CN1429701A - Manufacturing method of continuous long fiber reinforced reaction type resin - Google Patents
Manufacturing method of continuous long fiber reinforced reaction type resin Download PDFInfo
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- CN1429701A CN1429701A CN 01145281 CN01145281A CN1429701A CN 1429701 A CN1429701 A CN 1429701A CN 01145281 CN01145281 CN 01145281 CN 01145281 A CN01145281 A CN 01145281A CN 1429701 A CN1429701 A CN 1429701A
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- Prior art keywords
- continuous long
- long fiber
- fiber reinforced
- reaction type
- type resin
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Links
- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 239000000835 fiber Substances 0.000 title claims description 72
- 238000006757 chemical reactions by type Methods 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 27
- 239000000284 extract Substances 0.000 claims description 18
- 238000002803 maceration Methods 0.000 claims description 18
- 238000007598 dipping method Methods 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- -1 methyl acrylic ester Chemical class 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 238000007493 shaping process Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229920005479 Lucite® Polymers 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical class OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WCJQKTUPBIICNI-UHFFFAOYSA-N octoxycarbonyloxyperoxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOOOC(=O)OCCCCCCCC WCJQKTUPBIICNI-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Abstract
A continuous long fibre-reinforced reactive resin product is made up from the monomer able to be polymerized by free radicals through immersing long fibres, pre-shaping by a mould, microwave reactive cavity for polymerizing and curing, moulding, cooling and solidifying. Its advantages are high polymerizing speed, and high adhesion between fibres and resin.
Description
Technical field
The present invention relates to the manufacture method of resin, relate in particular to a kind of manufacture method of continuous long fiber reinforced reaction type resin.
Background technology
Manufacturing fiber-reinforced thermoplastic resin method in common the most is exactly by screw extruder, resin melting and fiber extrusion molding.Because the shear action of screw rod, fiber are cut off and become very short (approximately 0.3-0.5mm), have limited the performance of fiber as reinforcing material.In addition, screw rod is extruded needs high temperature, and melt viscosity is very big, makes resin be difficult to soak into fiber, also just is difficult to obtain resin-fiber good composite that bonds.Secondly, be difficult to every fiber surface is carried out surface treatment, improve resin and combine with the interface of fiber and improve performance of composites.
By continuous fiber reinforced thermoplastic resin, and resin can well soak into fiber and make the interface of the two that good bonding be arranged, and is expected to improve greatly the strength and toughness of material.Can make the material that continuous fiber strengthens by pultrude process now.The dipping of fiber is mainly by melt impregnation and powder impregnation, as United States Patent (USP): U.S.Pat.4,640,861; U.S.Pat.4,828,776.Melt impregnation be fiber by dipping tank, by molten resin liquid dipping, under the effect of tractive force, make the fibre reinforced materials of a definite form by mould molding, curing, cooling.This method often needs high temperature so that resin fusion and keep the dipping of certain viscosity in order to fiber, but be difficult to obtain desirable effect of impregnation may owing to melt resin viscosity is very big, resin-fiber is difficult to obtain desirable must the bonding, and the composite of making is prone to phenomenon such as reel off raw silk from cocoons.Powder impregnation more is difficult to obtain desirable composite by its characteristics.All these is owing to resin causes the fiber-resin interface in conjunction with bad to the wellability of fiber inadequately.
By low viscous polymerisable monomer or oligomer, impregnation of fibers then polymerization forming prepares the existing a lot of patent reports of continuous fiber reinforced composite materials.As United States Patent (USP): U.S.Pat5,891,560, but these resins mostly are some thermosetting resins such as epoxy resin, phenolic resins, polyurethane resin etc.Polymer monomer is in liquid or has lower fusing point because molecular weight is little under the normal temperature, have very little viscosity, and this is very beneficial for the infiltration of fiber, and fiber and resin have good interface.Recently occur making the patent of fibre reinforced composites by pultrude process, as patent: U.S.Pat.5,935,508, EP0,290,849 by radiation polymerization such as ultra-violet radiation polymerization.By light trigger, under the irradiation of ultraviolet rays, cause acrylic monomer or epoxies open loop monomer polymerization, make fibre reinforced composites by pultrude process.This new technology greatly reduces the viscosity of maceration extract, has improved the saturating machine of fiber, and can carry out at a lower temperature.But the light radiation initiated polymerization owing to be subjected to the restriction of light penetration capacity, can only make extremely thin sample, is difficult to make thicker material, thereby application is restricted.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists that a kind of technology is simple, energy consumption is lower, the manufacture method of continuous long fiber reinforced reaction type resin that fiber and resin-bonded property are good.
Purpose of the present invention can be achieved through the following technical solutions: the manufacture method of continuous long fiber reinforced reaction type resin, it is characterized in that, comprise following processing step: (1) preparation maceration extract, the alkene monomer that can carry out radical polymerization is as maceration extract, and the alkene monomer that perhaps can carry out radical polymerization dissolves the resin of back formation as maceration extract with the thermoplastic polymer that can be dissolved in this monomer; (2) dipping is long fine, and continuous long fiber is being flooded in above-mentioned maceration extract under 10～50 ℃ the temperature; (3) hot briquetting will be passed through mould through the continuous long fiber of above-mentioned dipping, and via microwave reaction chamber heated polymerizable curing molding, obtain the continuous long fiber reinforced reaction type resin product after the cooling.
Also comprise continuous long fiber is carried out surface treatment and stoving process, this technology is located at before the described impregnation technology.
Described alkene monomer is a methyl acrylic ester, or the simple function group alpha-olefin, or the polyfunctional group alkene monomer.
Described methyl acrylic ester is selected from one or more in methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester, GMA, dimethylaminoethyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid benzene methyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate, maleic anhydride, the furoate clothing.
Described simple function group alpha-olefin is selected from that styrene, propylene are fine, in the methyl styrene one or more.
Described polyfunctional group alkene monomer is selected from divinylbenzene, glycol diacrylate, propylene glycol diacrylate, the terephthalic acid (TPA) two propylene esters one or more.
According to the needs of material can be above appropriate combination that may monomer, can add a certain amount of polyfunctional monomer, makes resin be improved the serviceability of material by to a certain degree crosslinked.
Described thermoplastic polymer be selected from polymethyl methacrylate, methacrylate homopolymers and two, three or the copolymer of multiple copolymer, polystyrene or styrene and other monomers, ABS resin, MBS resin in one or more.
Can also add antioxidant, fire retardant and calcium carbonate, white carbon black, clay, diatomite, graphite packing in the described maceration extract.The adding of these additives and filler can be satisfied the different requirements of material, as antioxygen, anti-flammability, shrinkage etc.
Described continuous long fiber is selected from one or more in glass fibre, carbon fiber, organic polymer fiber, fiber cloth, the glass felt.
The present invention through microwave radiation polymerization, makes fiber-resin composite by pultrude process by the monomer of free redical polymerization.Comprise that continuous fiber is through the dipping tank dipping, by mould preformed, via microwave reaction chamber polymerizing curable, by the mould molding cooling curing.Can make forms such as bar-shaped, tubulose, abnormal shape according to the difference of mould, also can pelletizing as extruding intermediate.Compared with prior art, the present invention has the following advantages:
1. fiber floods under room temperature or lower temperature, and maceration extract viscosity is lower, and fiber wetness is good, and dipping rapidly can impregnation of fibers cloth, fibrofelt etc.
2. polymerization speed is fast, and sample is not subjected to the restriction of thickness, and sample interior and outside polymerization are even.
3. resin and fiber caking property are good, have the combination of extraordinary interface, and fiber plays good humidification.
4. microwave polymerization, consumed energy is low, energy savings.
The continuous long fibre of the present invention can be surface treated, also can be not surface treated.By the maceration extract dipping that contains a kind of free radical polymerizable monomer at least, maceration extract at room temperature or lower temperature (＜50 ℃) has lower viscosity and than long stabilization time, fiber has very fast good wellability like this.
According to the prescription of maceration extract, the resin of composite can be linear, also can be crosslinked, is that thermoplasticity or thermosetting are applicable to different demands thereby demonstrate material.
Can be used for resin of the present invention can be some thermoplastic polymers, and these resins are dissolved in above-mentioned possibility monomer, and concentration can be 0%-50%, and viscosity is adjustable as requested, can regulate accordingly according to the amount of resin of composite, is beneficial to the dipping of fiber.
Resin of the present invention also can be the performed polymer of one or more monomers.The polymerization under suitable temperature of monomer and initator obtains the performed polymer of certain conversion ratio, certain viscosity, and its viscosity is generally at 0.1～5Pas, and optimum viscosity should be at 0.5～2Pas.
The required initator of above polymerisable monomer polymerization can use the azo-bis-isobutyl cyanide of some initators commonly used such as azo class, and peroxide is as dibenzoyl peroxide.Also can be some active initators as free agent initators such as the peroxidating isooctyl acid tert-butyl esters of the dioctyl peroxy dicarbonate of peroxy dicarbonates, peroxycarboxylic acid esters.It also can be oil-soluble oxidation-reduction initiator.The consumption of initator is generally the 0.1%-5.0% of amount of monomer among the present invention.
The used fiber of the present invention can be handled its surface, and used inorganic agent is the coupling agent that organo-silicon coupling agent, titanate coupling agent or other can be handled fiber surface.These crosslinking agents mainly comprise: ethyl orthosilicate, methyl (alkyl such as ethyl, propyl group, phenyl) front three-(second, the third gradegrade C) TMOS, glycidyl front three (second, the third gradegrade C) TMOS, methacryloxypropyl front three (second, the third gradegrade C) TMOS (KH570/A-174), vinyl front three (second, the third gradegrade C) TMOS (A-151), tetrabutyl titanate etc.Coupling agent is made into certain density solution impregnation fiber, then the oven dry make fiber surface be connected with a certain amount of coupling agent, improved fiber and resin-based interface interaction, thus make fiber and resin-based have extraordinary bonding and the raising material performance.
The microwave generator of wanting required for the present invention can be the microwave applicator of the adjustable power of CF (as 2450MHz), also can be the pulsed microwave applicator.Microwave applicator can make mould produce uniform electric magnetic field, evenly heats so that have the monomer of dielectricity, and polymerisation is carried out rapidly uniformly.Use microwave applicator can improve the speed of polymerisation to be fit to the demand of pultrude process.In addition, by heating using microwave, can make the inner and outside while of sample and uniform heating, the different phenomenon of internal and external temperature that is produced by the heat conducting existence of resin that does not exist common heating to cause makes polymerisation inside and outside inhomogeneous.Therefore can make thick massive article.
Mould can be that the material that no microwave absorbs is made, as: polytetrafluoroethylene (PTFE), glass, pottery etc.With polytetrafluoroethylmaterial material the best, it can provide good lubricity and good release property, does not need to add in material releasing agent.Mould of the present invention can provide pressure to reduce the rapid rising of polymerization single polymerization monomer Yin Wendu and the monomer volatilization that causes in whole microwave heating chamber like this, improves the utilization rate of monomer.Mould can be according to the demand of material requested, can be designed to excellent type, plate or shape that other is possible.
The resulting composite of the present invention can carry out pelletizing by Len req, as extruding intermediate, carries out the blend extrusion molding with other polymer.Like this through the fiber of resin-coating, can keep former length and further do not cut off and obtain long fine reinforced composite materials.Also can design difform mould, that pultrusion goes out is bar-shaped, the composite of sheet material, profile shapes or other shapes.
Description of drawings
Fig. 1 is a process chart of the present invention.
The specific embodiment
Below in conjunction with drawings and the specific embodiments, the invention will be further described.
As shown in Figure 1; microwave radiation polymerization of the present invention prepares the technological process of continuous fibre enhancement resin method; the preparation process of composite is that fibre bundle is drawn from creel 1; under the traction of hauling machine 8; carry out surface treatment through the process chamber 2 that fills surface conditioning agent, by dryer 3 oven dry, through impregnation chamber 4 dippings; impregnated fiber enters mould 7 and react moulding under the effect of microwave generator 5, then as requested by the pelleter pelletizing.The two ends of mould 7 are in the outside of microwave cavity 6, and the evaporation leakage of polymerization single polymerization monomer is increased operation rate when heating to reduce, and prevent the pollution to microwave cavity.
Embodiment 1
The polymethyl methacrylate of 20 parts of weights (lucite) is dissolved in the methyl methacrylate monomer of 80 parts of weights under heating, adds the azo-bis-isobutyl cyanide (AIBN) of 1 part of weight, dissolving is as maceration extract.The non-twist glass fibre of low alkali, flood in the acetone soln of ethyl trimethoxy silane 10%, oven dry then, through the impregnation chamber dipping, under the traction of hauling machine, enter mould, transferring the power of microwave applicator is 500W, and obtaining diameter is the polymethyl methacrylate of the bar-shaped continuous fiber enhancing of 2mm.
Embodiment 2
The high impact styrene of 25 parts of weights (HIPS) is dissolved in the methyl methacrylate and EHMA mix monomer of 75 parts of weights under heating, add 5 parts of heavy terephthalic acid (TPA) two propylene esters dissolvings, the peroxidating isooctyl acid tert-butyl ester (TBPO) that adding monomer 1.5% then weighs, dissolving is as maceration extract.The non-twist glass fibre of low alkali, flood in the acetone soln of the vinyltrimethoxy silane 10% (A-151), oven dry then, through the impregnation chamber dipping, under the traction of hauling machine, enter mould, transferring the power of microwave applicator is 500W, and obtaining diameter is the crosslinked high-impact composite of the bar-shaped continuous fiber enhancing of 2mm.
Embodiment 3
100 parts of heavy propylene glycol diacrylates are dissolved with the azo-bis-isobutyl cyanide (AIBN) of 1 part of weight as maceration extract, the glass fibre that handle through silane coupler-methyl allyl acyloxypropyl trimethoxysilane on the dipping surface, through extruder, under microwave applicator 600W, obtain the same with thermosetting compound material that glass strengthens.
Embodiment 4
The methyl methacrylate of 75 parts of weights, the Isooctyl acrylate monomer of 25 parts of weights, 1.5 parts of heavy dibenzoyl peroxides are polymerized to viscosity under 65 ℃ be 0.8Pas, cooling stops polymerisation, is preserving below 20 ℃.Impregnation of carbon fibers under the traction of hauling machine,, obtains through the carbon fiber reinforced thermoplastic resin under 650w through mould.
Embodiment 1～4 is test data as a result
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Fiber content % | ????65 | ????70 | ????50 | ????60 |
| Hot strength MPa | ????805 | ????623 | ????1035 | ????1230 |
| Bending strength MPa | ????466 | ????121 | ????546 | ????518 |
| Bending modulus GPa | ????18 | ????13 | ????31 | ????25 |
Claims (9)
1. the manufacture method of continuous long fiber reinforced reaction type resin, it is characterized in that, comprise following processing step: (1) preparation maceration extract, the alkene monomer that can carry out radical polymerization is as maceration extract, and the alkene monomer that perhaps can carry out radical polymerization dissolves the resin of back formation as maceration extract with the thermoplastic polymer that can be dissolved in this monomer; (2) dipping is long fine, and continuous long fiber is being flooded in above-mentioned maceration extract under 10～50 ℃ the temperature; (3) hot briquetting will be passed through mould through the continuous long fiber of above-mentioned dipping, and via microwave reaction chamber heated polymerizable curing molding, obtain the continuous long fiber reinforced reaction type resin product after the cooling.
2. the manufacture method of continuous long fiber reinforced reaction type resin according to claim 1 is characterized in that, also comprises continuous long fiber is carried out surface treatment and stoving process, and this technology is located at before the described impregnation technology.
3. the manufacture method of continuous long fiber reinforced reaction type resin according to claim 1 is characterized in that, described alkene monomer is a methyl acrylic ester, or the simple function group alpha-olefin, or the polyfunctional group alkene monomer.
4. the manufacture method of continuous long fiber reinforced reaction type resin according to claim 3, it is characterized in that described methyl acrylic ester is selected from methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester, GMA, dimethylaminoethyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, the methacrylic acid benzene methyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate, maleic anhydride, in the furoate clothing one or more.
5. the manufacture method of continuous long fiber reinforced reaction type resin according to claim 3 is characterized in that, described simple function group alpha-olefin is selected from that styrene, propylene are fine, in the methyl styrene one or more.
6. the manufacture method of continuous long fiber reinforced reaction type resin according to claim 3, it is characterized in that described polyfunctional group alkene monomer is selected from divinylbenzene, glycol diacrylate, propylene glycol diacrylate, the terephthalic acid (TPA) two propylene esters one or more.
7. the manufacture method of continuous long fiber reinforced reaction type resin according to claim 1, it is characterized in that, described thermoplastic polymer be selected from polymethyl methacrylate, methacrylate homopolymers and two, three or the copolymer of multiple copolymer, polystyrene or styrene and other monomers, ABS resin, MBS resin in one or more.
8. the manufacture method of continuous long fiber reinforced reaction type resin according to claim 1 is characterized in that, can also add antioxidant, fire retardant and calcium carbonate, white carbon black, clay, diatomite, graphite packing in the described maceration extract.
9. the manufacture method of continuous long fiber reinforced reaction type resin according to claim 1 is characterized in that, described continuous long fiber is selected from one or more in glass fibre, carbon fiber, organic polymer fiber, fiber cloth, the glass felt.
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