CN1580099A - Continuous fiber reinforced thermoplastic composite material - Google Patents
Continuous fiber reinforced thermoplastic composite material Download PDFInfo
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- CN1580099A CN1580099A CN 03142206 CN03142206A CN1580099A CN 1580099 A CN1580099 A CN 1580099A CN 03142206 CN03142206 CN 03142206 CN 03142206 A CN03142206 A CN 03142206A CN 1580099 A CN1580099 A CN 1580099A
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- continuous fiber
- composite material
- fiber reinforced
- reinforced thermoplastic
- thermoplastic composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 title claims description 19
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 18
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 15
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 polypropylene Polymers 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 17
- 239000003365 glass fiber Substances 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 239000004417 polycarbonate Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 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 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 5
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 5
- 230000035939 shock Effects 0.000 abstract description 2
- 239000011324 bead Substances 0.000 abstract 2
- 238000005452 bending Methods 0.000 abstract 2
- 239000003607 modifier Substances 0.000 abstract 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 10
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 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 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005421 electrostatic potential Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
Abstract
A kind of continuous fiber thermoplastics material includes the following component and content (percent by weight): continuous fiber of between 25 and 80, thermoplastic resin of between 20 and 75, micro glass bead of between 0 and 10 and nucleater of between 0.05 and 1.5. This composite of continuous fiber thermoplastics rosin provided by the invention improves its resinousness greatly after being added the micro glass bead, nucleater and modifier. Therefore, this continuous fiber thermoplastics material of the invention is characterized with high rigidity, tensile-and- bending strength and the high shock resistance and heat distortion temperature at low and high temperature, which increases the material's tensile strength from 220MPa to 300MPa and bending modulus from 15GPa to 22GPa, which is increased by nearly 50%.
Description
Technical field
The present invention relates to a kind of continuous glass fibre enhanced thermoplastic composite.
Background technology
In continuous fiber reinforced thermoplastic resin composite material, the existing way of fiber is not only successive, but also arranges in the mode of almost parallel.Fiber can be given full play to the high-strength and high-modulus characteristic of fiber on its length direction.The level that can reach steel alloy that has is so it is substituting steel in the use aspect a lot.
Existing continuous fiber reinforced thermoplastic composite material has better comprehensive mechanical property, because it does not consider the improvement to resin property, so its rigidity, flexural strength and tensile strength often do not reach requirement.The technology that disclose as Chinese patent 01145415 and 88102218 are owing to the adhesive property of only considering fiber surface and resin and fiber have been ignored improvement to resin by the impregnability of resin.
Summary of the invention
The technology that the present invention need solve is to disclose a kind of continuous fiber reinforced thermoplastic composite material, to overcome the not high defective of rigidity of material, flexural strength and tensile strength that prior art exists.
Technical conceive of the present invention is such:
Rigidity, flexural strength and the tensile strength of the present invention in order to promote continuous fiber reinforced thermoplastic composite material added glass microballon and nucleator in matrix material, thereby obtained comparatively ideal results.
The fiber-reinforced thermoplastic resin matrix material, its performance is by the performance decision of strongthener and resin two aspects.The arrangement mode of continuous fibre and almost parallel thereof is not fully exerted its performance in matrix material, but because resin itself also is the important component part of material, its performance has restricted the overall performance of material to a great extent.
Technical scheme of the present invention:
The said continuous fiber reinforced composite materials of the present invention comprises following component and content (parts by weight):
Continuous fibre 25～80
Thermoplastic resin 20～75
Glass microballon 0～10
Nucleator 0.05～1.5
Said thermoplastic resin comprises current commercial all thermoplastic resin kinds, comprise a kind of and composition thereof in nylon, polycarbonate, polypropylene, polyethylene, polystyrene type, polyphenylene oxide, polyphenylene sulfide, polyoxymethylene, the polymethylmethacrylate etc., or resin alloy, to satisfy various needs, the optimization polypropylene grafts, as maleic anhydride inoculated polypropylene, or the blend of polypropylene and polycarbonate
Said continuous fibre comprises wherein one or more such as glass fibre, carbon fiber, steel fiber, and they exist in sheet material in a continuous manner.
Said glass microballon is a kind of uniqueness and the nonpoisonous and tasteless nonmetal hollow minute particle of stable performance, sky contains rare gas elementes such as nitrogen and carbonic acid gas, mainly be made up of silicon-dioxide and aluminium sesquioxide etc., particle size range is 10～250um, and tap density is 0.35～0.45g/cm
3Hollow glass micropearl has characteristics such as easily disperse, good fluidity, proportion are little, wear-resisting, high temperature resistant, acid and alkali-resistance because of its special structure.So, add the density that hollow glass micropearl has reduced material, improved the stretching and the flexural strength of matrix material, improved the heat-drawn wire of material.
Said nucleator can be an inorganic additives, such as talcum powder, silicon-dioxide, kaolin; The organic compound nucleator is such as monobasic or polycarboxylate, organophosphate, diphenylmethylene sorbyl alcohol, rosin based nucleator; The NA series nucleator of polymer novel material company limited is moulded by preferred Shanghai section, is the nucleator of NA-45, NA-9930T such as the trade mark.Thermoplastic resin is exactly the poor rigidity of material with respect to the weakness of a maximum of thermosetting resin.This is because most of thermoplastic resins all are unformed shape or half hitch crystalline state, lacks crosslinked cause between the macromole.In the present invention,, impel its quick nucleation, crystallization, improve percent crystallization in massecuite and crystal grain thinning and make its arrangement regular, reach and improve intensity and inflexible purpose by adding NA series nucleator.
Continuous fiber reinforced thermoplastic resin composite material provided by the invention adds after the properties-correcting agent owing to added glass microballon and nucleator in resin, and resin property is significantly improved.So continuous fibre enhanced thermoplastic composite of the present invention has shock resistance high under very high rigidity, stretching and flexural strength and low, the high temperature and high heat-drawn wire, make the tensile strength of material bring up to 400Mpa from 220Mpa, modulus in flexure rises to 30Gpa by 15Gpa, has improved nearly 100%.
Continuous fiber reinforced thermoplastic composite material provided by the invention can conventional employing powder electrostatic absorption method also can adopt conventional melt impregnation and reaction method preparation.Continuous fibre fully plastifies by baking oven and high temperature die head through after fully flooding, and is pressed into flaky composite material through multi-rolling mill again, and its thickness is preferably between 0.3～2.0mm.Sheet material is cut into certain-length and width, and on demand angle and mode stack, and place mould compression moulding, obtain the goods that need.
Embodiment
Below in conjunction with embodiment, the performance of continuous fiber reinforced thermoplastic resin flaky composite material is described in further detail.
In the following example, antioxidant 1010 is: four (β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid) pentaerythritol ester; Oxidation inhibitor DSTP is: thio-2 acid (octadecyl ester); Nucleator NA-45, NA-9930T mould the NA series nucleator trade mark of polymer novel material company limited for Shanghai section.
Embodiment 1
Maleic anhydride inoculated polypropylene powder with 70 kilograms, 1 kilogram of hollow glass micropearl, 0.5 kilogram nucleator NA-45 (series of phosphate, Shanghai section moulds macromolecular material company limited and produces), 0.5 kilogram antioxidant 1010,0.5 kilogram oxidation inhibitor DSTP mixes, and places the high pressure static electricity fluidized-bed.30 kilograms of glass fibre are passed through from fluidized-bed continuously.The electrostatic potential of regulating fluidized-bed makes the weight fraction of maleic anhydride inoculated polypropylene remain on 70 to regulate the amount of glass fibre polymeric adsorbent.The glass fibre that is adsorbed with resin passes through from baking oven and high temperature die head continuously, passes through multi-rolling mill again, and compacting is into about the sheet material of 1mm thickness.Continuous sheet is cut into the sheet material of certain-length and width, according to the vertical and horizontal sheet material number of plies than being n: ratio (n-1) is arranged, and places mould, at 200 ℃, is pressed into plate under the pressure of 16Mpa.Plate is processed into stretching, crooked and impact batten by GB, tests its performance and list in the table 1.
Embodiment 2
Regulate each components contents, the weight fraction of control maleic anhydride inoculated polypropylene remains on about 30, and concrete component is as follows, and all the other are as embodiment 1.Testing its performance lists in the table 1.Concrete component is as follows:
Glass fibre 70
Maleic anhydride inoculated polypropylene 30
Hollow glass micropearl 1
Nucleator NA-45 0.5
Oxidation inhibitor DSTP 0.5
Antioxidant 1010 0.5
Embodiment 3
The content of regulating polypropylene grafted thing/polycarbonate (80/20) is weight fraction about 30, and concrete component is as follows, and all the other are with embodiment 1.Testing its performance lists in the table 1.Concrete component is as follows:
Glass fibre 70
Maleic anhydride inoculated polypropylene/polycarbonate 30
Nucleator NA-9930T 1
Oxidation inhibitor DSTP 0.5
Antioxidant 1010 0.5
Embodiment 4
The content of regulating maleic anhydride inoculated polypropylene/polycarbonate (80/20) is weight fraction about 30, and concrete component is as follows, and all the other are with embodiment 1.Testing its performance lists in the table 1.Concrete component is as follows:
Glass fibre 70
Maleic anhydride inoculated polypropylene/polycarbonate 30
Hollow glass micropearl 10
1,3:2,4-two (benzylidene)-D-sorbyl alcohol 0.06
Oxidation inhibitor DSTP 0.5
Antioxidant 1010 0.5
Embodiment 5
With 6,1 kilograms of hollow glass micropearls of 70 kilograms nylon, 1.5 kilograms of nucleator NA-45,0.5 kilogram of antioxidant 1010,0.5 kilogram of oxidation inhibitor DSTP mixes, and places the high pressure static electricity fluidized-bed.30 kilograms of glass fibre are passed through from fluidized-bed continuously.The electrostatic potential of regulating fluidized-bed makes the weight fraction of nylon 6 remain on 70 to regulate the amount of glass fibre polymeric adsorbent.The glass fibre that is adsorbed with resin passes through from baking oven and high temperature die head continuously, passes through multi-rolling mill again, and compacting is into about the sheet material of 1mm thickness.Continuous sheet is cut into the sheet material of certain-length and width, according to the vertical and horizontal sheet material number of plies than being n: ratio (n-1) is arranged, and places mould, at 210 ℃, is pressed into plate under the pressure of 16Mpa.Plate is processed into stretching, crooked and impact batten by GB, tests its performance and list in the table 1.
To intensity and inflexible effect, two comparing embodiments of special row are as follows in this material for explanation adding hollow glass micropearl and nucleator better.
Comparative example 1
In this comparative example, do not add glass microballon and nucleator.Its concrete component is as follows, and all the other together
Embodiment 1.
Glass fibre 30
Maleic anhydride inoculated polypropylene 70
Oxidation inhibitor DSTP 0.5
Antioxidant 1010 0.5
Comparative example 2
In this comparative example, do not add glass microballon and nucleator.Its concrete component is as follows, and all the other together
Embodiment 1.
Glass fibre 70
Maleic anhydride inoculated polypropylene 30
Oxidation inhibitor DSTP 0.5
Antioxidant 1010 0.5
Each embodiment of table 1 and comparative example performance
Claims (10)
1. continuous fiber reinforced thermoplastic composite material is characterized in that comprising following component and parts by weight content:
Continuous fibre 25～80
Thermoplastic resin 20～75
Glass microballon 0～10
Nucleator 0.05～1.5.
2. continuous fiber reinforced thermoplastic composite material according to claim 1 is characterized in that, said thermoplastic resin comprises current commercial all thermoplastic resin kinds.
3. continuous fiber reinforced thermoplastic composite material according to claim 2, it is characterized in that, said thermoplastic resin comprises a kind of and composition thereof in nylon, polycarbonate, polypropylene, polyethylene, polystyrene type, polyphenylene oxide, polyphenylene sulfide, polyoxymethylene, the polymethylmethacrylate or resin alloy.
4. continuous fiber reinforced thermoplastic composite material according to claim 2 is characterized in that, said thermoplastic resin is the blend of polypropylene grafted thing or polypropylene and polycarbonate.
5. continuous fiber reinforced thermoplastic composite material according to claim 1 is characterized in that said continuous fibre comprises one or more in glass fibre, carbon fiber, the steel fiber.
6. continuous fiber reinforced thermoplastic composite material according to claim 5 is characterized in that, continuous fibre is to exist in a continuous manner in sheet material.
7. continuous fiber reinforced thermoplastic composite material according to claim 1 is characterized in that said glass microballon is a hollow minute particle, and sky contains rare gas element.
8. continuous fiber reinforced thermoplastic composite material according to claim 7 is characterized in that, said glass microballon particle size range is 10～250um, and tap density is 0.35～0.45g/cm
3
9. continuous fiber reinforced thermoplastic composite material according to claim 1, it is characterized in that described nucleator comprises a kind of and composition thereof in talcum powder, silicon-dioxide, kaolin, monobasic or polycarboxylate, organophosphate, diphenylmethylene sorbyl alcohol or the rosin.
10. continuous fiber reinforced thermoplastic composite material according to claim 1 is characterized in that, said nucleator is moulded the NA series nucleator that macromolecular material company limited produces for Shanghai section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031422063A CN100404593C (en) | 2003-08-11 | 2003-08-11 | Continuous fiber reinforced thermoplastic composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031422063A CN100404593C (en) | 2003-08-11 | 2003-08-11 | Continuous fiber reinforced thermoplastic composite material |
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| Publication Number | Publication Date |
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| CN1580099A true CN1580099A (en) | 2005-02-16 |
| CN100404593C CN100404593C (en) | 2008-07-23 |
Family
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| CNB031422063A Expired - Fee Related CN100404593C (en) | 2003-08-11 | 2003-08-11 | Continuous fiber reinforced thermoplastic composite material |
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| CN102532681A (en) * | 2010-12-14 | 2012-07-04 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flame-retardant continuous fiber reinforced polypropylene composite material and preparation method thereof |
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2003
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