolymer-epoxy resin pre-composition and
Its preparation method, carbon fiber prepreg resin combination and preparation method thereof.
Background technology
It is a kind of fragility because carbon fiber prepreg ordinary epoxy resin is a kind of three-dimensional netted thermosetting polymer
Very strong material, its toughening modifying is the important research content of polymer science and Material Field basic research and application and development,
All receive significant attention all the time.
But merely using rubber, either elastomer or rigid particles all have some shortcomings to epoxy resin roughening.
For example, 1）The simple addition content requirement using rubber or Toughened Epoxy Resin by Elastomer, rubber or elastomer is very high, generally needs
Reaching more than 20% volume can just play toughening effect, and so, although impact flexibility is improved, but this often leads
Cause the intensity and modulus lost of material too many.2）And toughness reinforcing is carried out to it using inorganic rigid particle, although the intensity of material and
Modulus will not lose, but the toughness of material cannot be improved substantially, and due to inorganic particulate and the phase of organic resin epoxy
Capacitive is poor, it will usually there is a problem of that inorganic particulate cannot be dispersed in epoxy resin-base, particularly micro-or nano size
Inorganic Fillers Filled epoxy-resin systems, because particle size is little, with very high surface energy, easily occur in the base big
Area agglomeration, so that larger defect is produced in epoxy resin, so, however reduce the toughness of epoxy resin, epoxy
The enhancing of resin becomes a kind of contradiction with toughness reinforcing, restricts the product further to the development of more dominance energy.
Meanwhile, patent CN201410273158.6（Composition epoxy resin, prepreg and fibre reinforced composites）
In mention and being used in prepreg industry with block copolymer-toughened epoxy resin, but without solving consistency problem well.
The content of the invention
It is an object of the invention to provide a kind of block copolymer-epoxy resin pre-composition and preparation method thereof, carbon fiber are pre-
Leaching material resin combination and preparation method thereof, the block copolymer-epoxy resin pre-composition has excellent toughness, Jin Erti
The high impact strength of carbon fiber prepreg resin combination, while two groups of preparation methods are respectively provided with raw material and are easy to get, operate letter
Just the characteristics of.
To achieve these goals, the invention provides a kind of block copolymer-epoxy resin pre-composition, containing Breakup of Liquid Ring
Oxygen tree fat, block copolymer and compatilizer；Liquid epoxies, block copolymer, the weight ratio of compatilizer are 50-95：5-50：
0.5-5。
Present invention also offers a kind of preparation method of block copolymer-epoxy resin pre-composition described above, including：
1）Liquid epoxies, compatilizer are warming up into 50-80 DEG C and stirring reaction 0.1-1h, are well mixed and are obtained mixture；
2）Block copolymer is added into mixture, 100-150 DEG C and stirring reaction 0.5-3h is warming up to, obtaining viscosity degree is
Block copolymer-the epoxy resin pre-composition of 1500-25000mPas；
Wherein, liquid epoxies, block copolymer, the weight ratio of compatilizer are 50-95：5-50：0.5-5.
Invention further provides a kind of carbon fiber prepreg resin combination, containing block copolymerization described above
Thing-epoxy resin pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator；Block copolymer-asphalt mixtures modified by epoxy resin
The weight ratio of fat pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator is 1-25：2-30：5-35：1-
10：0.2-2.
The present invention further provides a kind of preparation method of carbon fiber prepreg resin combination described above,
Including：
1）Block copolymer-epoxy resin pre-composition, liquid epoxies and solid epoxy are mixed at 60-90 DEG C
It is even；
2）By in curing agent, accelerator addition system, stirring mixing 0.5-1h obtains end-product；
3）End-product is solidified into 0.5-4h at 120-150 DEG C and obtains carbon fiber prepreg resin combination；
Wherein, block copolymer-epoxy resin pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator
Weight ratio is 1-25：2-30：5-35：1-10：0.2-2.
In above-mentioned technical proposal, the present invention is carried out first by block copolymer and compatilizer to liquid epoxies
It is modified（Block copolymer fusing point is high, polarity is poor, uneven after being directly appended to solidify in epoxy resin, affects the mechanical properties）Make
Obtain block copolymer-epoxy resin pre-composition and there is excellent toughness（Toughness improves 50-120%）；Then pass through block copolymerization
The synergy of thing-epoxy resin pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator causes to be obtained
Carbon fiber prepreg resin combination there is excellent shock resistance.Meanwhile, above-mentioned two groups of preparation methods are respectively provided with original
Material be easy to get, it is easy to operate the characteristics of, consequently facilitating promote.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of block copolymer-epoxy resin pre-composition, containing liquid epoxies, block copolymer
And compatilizer；Liquid epoxies, block copolymer, compatilizer（Improve the dispersion effect of block copolymer）Weight ratio be
50-95：5-50：0.5-5.
In the present invention, the species of liquid epoxies can be selected in wide scope, but in order that obtained embedding
Section copolymer-epoxy resin pre-composition has more excellent toughness, it is preferable that liquid epoxies is selected from liquid bisphenol A type ring
Oxygen tree fat, liquid bisphenol F type epoxy resin, liquid bisphenol S type epoxy resin, liquid alicyclic epoxy resin, liquid phenolic ring
At least one in oxygen tree fat, liquid modifying epoxy resin and liquid glycidyl amine epoxy resin.
In the present invention, block copolymer is generally thermoplastic polymer, to directly apply to be difficult in epoxy resin and plays
The effect of toughness reinforcing, needs to carry out pre-reaction；The shape and molecular weight of block copolymer shape can be selected in wide scope,
But in order to improve the dispersion effect of block copolymer and then make obtained block copolymer-epoxy resin pre-composition with more excellent
Different toughness, it is preferable that block copolymer is the grade amorphous particle of millimeter；More preferably A-B-A types di-block copolymer（Its
In, A is the active rigid molecular segments with epoxy radicals, vinyl, pi-allyl, hydroxyl or carboxyl, and B is soft segment）In extremely
Few one kind.
In the present invention, the concrete species of compatilizer can be selected in wide scope, but in order that obtained block
Copolymer-epoxy resin pre-composition has more excellent toughness and then makes obtained block copolymer-epoxy resin pre-composition tool
Have more excellent toughness, it is preferable that compatilizer selected from triphenylphosphine, acid acetic triphenyl phosphorus, tetraethylammonium bromide, four
At least one in butylammonium bromide, triethyl benzyl ammonia chloride.
Present invention also offers a kind of preparation method of block copolymer-epoxy resin pre-composition described above, including：
1）Liquid epoxies, compatilizer are warming up into 50-80 DEG C and stirring reaction 0.1-1h, are well mixed and are obtained mixture；
2）Block copolymer is added into mixture, 100-150 DEG C and stirring reaction 0.5-3h is warming up to, obtaining viscosity degree is
Block copolymer-the epoxy resin pre-composition of 1500-25000mPas；
Wherein, liquid epoxies, block copolymer, the weight ratio of compatilizer are 50-95：5-50：0.5-5.
Invention further provides a kind of carbon fiber prepreg resin combination, containing block copolymerization described above
Thing-epoxy resin pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator；Block copolymer-asphalt mixtures modified by epoxy resin
The weight ratio of fat pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator is 1-25：2-30：5-35：1-
10：0.2-2.
In the present invention, the species of liquid epoxies can be selected in wide scope, but in order that obtained carbon
Fiber prepreg material has more excellent shock resistance with resin combination, it is preferable that liquid epoxies is selected from liquid bisphenol A
Type epoxy resin, liquid bisphenol F type epoxy resin, liquid bisphenol S type epoxy resin, liquid alicyclic epoxy resin, liquified phenol
At least one in formaldehyde epoxy resin, liquid modifying epoxy resin and liquid glycidyl amine epoxy resin.
In the present invention, the species of solid epoxy can be selected in wide scope, but in order that obtained carbon
Fiber prepreg material has more excellent shock resistance with resin combination, it is preferable that solid epoxy is selected from solid bisphenol A
Type epoxy resin, solid phenol-formaldehyde epoxy resin, solid orthoresol type epoxy resin, solid biphenyl type epoxy resin and Solid Modified
At least one in epoxy resin.
In the present invention, the species of curing agent can be selected in wide scope, but in order that obtained carbon fiber is pre-
Leaching material has more excellent shock resistance with resin combination, it is preferable that curing agent is selected from dicyandiamide, alkyl hydrazine, fragrance
At least one in amine and modified amine.
In the present invention, the species of accelerator can be selected in wide scope, but in order that obtained carbon fiber is pre-
Leaching material has more excellent shock resistance with resin combination, it is preferable that accelerator is selected from substitute urea compound, triphenyl
At least one of phosphine, glyoxaline compound, tertiary amine and quaternary ammonium salt.
The present invention further provides a kind of preparation method of carbon fiber prepreg resin combination described above,
Including：
1）Block copolymer-epoxy resin pre-composition, liquid epoxies and solid epoxy are mixed at 60-90 DEG C
It is even；
2）By in curing agent, accelerator addition system, stirring mixing 0.5-1h obtains end-product；
3）End-product is solidified into 0.5-4h at 120-150 DEG C and obtains carbon fiber prepreg resin combination；
Wherein, block copolymer-epoxy resin pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator
Weight ratio is 1-25：2-30：5-35：1-10：0.2-2.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
1）It is prepared by block copolymer-epoxy resin pre-composition：
1kg is preheating into 50 DEG C of liquid bisphenol A epoxy resin NPEL-128E（Is produced from Taiwan South Asia, epoxide equivalent 187g/eq）
With 0.05kg acidity acetic triphenyl phosphorus（LG-DOW is produced）In being added to 2L cool-bags, then stirred with mixer
0.1-1h is mixed, while stirring in five times（It is judged as that content is as clear as crystal between batch）Add 0.2kg block copolymers
Nanostrength M22N（French A Kema is produced）, be heated to 120 DEG C, stirring reaction 30-180min, obtain block copolymer-
Epoxy resin pre-composition, viscosity is 3500 mPas at 90 DEG C of test, standby.
2）Carbon fiber is prepared with epoxy prepreg resin combination：
15 parts of above-mentioned block copolymer-epoxy resin pre-composition, liquid bisphenol A epoxy resin NPEL-128E（Taiwan South Asia
Produce）10 parts, solid bisphenol A type epoxy resin NPES-901（Is produced from Taiwan South Asia, epoxide equivalent 475g/eq）25 parts, solid phenol-formaldehyde
Epoxy resin NPPN-638S（Is produced from Taiwan South Asia, epoxide equivalent 180g/eq）, and micronizing dicyandiamide Dyhard 100S（Germany
A Ziken chemical industry is produced）5 parts and substituted urea diphenylguanidine yhard UR200（German A Ziken chemical industry is produced）It is 1 part, uniform in 80 DEG C
Mixing 05-1h obtains end-product.
3）Cast testing bar and evaluation toughening effect：
Above-mentioned end-product is solidified into 0.5-4h at 120-150 DEG C and obtains material cast impact specimen bar（Specification be 100mm ×
10mm×4mm）, impact specimen bar is tested according to GB/T 1043.1-2008, impact strength is 19.56kJ/m2, relative to equal
Under the conditions of without block copolymer impact specimen bar impact strength（10.26 kJ/m2）Improve 90.64%.
Embodiment 2
1）It is prepared by block copolymer-epoxy resin pre-composition：
1kg is preheating into 60 DEG C of liquid bisphenol A epoxy resin NPEL-128E（Is produced from Taiwan South Asia, epoxide equivalent 187g/eq）
With 0.04kg triphenyl phosphorus（LG-DOW is produced）In being added to 2L cool-bags, then 0.1-1h, side are stirred with mixer
Stirring side is in four times（It is judged as that content is as clear as crystal between batch）Add 0.2kg block copolymer Nanostrength
M52N（French A Kema is produced）, 130 DEG C are heated to, stirring reaction 30-180min obtains block copolymer-epoxy resin premix
Thing, viscosity is 10000mPas at 90 DEG C of test, standby.
2）Carbon fiber is prepared with epoxy prepreg resin combination：
The above-mentioned weight portion of block copolymer-epoxy resin pre-composition 15, liquid bisphenol A epoxy resin NPEL-128E（Tai Wannan
Produce Asia）12 weight portions, solid bisphenol A type epoxy resin NPES-901（Is produced from Taiwan South Asia, epoxide equivalent 475g/eq）25 weight
Part, semi-solid novolac epoxy resin NPPN-638S（Is produced from Taiwan South Asia, epoxide equivalent 180g/eq）, and micronizing dicyandiamide
Dyhard 100S（German A Ziken chemical industry is produced）5 weight portions and substituted urea diphenylguanidine yhard UR700（German A Zikenization
Work is produced）1 weight portion, in 80 DEG C of uniform mixing 0.5-1h end-product is obtained.
3）Cast testing bar and evaluation toughening effect：
Above-mentioned end-product is solidified into 0.5-4h at 120-150 DEG C and obtains material cast impact specimen bar（Specification be 100mm ×
10mm×4mm）, impact specimen bar is tested according to GB/T 1043.1-2008, impact strength is 23.59kJ/m2, relative to equal
Under the conditions of without block copolymer impact specimen bar impact strength（11.48kJ/m2）Improve 105.49%.
Embodiment 3
1）It is prepared by block copolymer-epoxy resin pre-composition：
1kg is preheating into 60 DEG C of liquid bisphenol A epoxy resin NPEL-128E（Is produced from Taiwan South Asia, epoxide equivalent 187g/eq）
With 0.04kg TBABs（It is commercially available）In being added to 2L cool-bags, then 0.1-1h is stirred with mixer, while stirring
Mix side in four times（It is judged as that content is as clear as crystal between batch）Add 0.2kg block copolymer Nanostrength M53
（French A Kema is produced）, 150 DEG C are heated to, stirring reaction 30-180min obtains block copolymer-epoxy resin pre-composition, surveys
Viscosity is 35000 mPas at 90 DEG C of examination, standby.
2）Carbon fiber is prepared with epoxy prepreg resin combination：
The above-mentioned weight portion of block copolymer-epoxy resin pre-composition 15, liquid bisphenol A epoxy resin NPEL-128E（Tai Wannan
Produce Asia）12 weight portions, solid bisphenol A type epoxy resin NPES-901（Is produced from Taiwan South Asia, epoxide equivalent 475g/eq）25 weight
Part, semi-solid novolac epoxy resin NPPN-638S（Is produced from Taiwan South Asia, epoxide equivalent 180g/eq）, and micronizing dicyandiamide
Dyhard 100SF（German A Ziken chemical industry is produced）5 weight portions and substituted urea diphenylguanidine yhard UR500（German A Ziken
Chemical industry is produced）1 weight portion, in 80 DEG C of uniform mixing 0.5-1h end-product is obtained.
3）Cast testing bar and evaluation toughening effect：
Above-mentioned end-product is solidified into 0.5-4h at 120-150 DEG C and obtains material cast impact specimen bar（Specification be 100mm ×
10mm×4mm）, impact specimen bar is tested according to GB/T 1043.1-2008, impact strength is 19.26kJ/m2, relative to equal
Under the conditions of without block copolymer impact specimen bar impact strength（12.58kJ/m2）Improve 53.10%.
Embodiment 4
1）It is prepared by block copolymer-epoxy resin pre-composition：
1kg is preheating into 60 DEG C of liquid glycidyl amine type epoxy resin AG-80（Shanghai China friendship is produced, epoxide equivalent 125g/
eq）With 0.04kg triphenyl phosphorus（LG-DOW is produced）In being added to 2L cool-bags, then 0.1-1h is stirred with mixer,
While stirring in four times（It is judged as that content is as clear as crystal between batch）Add 0.2kg block copolymer Nanostrength
M53（French A Kema is produced）, 130 DEG C are heated to, stirring reaction 30-180min obtains block copolymer-epoxy resin pre-composition,
Viscosity is 18000 mPas at 90 DEG C of test, standby.
1）Carbon fiber is prepared with epoxy prepreg resin combination：
The above-mentioned weight portion of block copolymer-epoxy resin pre-composition 15, liquid bisphenol A epoxy resin NPEL-128E（Tai Wannan
Produce Asia）12 weight portions, solid bisphenol A type epoxy resin NPES-901（Is produced from Taiwan South Asia, epoxide equivalent 475g/eq）25 weight
Part, semi-solid novolac epoxy resin NPPN-638S（Is produced from Taiwan South Asia, epoxide equivalent 180g/eq）, and micronizing dicyandiamide
Dyhard 100S（German A Ziken chemical industry is produced）5 weight portions and substituted urea diphenylguanidine yhard UR700（German A Zikenization
Work is produced）1 weight portion, in 80 DEG C of uniform mixing 0.5-1h end-product is obtained.
1）Cast testing bar and evaluation toughening effect：
Above-mentioned end-product is solidified into 0.5-4h at 120-150 DEG C and obtains material cast impact specimen bar（Specification be 100mm ×
10mm×4mm）, impact specimen bar is tested according to GB/T 1043.1-2008, impact strength is 25.55kJ/m2, relative to equal
Under the conditions of without block copolymer impact specimen bar impact strength（13.56kJ/m2）Improve 88.42%.
Embodiment 5
1）It is prepared by block copolymer-epoxy resin pre-composition：
1kg is preheating into 60 DEG C of liquid bisphenol A epoxy resin NPEL-128E（Is produced from Taiwan South Asia, epoxide equivalent 187g/eq）
With 0.04kg TBABs（It is commercially available）In being added to 2L cool-bags, then 0.1-1h is stirred with mixer, while stirring
Mix side in four times（It is judged as that content is as clear as crystal between batch）Add 0.2kg block copolymer Nanostrength M53
（French A Kema is produced）, 150 DEG C are heated to, stirring reaction 30-180min obtains block copolymer-epoxy resin pre-composition, surveys
Viscosity is 35000 mPas at 90 DEG C of examination, standby.
2）Carbon fiber is prepared with epoxy prepreg resin combination：
The above-mentioned weight portion of block copolymer-epoxy resin pre-composition 20, liquid bisphenol A epoxy resin NPEL-128E（Tai Wannan
Produce Asia）12 weight portions, solid bisphenol A type epoxy resin NPES-901（Is produced from Taiwan South Asia, epoxide equivalent 475g/eq）25 weight
Part, solid o-cresol epoxy resin NPCN-704（Is produced from Taiwan South Asia, epoxide equivalent 225g/eq）, and micronizing dicyandiamide
Dyhard 100S（German A Ziken chemical industry is produced）5 weight portions and substituted urea diphenylguanidine yhard UR500（German A Zikenization
Work is produced）1 part, in 80 DEG C of uniform mixing 0.5-1h end-product is obtained.
3）Cast testing bar and evaluation toughening effect：
Above-mentioned end-product is solidified into 0.5-4h at 120-150 DEG C and obtains material cast impact specimen bar（Specification be 100mm ×
10mm×4mm）, impact specimen bar is tested according to GB/T 1043.1-2008, impact strength is 26.75kJ/m2, relative to equal
Under the conditions of without block copolymer impact specimen bar impact strength（12.50kJ/m2）Improve 114.00%.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as it is without prejudice to this
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of block copolymer-epoxy resin pre-composition, it is characterised in that containing liquid epoxies, block copolymer and
Compatilizer；The liquid epoxies, block copolymer, the weight ratio of compatilizer are 50-95：5-50：0.5-5.
2. block copolymer-epoxy resin pre-composition according to claim 1, wherein, the liquid epoxies is selected from
Liquid bisphenol A epoxy resin, liquid bisphenol F type epoxy resin, liquid bisphenol S type epoxy resin, liquid alicyclic asphalt mixtures modified by epoxy resin
At least one in fat, liquid phenolic epoxy resin, liquid modifying epoxy resin and liquid glycidyl amine epoxy resin.
3. block copolymer-epoxy resin pre-composition according to claim 1, wherein, the block copolymer is millimeter
Grade amorphous particle；Preferably A-B-A types di-block copolymer（Wherein, A is band epoxy radicals, vinyl, pi-allyl, hydroxyl
Or the active rigid molecular segments of carboxyl, B is soft segment）In at least one.
4. block copolymer-epoxy resin pre-composition according to claim 1, wherein, the compatilizer is selected from triphenyl
In phosphine, acid acetic triphenyl phosphorus, tetraethylammonium bromide, TBAB, triethyl benzyl ammonia chloride at least one
Kind.
5. a kind of preparation method of the block copolymer-epoxy resin pre-composition as described in any one in claim 1-4, its
It is characterised by, including：
1）The liquid epoxies, compatilizer are warming up into 50-80 DEG C and stirring reaction 0.1-1h obtains mixture；
2）The block copolymer is added into the mixture, 100-150 DEG C and stirring reaction 0.5-3h is warming up to, is obtained
Viscosity degree is the block copolymer-epoxy resin pre-composition of 1500-25000mPas；
Wherein, the liquid epoxies, block copolymer, the weight ratio of compatilizer are 50-95：5-50：0.5-5.
6. a kind of carbon fiber prepreg resin combination, it is characterised in that containing as described in any one in claim 1-4
Block copolymer-epoxy resin pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator；The block
The weight ratio of copolymer-epoxy resin pre-composition, liquid epoxies, solid epoxy, curing agent and accelerator is 1-25：
2-30：5-35：1-10：0.2-2.
7. according to the carbon fiber prepreg resin combination of claim 6, wherein, the liquid epoxies is selected from liquid bisphenol
A type epoxy resin, liquid bisphenol F type epoxy resin, liquid bisphenol S type epoxy resin, liquid alicyclic epoxy resin, liquified phenol
At least one in formaldehyde epoxy resin, liquid modifying epoxy resin and liquid glycidyl amine epoxy resin.
8. the carbon fiber prepreg resin combination of claim 6, wherein, the solid epoxy is selected from solid bisphenol A
Type epoxy resin, solid phenol-formaldehyde epoxy resin, solid orthoresol type epoxy resin, solid biphenyl type epoxy resin and Solid Modified
At least one in epoxy resin.
9. the carbon fiber prepreg resin combination of claim 6, wherein, the curing agent selected from dicyandiamide, alkyl hydrazine,
At least one in aromatic amine and modified amine；
Preferably, the accelerator is selected from substitute urea compound, triphenylphosphine, glyoxaline compound, tertiary amine and quaternary ammonium salt
It is at least one.
10. a kind of preparation method of the carbon fiber prepreg resin combination as described in any one in claim 6-9, its
It is characterised by, including：
1）Block copolymer-the epoxy resin pre-composition, liquid epoxies and solid epoxy are mixed at 60-90 DEG C
Close uniform；
2）By in the curing agent, accelerator addition system, stirring mixing 0.5-1h obtains end-product；
3）The end-product is solidified into 0.5-4h at 120-150 DEG C and obtains the carbon fiber prepreg resin combination；
Wherein, the block copolymer-epoxy resin pre-composition, liquid epoxies, solid epoxy, curing agent and promotion
The weight ratio of agent is 1-25：2-30：5-35：1-10：0.2-2.
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| CN109760385A (en) * | 2017-11-08 | 2019-05-17 | 广东生益科技股份有限公司 | Can static bending copper-clad plate and preparation method thereof and bending and molding method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107474772A (en) * | 2017-08-22 | 2017-12-15 | 株洲时代新材料科技股份有限公司 | A kind of wind power motor stator end protection epoxy glue and preparation method thereof |
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| CN109760385A (en) * | 2017-11-08 | 2019-05-17 | 广东生益科技股份有限公司 | Can static bending copper-clad plate and preparation method thereof and bending and molding method |
| CN109760385B (en) * | 2017-11-08 | 2022-08-16 | 广东生益科技股份有限公司 | Copper-clad plate capable of being bent statically, manufacturing method thereof and bending forming method |
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