CN100404238C - Thermosetting-heat plasticity compound resin based continuous fiber reinforced composite material - Google Patents
Thermosetting-heat plasticity compound resin based continuous fiber reinforced composite material Download PDFInfo
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- CN100404238C CN100404238C CNB2003101078486A CN200310107848A CN100404238C CN 100404238 C CN100404238 C CN 100404238C CN B2003101078486 A CNB2003101078486 A CN B2003101078486A CN 200310107848 A CN200310107848 A CN 200310107848A CN 100404238 C CN100404238 C CN 100404238C
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- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 title claims description 12
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 26
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 25
- 239000000805 composite resin Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 14
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 14
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000012779 reinforcing material Substances 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 31
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 239000003365 glass fiber Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- -1 tertiary amine compounds Chemical class 0.000 claims description 17
- 229920005990 polystyrene resin Polymers 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000001294 propane Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000914 Metallic fiber Polymers 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- CAWGQUPKYLTTNX-UHFFFAOYSA-N 3,4,5,6-tetrahydro-2,7-benzodioxecine-1,8-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=CC=C12 CAWGQUPKYLTTNX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 229920006387 Vinylite Polymers 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- MAYCNCJAIFGQIH-UHFFFAOYSA-N buta-1,3-diene 5-phenylpenta-2,4-dienenitrile Chemical compound C=CC=C.N#CC=CC=CC1=CC=CC=C1 MAYCNCJAIFGQIH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000001451 organic peroxides Chemical group 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 13
- 235000006708 antioxidants Nutrition 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 8
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 7
- 239000011152 fibreglass Substances 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 229920001083 polybutene Polymers 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- 239000004412 Bulk moulding compound Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000003677 Sheet moulding compound Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
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- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
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- 229920006122 polyamide resin Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to a continuous fiber reinforced composite material of thermosetting and thermoplastic composite resin group, which is prepared from the following components by weight portion: 100 to 300 portions of thermosetting resin, 100 to 600 portions of thermoplastic resin, 100 to 500 portions of reinforcing materials, 50 to 300 portions of diluting agent, 10 to 30 portions of initiating agent, 0.5 to 5 portions of accelerating agent, 1 to 10 portions of antioxidant and 1 to 100 portions of other auxiliary agents. The present invention combines the advantages of the thermosetting fiber reinforced composite materials and the fiber reinforced composite materials of thermoplastic resin together and provides a fiber reinforced composite material which has a simple immersion process, has a mutual-penetration network structure and can be machined.
Description
Technical field
The present invention relates to a kind of fibre reinforced composites, particularly a kind of thermosetting-thermoplastic composite resin-based continuous fiber reinforced composite materials.
Background technology
Fibre reinforced composites are compared with traditional material has specific strength and specific modulus is big, and fatigue performance is good, the characteristics that damping shock absorption is good and fail-safety is high.In general, existing fibre reinforced composites mainly can be divided into two kinds of thermosetting resin base fiber reinforced composite material and thermoplastic resin base fiber reinforced composite materials, wherein the thermosetting resin base fiber reinforced composite material comprises sheet molding compound (SMC) and bulk molding compound (BMC) and high strength molding compound (HMC) etc., mainly used unsaturated polyester resin, epoxy resin and phenolic resins etc. is basic material.Because the viscosity of material resin is lower, can be resin is compound with continuous fiber or short fiber by simple maceration, the goods that under crosslinking agent, action of evocating, have definite shape and intensity by the formation that is heating and curing.The advantage of this technology and goods is: 1) designability; 2) homogeneity of material and structure; 3) superiority of performance complex effect.But have unsurmountable shortcoming simultaneously: 1) goods do not have plasticity yet, can not carry out the processing of secondary hot melt; 2) goods do not have recuperability.Current to the very high situation of environmental requirement under, the development space of thermosetting resin base fiber reinforced composite material just little by little is restricted.
The thermoplastic resin base fiber reinforced composite material comprises that short fiber strengthens thermoplas tic resin composite's (for example short fiber REINFORCED PET resin etc.) and continuous fiber reinforced thermoplastic resin composite, and wherein the continuous fiber reinforced thermoplastic resin composite was at first grown up by U.S. PPG company in nineteen seventies.Summary is got up, and thermoplastic composite has following property: 1) density is little, the intensity height; 2) free degree of performance designability is big; 3) the more former basic resin of hot property improves a lot.Simultaneously, because the fundamental character of thermoplastic resin has determined that thermoplastic resin fibre's reinforced composite has the advantages that the thermoset resin fibres reinforced composite is not had: but secondary workability and recuperability.
Specifically, short fiber enhancing thermoplastic composite is by fiber and base resin coextrusion are formed; The continuous fiber reinforced thermoplastic composite then is that base resin and continuous fiber are passed through melt impregnation, and means such as Electrostatic Absorption are compounded to form.Mechanical property such as hot strength, bending strength and the impact property of comparing short fiber reinforced composite with the continuous fiber reinforced composite are good inadequately.
The continuous fiber reinforced composite is the important development direction of composite from now on.
But under present technology status, also there is some deficiency in the continuous fiber reinforced composite on concrete implementing process.Its basic reason is that the melt viscosity of thermoplastic resin and solution viscosity are all bigger, causes thermoplastic resin to continuous fiber dipping difficulty, and resin and fiber interface binding ability are bad.Finally cause the continuous fiber reinforced thermoplastic composite can not reach desirable mechanical property.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of thermosetting-thermoplastic composite resin-based continuous fiber reinforced composite materials and preparation method thereof, to overcome thermosetting resin base fiber reinforced composite material and the existing defective of thermoplastic resin base fiber reinforced composite material, satisfy the needs in relevant field.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
A kind of thermosetting-thermoplastic composite resin-based continuous fiber reinforced composite materials, adopt following component preparation:
100～300 parts of thermosetting resins, 100～600 parts of thermoplastic resins,
100～500 parts of continuous fiber reinforcing materials, 50～300 parts of diluents,
10～30 parts of initators, 0.5～5 part of promoter,
1～10 part in antioxidant, 1～100 part of other auxiliary agent;
It more than is weight portion.
Described thermosetting resin is one or more in unsaturated polyester resin, epoxy resin, the vinylite;
Described thermoplastic resin comprises one or more in the common thermoplastic resins such as polystyrene resin, styrene-acrylonitrile-butadiene copolymer resins (ABS resin), poly terephthalic acid ethylene glycol resin, polyamide or acrylic resin;
Described continuous fiber reinforcing material can be glass fibre (alkali-free or alkali containing glass fibre is arranged), carbon fiber, one or more in metallic fiber or the synthetic resin fiber.As the preferred carbon fiber of the high intensity of needs, as there is not specific (special) requirements from the preferred alkali-free glass fibre of cost performance.
Described diluent is one or more in styrene, AMS, methacrylic acid, ethanol, acetone, butylene phthalate, epoxy propane butyl ether, benzyl shrink acid anhydride oil ether, the expoxy propane phenyl ether;
Described initator is an organic peroxide, is selected from benzoyl peroxide, diacetyl peroxide, cyclohexanone peroxide, one or more in the methyl ethyl ketone peroxide.
Described promoter is transition metal organic salt and/or tertiary amine compounds, transition metal-type compound such as manganese naphthenate, aphthenic acids vanadium, cobalt naphthenate, cobalt octoate etc.; Tertiary amine compounds such as dimethylaniline, diethylaniline, dimethyl-p-toluidine etc.
Described antioxidant is Hinered phenols, hindered amines, phosphite ester kind antioxidant, or the halide of periodic table of elements IB family metal, as antioxidant 1098 (3,5-di-t-butyl-4-hydroxy benzenes propionyl-hexamethylene diamine), antioxidant 168 (tricresyl phosphite (2,4-di-tert-butyl phenolic ester)), anti-oxidant DLTP (dilauryl thiodipropionate), antioxidant 1010 (four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), copper halide etc.
Described other auxiliary agents comprise fire retardant, antistatic additive, light stabilizer, colouring agent, lubricant, conventional additives such as releasing agent.Short fiber various commonly used and the particulate inorganic compound such as the talcum powder that can also add any kind in addition, calcium carbonate, mica etc.
Described fire retardant is selected from one or more in halogen-containing fire retardant, red phosphorus, the antimony oxide.
The preparation method of aforesaid thermosetting-thermoplasticity continuous fiber reinforced composite may further comprise the steps:
1) powder and the thermosetting resin blending of thermoplastic resin is even, and add an amount of diluent, form thick fluid, its addition is so that the viscosity of material is 0.1-5PaS is suitable;
2) continuous fiber is passed from resin compound, reach the purpose that thermosetting resin and thermoplastic resin flood continuous fiber simultaneously;
3) heating steps 2) flooded the continuous fiber of thermoplastic resin and thermosetting resin, make thermosetting resin be subjected to heat cure, the thermoplastic resin heating and melting, form the inierpeneirating network structure of thermosetting resin and thermoplastic resin, and wrap up continuous fiber securely, heating-up temperature is 140 ℃-280 ℃, and be 0.1-3 hour heat time heating time;
The present invention gets up the advantages of thermosetting and thermoplastic resin fibre's reinforced composite, provides a kind of impregnation technology simple, has inierpeneirating network structure, machinable fibre reinforced composites.
The specific embodiment
Come further to the present invention make an explanation (all components content is weight fraction among the present invention) below in conjunction with embodiment.
Embodiment 1
With 250 parts of polyacrylate, 150 parts of styrene, 10 parts of benzoyl peroxides, 0.5 part of cobalt naphthenate, polystyrene resin powder 300 parts (wherein adding 5 parts of antioxidant 1010s and 168 compound systems) mixes, make continuous glass fibre pass through this mixed system, thereby unsaturated polyester (UP) and polystyrene resin powder are sticked to fiberglass surfacing simultaneously.And heating solidifies polyacrylate, makes the polystyrene resin fusion subsequently under 180 ℃, and forming co-continuous is inierpeneirating network structure mutually.The control content of glass fiber is about 300 parts.
Embodiment 2
With 120 parts of diphenol propane epoxy resin, 80 parts of epoxy propane butyl ethers, 15 parts of cyclohexanone peroxides, 1 part of cobalt naphthenate, ABS resin powder 500 parts (wherein adding 8 parts of antioxidant 1010s and 168 compound systems) and 100 parts of composite flame-retardant agent systems (ten bromines and antimony oxide) mix, make continuous glass fibre pass through this mixed system, thereby diphenol propane epoxy resin and ABS resin powder are sticked to fiberglass surfacing simultaneously.And heating makes the diphenol propane epoxy resin cure, makes the ABS resin fusion subsequently under 215 ℃, and forming co-continuous is inierpeneirating network structure mutually.The control content of glass fiber is about 200 parts.
Embodiment 3
With 200 parts of diphenol propane epoxy resin, 100 parts of styrene, 10 parts of methyl ethyl ketone peroxides, 03 part of cobalt naphthenate, pet resin powder 300 parts (wherein adding 5 parts of antioxidant 1010s and 168 compound systems) mixes, make continuous glass fibre pass through this mixed system, thereby diphenol propane epoxy resin and pet resin powder are sticked to fiberglass surfacing simultaneously.And heating makes curable unsaturated polyester, makes the pet resin fusion subsequently under 280 ℃, and forming the co-continuous phase structure is inierpeneirating network structure.The control content of glass fiber is about 400 parts.
Embodiment 4
Phenolic aldehyde is encircled 250 parts of epoxy resin more, 150 parts of styrene, 10 parts of benzoyl peroxides, 0.5 part of cobalt naphthenate, polystyrene resin powder 300 parts (wherein adding 5 parts of antioxidant 1010s and 168 compound systems) mixes, make continuous glass fibre pass through this mixed system, thereby phenolic aldehyde is encircled epoxy resin and the polystyrene resin powder sticks to fiberglass surfacing simultaneously more.And heating makes phenolic aldehyde encircle epoxy resin cure more, makes the polystyrene resin fusion subsequently under 180 ℃, and forming co-continuous is inierpeneirating network structure mutually.The control content of glass fiber is about 300 parts.
Embodiment 5
With 100 parts of polybutene glycol esters, 50 parts of styrene, 10 parts of benzoyl peroxides, 0.5 part of cobalt naphthenate, polystyrene resin powder 300 parts (wherein adding 5 parts of antioxidant 1010s and 168 compound systems) mixes, make continuous glass fibre pass through this mixed system, thereby polybutene glycol ester and polystyrene resin powder are sticked to fiberglass surfacing simultaneously.And heating solidifies the polybutene glycol ester, makes the polystyrene resin fusion subsequently under 180 ℃, and forming co-continuous is inierpeneirating network structure mutually.The control content of glass fiber is about 300 parts.
Embodiment 6
Phenolic aldehyde is encircled 100 parts of epoxy resin 150, diphenol propane epoxy resin more, 50 parts in benzyl shrink acid anhydride oil ether, 10 parts of benzoyl peroxides, 0.5 part of cobalt naphthenate, polystyrene resin powder 300 parts (wherein adding 5 parts of antioxidant 1010s and 168 compound systems) mixes, make continuous glass fibre pass through this mixed system, stick to fiberglass surfacing simultaneously more thereby phenolic aldehyde is encircled epoxy resin, diphenol propane epoxy resin and polystyrene resin powder.And heating makes phenolic aldehyde encircle epoxy resin, diphenol propane epoxy resin cure more, makes the polystyrene resin fusion subsequently under 180 ℃, and forming co-continuous is inierpeneirating network structure mutually.The control content of glass fiber is about 300 parts.
The test data of the foregoing description is as shown in table 1.
Table 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Hot strength (Mpa) | 125 | 116.2 | 181.7 | 185.3 | 121 | 130 |
| Stretch modulus (Gpa) | 10.55 | 6.895 | 14.13 | 15.21 | 12.5 | 13.5 |
| Bending strength (Mpa) | 236.9 | 223.1 | 285.1 | 290.5 | 225.3 | 210 |
| The bending amount of touching (Gpa) | 11.03 | 5.17 | 13.10 | 14.10 | 8.56 | 12.63 |
| Cantilever beam impact strength (J/m) | 305 | 742 | 795 | 798 | 736 | 732 |
Claims (7)
1. thermosetting-thermoplastic composite resin-based continuous fiber reinforced composite materials is characterized in that, is to adopt following component preparation:
100～300 parts of thermosetting resins, 100～600 parts of thermoplastic resins,
100～500 parts of continuous fiber reinforcing materials, 50～300 parts of diluents,
10～30 parts of initators, 0.5～5 part of promoter,
1～10 part in antioxidant, 1～100 part of other auxiliary agent;
It more than is weight portion;
Described thermosetting resin is one or more in unsaturated polyester resin, epoxy resin, the vinylite; Described thermoplastic resin comprises one or more in polystyrene resin, styrene-acrylonitrile-butadiene copolymer resins, poly terephthalic acid ethylene glycol resin, polyamide or the acrylic resin thermoplastic resin;
Described initator is an organic peroxide;
Described antioxidant is Hinered phenols, hindered amines, phosphite ester kind antioxidant, or the halide of periodic table of elements IB family metal.
2. thermosetting according to claim 1-thermoplastic composite resin-based continuous fiber reinforced composite materials, it is characterized in that described continuous fiber reinforcing material comprises alkali-free or in alkali containing glass fibre, carbon fiber, metallic fiber or the synthetic resin fiber one or more are arranged.
3. thermosetting according to claim 1-thermoplastic composite resin-based continuous fiber reinforced composite materials, it is characterized in that described continuous fiber reinforcing material comprises alkali-free or in alkali containing glass fibre, carbon fiber, metallic fiber or the synthetic resin fiber one or more are arranged.
4. thermosetting according to claim 1-thermoplastic composite resin-based continuous fiber reinforced composite materials, it is characterized in that described diluent is one or more in styrene, AMS, methacrylic acid, ethanol, acetone, butylene phthalate, epoxy propane butyl ether, benzyl shrink acid anhydride oil ether, the expoxy propane phenyl ether.
5. thermosetting according to claim 1-thermoplastic composite resin-based continuous fiber reinforced composite materials is characterized in that described promoter is transition metal organic salt and/or tertiary amine compounds.
6. according to each described thermosetting of claim 1～5-thermoplastic composite resin-based continuous fiber reinforced composite materials, it is characterized in that described other auxiliary agents comprise fire retardant, antistatic additive, light stabilizer, colouring agent, lubricant, releasing agent and short fiber, particulate inorganic compound.
7. according to the preparation method of each described thermosetting of claim 1～6-thermoplastic composite resin-based continuous fiber reinforced composite materials, it is characterized in that may further comprise the steps:
1) powder and the thermosetting resin blending of thermoplastic resin is even, and add an amount of diluent, form thick fluid;
2) continuous fiber is passed from resin compound;
3) heating steps 2) flooded the continuous fiber of thermoplastic resin and thermosetting resin, heating-up temperature is 140-280 ℃, be 0.1-3 hour heat time heating time.
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| CN106893038A (en) * | 2015-12-18 | 2017-06-27 | 上海杰事杰新材料(集团)股份有限公司 | A kind of continuous fiber reinforced thermoplastic composite material and preparation method thereof |
| CN108929529A (en) * | 2018-07-12 | 2018-12-04 | 泉州特米斯高环保科技有限公司 | A kind of mold materials formula and preparation method thereof |
| CN109705438A (en) * | 2019-02-01 | 2019-05-03 | 贵州省材料产业技术研究院 | Thermoplastic sheet material and application method for fibrous mesh cloth enhancing |
| CN111560161A (en) * | 2020-06-03 | 2020-08-21 | 龙永南 | Glass fiber composite material and preparation method thereof |
| CN113997597A (en) * | 2021-11-11 | 2022-02-01 | 桐庐富力电力器材有限公司 | Method for manufacturing glass fiber reinforced plastic cable protection pipe |
| CN114836006B (en) * | 2022-03-25 | 2023-05-09 | 大连理工大学 | Fiber-reinforced thermosetting/thermoplastic resin matrix composite material for splicing and preparation method and application thereof |
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