CN107163478A - Can first heat cure, again unsaturated resin composition of light irradiation solidification and its production and use - Google Patents
Can first heat cure, again unsaturated resin composition of light irradiation solidification and its production and use Download PDFInfo
- Publication number
- CN107163478A CN107163478A CN201710498080.1A CN201710498080A CN107163478A CN 107163478 A CN107163478 A CN 107163478A CN 201710498080 A CN201710498080 A CN 201710498080A CN 107163478 A CN107163478 A CN 107163478A
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- China
- Prior art keywords
- unsaturated
- resin
- compound
- resin composition
- composition
- Prior art date
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- Granted
Links
- 238000007711 solidification Methods 0.000 title claims abstract description 59
- 230000008023 solidification Effects 0.000 title claims abstract description 59
- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 238000013007 heat curing Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 238000001723 curing Methods 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000003822 epoxy resin Substances 0.000 claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 230000009477 glass transition Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000005286 illumination Methods 0.000 claims abstract description 14
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 150000003254 radicals Chemical class 0.000 claims abstract description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 43
- -1 styrene compound Chemical class 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 21
- 229930185605 Bisphenol Natural products 0.000 claims description 20
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 15
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 15
- 239000003063 flame retardant Substances 0.000 claims description 15
- 150000002989 phenols Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims description 14
- 239000004917 carbon fiber Substances 0.000 claims description 13
- 229940106691 bisphenol a Drugs 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229920001169 thermoplastic Polymers 0.000 claims description 10
- 239000004416 thermosoftening plastic Substances 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000012965 benzophenone Substances 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 230000002708 enhancing effect Effects 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920003986 novolac Polymers 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 4
- 150000002460 imidazoles Chemical group 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- YDZIKFNRHXVDKZ-UHFFFAOYSA-N 1-phenylprop-2-ene-1-thiol Chemical compound C=CC(S)C1=CC=CC=C1 YDZIKFNRHXVDKZ-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000012796 inorganic flame retardant Substances 0.000 claims description 3
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000003642 hunger Nutrition 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims 2
- 230000031709 bromination Effects 0.000 claims 2
- 238000005893 bromination reaction Methods 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000010425 asbestos Substances 0.000 claims 1
- 239000010426 asphalt Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 230000002301 combined effect Effects 0.000 claims 1
- 150000001896 cresols Chemical class 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 229910052895 riebeckite Inorganic materials 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002131 composite material Substances 0.000 description 14
- 239000003292 glue Substances 0.000 description 13
- 239000004744 fabric Substances 0.000 description 7
- 229960003742 phenol Drugs 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- WYJABVVUXLVWOD-UHFFFAOYSA-N C=CC(C)=C.C(C=CC1=CC=CC=C1)(=O)O Chemical compound C=CC(C)=C.C(C=CC1=CC=CC=C1)(=O)O WYJABVVUXLVWOD-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical class OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(*)C(*)=C(*)[C@](*)CC(C)(C)*1(CC1)C(*)C(*c1cc(N)c(*)c(*)c1*)C(C)(C)C Chemical compound CCC(*)C(*)=C(*)[C@](*)CC(C)(C)*1(CC1)C(*)C(*c1cc(N)c(*)c(*)c1*)C(C)(C)C 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JEWRDQQMVIKXLO-UHFFFAOYSA-N buta-1,3-diene;4-ethenylphenol Chemical compound C=CC=C.OC1=CC=C(C=C)C=C1 JEWRDQQMVIKXLO-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical compound OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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Abstract
The present invention relates to can first heat cure, again unsaturated resin composition of light irradiation solidification and its production and use, it is characterised in that：The unsaturated resin composition is combined through chemical reaction by several monomeric substance and obtained, the several monomeric substance includes unsaturated-resin, epoxy resin, cure-crosslinking agent, curing accelerator and light trigger, and the weight/mass percentage composition of the material composition is：Unsaturated-resin 40 80%, epoxy resin 5 40%, cure-crosslinking agent 0.5 20%, curing accelerator 0.01 1% and light trigger 1 5%；With thermoplastic resin performance, used as simple thermoplastic resin and solidification crosslinking is carried out under the conditions of epoxy resin, can be under light trigger, UV illumination conditions containing unsaturated C=C keys, trigger free radical to carry out cross-linking reaction, obtain the high compound of crosslink density；The compound has high glass-transition temperature, high-fire resistance, high-intensity performance.The characteristics of present invention has high heat-resisting, high intensity and high accuracy and possesses post-forming process ability and beneficial effect.
Description
Technical field
The present invention relates to a kind of unsaturated resin composition, particularly it is a kind of can first heat cure, light irradiation solidification is not again
Saturated resin composition and its production and use, it is adaptable to high intensity, high heat-resisting, high glass-transition temperature place.
Belong to technical field of chemical products.
Background technology
At present, light-cured resin and heat reactive resin are used widely in different field.Light-cured resin is one
Plant under UV optical conditions, light trigger reaction generation free radical, then the resin that oligomer solidification is crosslinked is triggered by free radical.It is consolidated
Compound typically has the advantages that case hardness is high, chemical-resistant is good, weatherability is good, has been widely used for coating, ink, modeling
The fields such as material.But there are the following problems for the light-cured resin：(1) glass transition temperature is relatively low, high temperature resistant it is hot it is not enough,
Solidfied material surface smoothness is low；(2) if Photocurable composition makes special-shaped products, it is difficult to ensure the precision of special-shaped products.Greatly
Its purposes and application field are limited greatly.Thermosetting resin is smooth in glass transition temperature, rigidity, heat resistance, intensity, product
Property in terms of it is advantageous, but exist can not post-forming process the problem of.
Therefore, it is necessary to develop a kind of thermal curable and the undersaturated resin combination of photocuring simultaneously.
The content of the invention
An object of the present invention, is that to there is glass transition temperature relative in order to solve the light-cured resin of prior art
Hot not enough, the solidfied material surface smoothness of relatively low, high temperature resistant is low and heat reactive resin exist can not post-forming process the problem of,
Offer is a kind of can first heat cure, the unsaturated resin composition of light irradiation solidification again.It is high, high resistance to glass transition temperature
Heat, high intensity and high accuracy and the characteristics of possess post-forming process ability.
The second object of the present invention, be to provide for it is a kind of can first heat cure, the unsaturated-resin group of light irradiation solidification again
The preparation method of compound.
The third object of the present invention, be for provide it is a kind of can first heat cure, light irradiation solidification again unsaturated-resin combination
The purposes of thing.
An object of the present invention can be reached by adopting the following technical scheme that：
Can first heat cure, the unsaturated resin composition of light irradiation solidification again, it is characterised in that：The unsaturated-resin is combined
Thing is combined through chemical reaction by several monomeric substance and obtained, and the several monomeric substance includes unsaturated-resin, epoxy
Resin, cure-crosslinking agent, curing accelerator and light trigger, the weight/mass percentage composition of the material composition is：Unsaturated-resin
40-80%, epoxy resin 5-40%, cure-crosslinking agent 0.5-20%, curing accelerator 0.01-1% and light trigger 1-5%；
It is dissolvable in water organic solvent；With thermoplastic resin performance, used as simple thermoplastic resin and in epoxy resin condition
Lower progress solidification crosslinking, shows the property between thermoplastic and thermosetting resin；, can be in light containing unsaturated C=C keys
Under initiator, UV illumination conditions, trigger free radical to carry out cross-linking reaction, obtain the high compound of crosslink density；The compound has
There are high glass-transition temperature, high-fire resistance, high-intensity performance.
An object of the present invention can also be reached by adopting the following technical scheme that：
Further, unsaturated-resin is represented with below general formula (I)：Formula I
The monomeric substance is comprising styrene compound and by its derivative compound, alkadiene compound and by it
Derivative compound；The styrene compound and by its derivative compound, can be represented by formula II, wherein each R bases
It is independently hydrogen, hydroxyl, amino, carboxyl, C1-C9 alkyl or alkoxy, bromine, phosphorus, DOPO；
Formula II
The alkadiene compound and by its derivative compound, can be represented by general formula III, wherein each R1 bases are independent
Ground can represent hydrogen, methyl, phenyl, bromine；
General formula III
Further, the epoxy resin can be bisphenol-A, Bisphenol F, bis-phenol M, bis-phenol P, bis-phenol E, phenol novolac epoxy
Compound, cresol novolac epoxy compound, dicyclopentadiene phenolic epoxide, tetramethyl Bisphenol F, bisphenol-A phenolic epoxy
Compound, brominated bisphenol A, brominated phenol novalac epoxy, 3 function phenols, 4 function phenols, naphthalene type phenols or biphenyl type
One or two or more kinds of combinations in phenols epoxy resin；Preferably, it can be bisphenol-A, Bisphenol F, bis-phenol M, bis-phenol P, bis-phenol
One or two or more kinds of combinations in E, phenol novolac epoxy resins.
Further, the curing agent can be amine curing agent, hydrazides class curing agent, lewis acid-amine complex class
Curing agent, acid anhydride type curing agent, one or two or more kinds of combinations of phenolic curing agent.
Further, the curing accelerator be imidazoles accelerator, peroxide accelerator, azo accelerator,
One or two or more kinds of groups in tertiary amines accelerator, phenol accelerant, organic metal salt accelerator, inorganic metal salt accelerator
Close.
Further, the light trigger can be benzoin derivatives, benzil ketals derivative, dialkoxy benzene second
Ketone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide, esterification assimilation compound, aryl peroxide ester compounds, halo
One or two or more kinds of combinations in methyl arone, sulfur-containing organic compound, benzoyl formiate.Preferably, from acylphosphanes
Oxide, alpha-hydroxyalkyl benzophenone, one or two or more kinds of combinations of benzil ketals derivative.
Further, material composition can also be added as needed on fire retardant, surface conditioning agent.The fire retardant, can be with
It is phosphorus flame retardant, nitrogenated flame retardant, bromide fire retardant, inorganic flame retardant etc..May be selected from organic phosphorus compound, nitrogenous three
Piperazine compound, brominated epoxy resin, tetrabromo-phthalic diformamide and one kind or two kinds of collocation groups in inorganic aluminium hydroxide
Close；The surface conditioning agent includes silane coupler, size or defoamer.
The second object of the present invention can be reached by adopting the following technical scheme that：
Can first heat cure, the preparation method of the unsaturated resin composition of light irradiation solidification again, it is characterised in that：By certainly
It is polymerize by base and is obtained, specifically includes following steps：
1) under normal temperature and pressure conditionses, polymer solvent is added in reactor；
2) weight/mass percentage composition is pressed by unsaturated-resin, epoxy resin, cure-crosslinking agent, curing accelerator and light trigger
Add in reactor, the weight/mass percentage composition of the material composition is：It is unsaturated-resin 40-80%, epoxy resin 5-40%, solid
Change crosslinking agent 0.5-20%, curing accelerator 0.01-1% and light trigger 1-5%；In 100-500 revs/min of stirring condition
It is lower to be dissolved, mixed solution is made；
3) by step 2) obtained mixed solution under anaerobic, be heated to 60-120 DEG C, react 0.5-3 hour, make
Unsaturated resin composition liquid；
4) unsaturated resin composition liquid made from step (3) is filtered, solidified, then cleaned, dried,
Be made can first through heat cure, again UV light irradiations solidification unsaturated resin composition.
The second object of the present invention can also be reached by adopting the following technical scheme that：
Further, the polymer solvent can be the one of hexamethylene, butanone, cyclohexanone, methanol, toluene, dimethylbenzene etc.
Plant or several；Described styrene compound and the mass ratio of alkadiene compound are：30-60%:40-70%；It is described
Initiator includes but is not limited to various lithium alkylides such as n-BuLi, the organic peroxide such as cyclohexanone peroxide of anionic polymerisation
Deng；Mass ratio of the initiator addition scope control in 0.1%-3%；The solvent include but is not limited to butanone, cyclohexanone,
The one or more of toluene, dimethylbenzene, propylene glycol monomethyl ether etc.；The activator includes but is not limited to such as tetrahydrofuran, vinyl
Benzyl mercaptan, lauryl mercaptan etc., the addition of activator are 2-5% mass ratio.
Further, prepare it is described can first through heat cure, the unsaturated resin composition of UV light irradiations solidification again, may be used also
According to regulation viscosity, the function of dissolved compound, to add organic solvent, organic solvent is not calculated in thermoset composition composition
It is interior, regulation viscosity, dissolved compound and the function of adjusting outward appearance are only served, in process of production by whole by way of heating
Drive out of.Organic solvent can be n-butanol, butanone, toluene, dimethylbenzene, propylene glycol monomethyl ether, propylene glycol methyl ether acetate etc..It is above-mentioned
Solvent can be used alone one kind, two kinds or two or more can also be used in mixed way.
The third object of the present invention can be reached by adopting the following technical scheme that：
Can first heat cure, the purposes of the unsaturated resin composition of light irradiation solidification again, it is characterised in that：Obtained insatiable hunger
With molecular resin amount in 4,000-200,000, molecule containing the group that polarized is big, including hydroxyl or amino, be dissolvable in water
Machine solvent；With thermoplastic resin performance, use and carried out under the conditions of epoxy resin certain as simple thermoplastic resin
The solidification crosslinking of degree, shows the property between thermoplastic and thermosetting resin；, can be in light containing unsaturated C=C keys
Under initiator, UV illumination conditions, trigger free radical to carry out cross-linking reaction, obtain the higher compound of crosslink density；The compound
High glass-transition temperature, high-fire resistance, high intensity.
Further, for preparing prepreg and laminate：
Prepreg, refers to that enhancing base materials are impregnated or coated with above-mentioned unsaturated resin composition to be formed, can be various
Used in the fields such as moulding material, supporting material.The enhancing base materials can be glass fibre, carbon fiber, silicon carbide fibre, stone
Cotton fiber, superhigh molecular weight polyethylene fibers, aramid fiber etc.；Unsaturated resin composition impregnates to above-mentioned enhancing base materials
Or after coating, in order to drive solvent out of and unsaturated resin composition is reached semi-solid preparation, it will usually in 100-250 DEG C of temperature range
It is interior, heat 1-3 minutes, so that prepreg is made, counted by 100 mass parts of prepreg, unsaturated-resin in drier
The content in prepreg of composition is preferably 25-95%.
Further, can be with compression molding, mold shape, die size etc. by prepreg made from the above method
It can be selected, be solidified 0.5-2 hours in the range of 100-250 DEG C of selection according to application field, shape, size required for being made
Low solidfied material, then UV intensities of illumination be 100-300uW/cm2Irradiation solidification 0.5-60 minutes；Moulding material can be applicable to army
The fields such as work, Aero-Space, sports goods, vehicle.
Further, the thickness requirement of prepreg made from the above method as required is laminated, and according to
Way configures in its one side or upper and lower surface and is laminated mould release membrance, in blocks in certain temperature, pressure, the shaping of vacuum condition laminated
Material, sheet material has a post-forming process ability, carries out after secondary or multiple processing and forming, shape required for being made, size it is low
Solidfied material, then UV further solidify.Moulding material can be applied to the fields such as military project, Aero-Space, sports goods, vehicle；It is used
Release film type and thickness do not limit；For lamination, temperature is 100-350 DEG C, pressure is 0.1-10PMa, vacuum 0-
100 millimetress of mercury, heat time are 0.5-5 hours；For UV conditions of cure：Intensity of illumination 100-300uW/cm2Irradiation solidification
0.5-60 minutes.
The present invention has beneficial effect prominent as follows：
1st, it is of the present invention can first heat cure, the unsaturated resin composition of light irradiation solidification again, be dissolvable in water organic
Solvent；With thermoplastic resin performance, used as simple thermoplastic resin and solidification friendship is carried out under the conditions of epoxy resin
Connection, shows the property between thermoplastic and thermosetting resin；, can be in light trigger, UV light containing unsaturated C=C keys
According under the conditions of, trigger free radical to carry out cross-linking reaction, obtain the high compound of crosslink density；There is the compound high-vitrification to turn
Temperature, high-fire resistance, high-intensity performance；There is glass transition temperature therefore, it is possible to the light-cured resin that solves prior art
Hot not enough, the solidfied material surface smoothness of relatively low, high temperature resistant is low and heat reactive resin exist can not post-forming process
Problem, with high glass transition temperature, high heat-resisting, high intensity and high accuracy and the characteristics of possess post-forming process ability
And beneficial effect.
2nd, the present invention is a kind of thermal curable and undersaturated resin combination of photocuring simultaneously, said composition be first heated into
Post-forming process ability is also equipped with after the solidification of row certain proportion and degree, heat cure, after post forming or repeatedly shaping again
Further solidify through UV light irradiations, product has high glass transition temperature, high heat-resisting, high intensity and high accuracy, combines
Heat cure and the advantage of photocuring, resulting product can be widely applied to the fields such as military project, Aero-Space, sports goods and vehicle.
3rd, the present invention can first carry out a certain proportion of heat cure, because solidification ratio is relatively low, with post forming plus
Product after further solidifying after work ability, processing and forming through UV has high glass transition temperature, high heat-resisting, high intensity
And high accuracy, the advantage of heat cure and photocuring is combined, and impart the ability of post-forming process.Thermosetting can be improved
Resin impact resistance and can not post-forming process, and curing degree can further be lifted by photocuring again after post forming, from
And lift heat resistance and glass transition temperature.
Embodiment：
The illustrative embodiments of the present invention are hereinafter will be described in detail, however, these embodiments are only examples
Property, but the present invention do not limited by these embodiments and ratio.
Specific embodiment 1：
The present embodiment be related to can first heat cure, the unsaturated resin composition of light irradiation solidification again, its preparation method is such as
Under：
1) it is 2 by 6000g and mass ratio under normal temperature and pressure conditionses：1 hexamethylene, cyclohexanone mixed solvent are added to
In reactor；
2) 2600g 4-Vinyl phenols, 3400g divinylic monomers, 100g n-BuLis, 150g vinylbenzyl mercaptans are thrown
Enter in reactor, dissolved under 500 revs/min of stirring conditions；
3) 90 DEG C by resulting solution under anaerobic, are heated to, is reacted 1 hour；
4) solid made from step (3) filtered, cleaned, dried, be made can first through heat cure, UV light irradiations again
The unsaturated resin composition of solidification, is 4-Vinyl phenol-butadiene block copolymer.
The purposes of the present embodiment 1 is as follows：
By prepare can first through heat cure, again UV light irradiations solidification unsaturated resin composition (para hydroxybenzene second
Alkene-butadiene block copolymer) 100 mass parts are added in 200 mass parts butanone solvents, and 60 DEG C are stirred 3 hours, are treated to hydroxyl
After styrene-butadiene block copolymer is completely dissolved, 18 mass parts bisphenol f type epoxy resins, 8 mass parts hydrazides classes are added
Curing agent, 0.1 mass parts Imidizole accelerator, the acylphosphine oxide of 3 mass parts, stir and prepare glue.Use base
Weight is 200g/m2Carbon fiber cloth impregnate above-mentioned glue, toasted under the conditions of 170 DEG C 3 minutes and remove solvent, resin content is made
For 43% prepreg.Obtained prepreg 2 is stacked, the mould release membrance of 35 microns of thickness is configured above and below it, is placed in
In the vacuum press of programmable temperature-control pressure-control, in vacuum state, in 0.5PMa pressure condition, products temperature is in 170 DEG C of conditions
Lower solidification 1 hour, is made the laminar composite of 0.5mm thickness, then by the secondary thermoplastic machine-shaping of laminar composite after
UV intensities of illumination 200uW/cm2 Under the conditions of, irradiation solidification 1 minute.
Specific embodiment 2：
The present embodiment be related to can first through heat cure, again UV light irradiations solidification unsaturated resin composition, its preparation side
Method is as follows：
1) it is in atmospheric conditions, 1 by 5500g and mass ratio：1 hexamethylene, butanone mixed solvent are added to reactor
In；
2) by 2400g to amido styrene, 2800g divinylic monomers, 90g cyclohexanone peroxides, 140g dodecyl sulphur
In alcohol input reactor, dissolved under 300 revs/min of stirring conditions；
3) 80 DEG C by resulting solution under anaerobic, are heated to, is reacted 1 hour；
4) by step 3) made from solid filtered, cleaned, dried, be made can first through heat cure, again UV light irradiations consolidate
The unsaturated resin composition of change, for amido styrene-butadiene block copolymer.
The purposes of the present embodiment 2 is as follows：
By it is above-mentioned prepare can first through heat cure, again UV light irradiations solidification unsaturated resin composition (to amido
Styrene-butadiene block copolymer) 100 mass parts are added to 200 mass parts and mass ratio is 1：2 toluene, butanone mixing
In solvent, 65 DEG C are stirred 3 hours, after being completely dissolved to amido styrene-butadiene block copolymer, add 25 mass parts double
Phenol A types epoxy resin, 5 mass parts phenolic curing agent, 0.2 mass parts Imidizole accelerator, the alpha-hydroxyalkyl benzophenone of 3 mass parts,
Stir and prepare glue.It is 200g/m with base weight2Carbon fiber cloth impregnate above-mentioned glue, toast 2 under the conditions of 180 DEG C
Minute removes solvent, and the prepreg that resin content is 43% is made.Obtained prepreg 2 is stacked, matched somebody with somebody above and below it
Put in the mould release membrance of 35 microns of thickness, the vacuum press for being placed in programmable temperature-control pressure-control, in vacuum state, in 0.5PMa pressure
Condition, products temperature solidifies 1 hour under the conditions of 170 DEG C, and the laminar composite of 0.5mm thickness is made.It is again that lamination is compound
Material secondary thermoplastic processing is molded after UV intensities of illumination 150uW/cm2Under the conditions of, irradiation solidification 0.7 minute.
Specific embodiment 3：
The present embodiment be related to can first through heat cure, again UV light irradiations solidification unsaturated resin composition preparation method
It is as follows：
1) it is in atmospheric conditions, 1 by 4000g and mass ratio：1 hexamethylene, cyclohexanone mixed solvent are added to reaction
In kettle；
2) 1800g is put into carboxyl styrene, 2800g isoprene monomers, 70g n-BuLis, 140g tetrahydrofurans
In reactor, dissolved under 250 revs/min of stirring conditions；
3) 80 DEG C by resulting solution under anaerobic, are heated to, is reacted 1 hour；
4) solid made from step (3) filtered, cleaned, dried, be made can first through heat cure, UV light irradiations again
The unsaturated resin composition of solidification, for carboxyl styrene-isoprene block copolymer.
The purposes of the present embodiment 3 is as follows：
By it is above-mentioned prepare can first through heat cure, again UV light irradiations solidification unsaturated resin composition (to carboxyl
Styrene-isoprene block copolymer) 80 mass parts are added in 200 mass parts toluene solvants, and 70 DEG C are stirred 3 hours, are treated
After being completely dissolved to carboxyl styrene-isoprene block copolymer, 20 mass parts bisphenol A type epoxy resins, 10 mass are added
Part phenolic curing agent, 0.5 mass parts Imidizole accelerator, the acylphosphine oxide of 3 mass parts, stir and prepare glue
Liquid.It is 200g/m with base weight2Carbon fiber cloth impregnate above-mentioned glue, toasted under the conditions of 165 DEG C 4 minutes and remove solvent, tree is made
Fat content is 43% prepreg.Obtained prepreg 2 is stacked, the release of 40 microns of thickness is configured above and below it
In film, the vacuum press for being placed in programmable temperature-control pressure-control, in vacuum state, in 0.5PMa pressure condition, products temperature is 170
Solidify 1.5 hours under the conditions of DEG C, the laminar composite of 0.5mm thickness is made.Again by the secondary thermoplastic processing of laminar composite
Shaping is after UV intensities of illumination 250uW/cm2Under the conditions of, irradiation solidification 2 minutes.
Specific embodiment 4：
The present embodiment be related to can first through heat cure, again UV light irradiations solidification unsaturated resin composition preparation method such as
Under：
1) it is in atmospheric conditions, 1 by 5000g and mass ratio：1 cyclohexanone：Butanone mixed solvent is added to reactor
In；
2) by 2500g 4-Vinyl phenols, 2500g 1,4- diphenyl -1,3- divinylic monomers, 120g peroxidating hexamethylenes
In ketone, 180g tetrahydrofurans input reactor, dissolved under 200 revs/min of stirring conditions；
3) 80 DEG C by resulting solution under anaerobic, are heated to, is reacted 1.5 hours；
4) solid made from step (3) filtered, cleaned, dried, be made can first through heat cure, UV light irradiations again
The unsaturated resin composition of solidification, is 4-Vinyl phenol-Isosorbide-5-Nitrae-diphenyl -1,3-butadiene block copolymer.
The purposes of the present embodiment 3 is as follows；
By it is above-mentioned prepare can first through heat cure, again UV light irradiations solidification unsaturated resin composition (to hydroxyl
Styrene-Isosorbide-5-Nitrae-diphenyl -1,3-butadiene block copolymer) 100 mass parts are added in 200 mass parts butanone solvents, and 70
DEG C stirring 2.5 hours, after 4-Vinyl phenol-Isosorbide-5-Nitrae-diphenyl -1,3-butadiene block copolymer is completely dissolved, add 35
Mass parts bisphenol A type epoxy resin, 10 mass parts phenolic curing agent, 0.5 mass parts Imidizole accelerator, the acyl group of 3 mass parts
Phosphine oxide, stirs and prepares glue.It is 200g/m with base weight2Carbon fiber cloth impregnate above-mentioned glue, in 170 DEG C of bars
Toasted under part 3 minutes and remove solvent, the prepreg that resin content is 43% is made.Obtained prepreg 2 is stacked,
It configures the mould release membrance of 35 microns of thickness up and down, in the vacuum press for being placed in programmable temperature-control pressure-control, in vacuum state,
0.3PMa pressure condition, products temperature solidifies 1.5 hours under the conditions of 170 DEG C, and the lamination composite wood of 0.5mm thickness is made
Material.Again by the secondary thermoplastic machine-shaping of laminar composite after UV intensities of illumination 250uW/cm2Under the conditions of, 2 points of irradiation solidification
Clock.
In above-mentioned each specific embodiment：
Can first through heat cure, again UV light irradiations solidification unsaturated resin composition, it is characterised in that：The unsaturated-resin
Composition by several monomeric substance through chemical reaction combine obtain, the several monomeric substance include unsaturated-resin,
Epoxy resin, cure-crosslinking agent, curing accelerator and light trigger, the weight/mass percentage composition of the material composition is：It is unsaturated
Resin 40-80%, epoxy resin 5-40%, cure-crosslinking agent 0.5-20%, curing accelerator 0.01-1% and light trigger 1-
5%；It is dissolvable in water organic solvent；With thermoplastic resin performance, used as simple thermoplastic resin and in epoxy resin
Under the conditions of carry out solidification crosslinking, show the property between thermoplastic and thermosetting resin；, can containing unsaturated C=C keys
Under light trigger, UV illumination conditions, trigger free radical to carry out cross-linking reaction, obtain the high compound of crosslink density；The chemical combination
Thing has high glass-transition temperature, high-fire resistance, high-intensity performance.
Further, unsaturated-resin is represented with below general formula (I)：Formula I
The monomeric substance is comprising styrene compound and by its derivative compound, alkadiene compound and by it
Derivative compound；The styrene compound and by its derivative compound, can be represented by formula II, wherein each R bases
It is independently hydrogen, hydroxyl, amino, carboxyl, C1-C9 alkyl or alkoxy, bromine, phosphorus, DOPO；
Formula II
The alkadiene compound and by its derivative compound, can be represented by general formula III, wherein each R1 bases are independent
Ground can represent hydrogen, methyl, phenyl, bromine；
General formula III
Further, the epoxy resin can be bisphenol-A, Bisphenol F, bis-phenol M, bis-phenol P, bis-phenol E, phenol novolac epoxy
Compound, cresol novolac epoxy compound, dicyclopentadiene phenolic epoxide, tetramethyl Bisphenol F, bisphenol-A phenolic epoxy
Compound, brominated bisphenol A, brominated phenol novalac epoxy, 3 function phenols, 4 function phenols, naphthalene type phenols or biphenyl type
One or two or more kinds of combinations in phenols epoxy resin；Preferably, it can be bisphenol-A, Bisphenol F, bis-phenol M, bis-phenol P, bis-phenol
One or two or more kinds of combinations in E, phenol novolac epoxy resins.
Further, the curing agent can be amine curing agent, hydrazides class curing agent, lewis acid-amine complex class
Curing agent, acid anhydride type curing agent, one or two or more kinds of combinations of phenolic curing agent.
Further, the curing accelerator be imidazoles accelerator, peroxide accelerator, azo accelerator,
One or two or more kinds of groups in tertiary amines accelerator, phenol accelerant, organic metal salt accelerator, inorganic metal salt accelerator
Close.
Further, the light trigger can be benzoin derivatives, benzil ketals derivative, dialkoxy benzene second
Ketone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide, esterification assimilation compound, aryl peroxide ester compounds, halo
One or two or more kinds of combinations in methyl arone, sulfur-containing organic compound, benzoyl formiate.Preferably, from acylphosphanes
Oxide, alpha-hydroxyalkyl benzophenone, one or two or more kinds of combinations of benzil ketals derivative.
Further, material composition can also be added as needed on fire retardant, surface conditioning agent.The fire retardant, can be with
It is phosphorus flame retardant, nitrogenated flame retardant, bromide fire retardant, inorganic flame retardant etc..May be selected from organic phosphorus compound, nitrogenous three
Piperazine compound, brominated epoxy resin, tetrabromo-phthalic diformamide and one kind or two kinds of collocation groups in inorganic aluminium hydroxide
Close；The surface conditioning agent includes silane coupler, size or defoamer.
Comparative example 1：
The mass parts of acrylic acid epoxy resin 100 are added in 20 mass parts Isooctyl acrylate monomers, add the acyl of 2 mass parts
Base phosphine oxide, stirs and prepares glue.It is 200g/m with base weight2Carbon fiber cloth impregnate above-mentioned glue, resin contains
Measure as 43%.The carbon fiber cloth 2 of above-mentioned dipping glue is stacked and placed in mould, in UV intensities of illumination 250uW/cm2Condition
Under, irradiation solidification 2 minutes.
Comparative example 2：
The mass parts of phenolic resin 30 are dissolved in the butanone solvent of 100 mass parts, after stirring is completely dissolved to resin, plus
Enter 60 mass parts bisphenol f type epoxy resins, 1 mass parts imidazoles accelerator, stir and be prepared into glue.Then it is with base weight
200g/m2Carbon fiber cloth impregnate above-mentioned glue, toasted under the conditions of 160 DEG C 5 minutes and remove solvent, it is 45% that resin content, which is made,
Prepreg.Obtained prepreg 2 is laminated in mould, the vacuum press of programmable temperature-control pressure-control is placed in
In, in vacuum state, in 0.5PMa pressure condition, products temperature solidifies 1.5 hours under the conditions of 170 DEG C, 0.5mm is made thick
The moulded products of degree.
Following table is each embodiment data：
Comparative example 1 and the difference of comparative example 2 are that comparative example 1 is light-cured resin-carbon fiber composite
Material, comparative example 2 is thermosetting resin-carbon-fiber composite material.According to upper table result, comparative example 2 glass transition temperature,
It is better than comparative example 1 in terms of heat resistance, bending strength, and comparative example 1 is better than comparative example in terms of stretch modulus, impact strength
2。
Contrast comparative example 1 and specific embodiment 1 understands that both differences are, comparative example 1 is photocuring tree
Fat-carbon fibre composite, specific embodiment 1 is the carbon-fiber composite material for stating unsaturated resin composition.According to upper table result,
Specific embodiment 1 is in terms of glass transition temperature, heat resistance, bending strength, stretch modulus, impact strength compared with comparative example
1 is greatly improved.
Comparative example 2 and specific embodiment 1 are contrasted, both are difference, comparative example 2 is thermosetting resin-carbon
Fibrous composite, specific embodiment 1 is the carbon-fiber composite material of unsaturated resin composition.It is specific real according to upper table result
Apply example 1 has greatly in terms of glass transition temperature, heat resistance, bending strength, stretch modulus, impact strength compared with comparative example 2
The lifting of amplitude.Meanwhile, the sheet material after its heat cure possesses secondary thermoforming ability.
In summary, compared with general thermoset composition, unsaturated resin composition of the invention can improve thermosetting
Resin impact resistance and the defect for being unable to post forming, can improve light-cured resin heat resistance, the deficiency of product precision again, and
Possess high intensity, high glass-transition temperature, high heat-resisting composite.It can be used extensively using military project, Aero-Space, physical culture
The fields such as product, vehicle.
Above example, not the content of composition to the present invention impose any restrictions, every technology according to the present invention
Essence or composition components or content are still fallen within to any trickle amendment made for any of the above embodiments, equivalent variations and modification
In the range of technical solution of the present invention.
Claims (10)
1. can first heat cure, the unsaturated resin composition of light irradiation solidification again, it is characterised in that：The unsaturated resin composition
Combined and obtained through chemical reaction by several monomeric substance, the several monomeric substance includes unsaturated-resin, asphalt mixtures modified by epoxy resin
Fat, cure-crosslinking agent, curing accelerator and light trigger, the weight/mass percentage composition of the material composition is：Unsaturated-resin 40-
80%th, epoxy resin 5-40%, cure-crosslinking agent 0.5-20%, curing accelerator 0.01-1% and light trigger 1-5%；It is solvable
Solution is in organic solvent；With thermoplastic resin performance, use and enter under the conditions of epoxy resin as simple thermoplastic resin
Row solidification crosslinking, shows the property between thermoplastic and thermosetting resin；, can be light-initiated containing unsaturated C=C keys
Under agent, UV illumination conditions, trigger free radical to carry out cross-linking reaction, obtain the high compound of crosslink density；The compound has height
Glass transition temperature, high-fire resistance, high-intensity performance.
2. it is according to claim 1 can first heat cure, the unsaturated resin composition of light irradiation solidification again, its feature exists
In：
Unsaturated-resin is represented with below general formula (I)：Formula I
The monomeric substance is comprising styrene compound and by its derivative compound, alkadiene compound and by its derivative
Compound；The styrene compound and by its derivative compound, can be represented by formula II, wherein each R bases are independent
Ground is hydrogen, hydroxyl, amino, carboxyl, C1-C9 alkyl or alkoxy, bromine, phosphorus, DOPO；
Formula II
The alkadiene compound and by its derivative compound, can be represented by general formula III, wherein each R1 bases independently may be used
To represent hydrogen, methyl, phenyl, bromine；
General formula III
3. according to claim 1 or 2 can first heat cure, the unsaturated resin composition of light irradiation solidification again, its feature
It is：The epoxy resin can be bisphenol-A, Bisphenol F, bis-phenol M, bis-phenol P, bis-phenol E, phenol novolac epoxy compound, cresols
Novalac epoxy, dicyclopentadiene phenolic epoxide, tetramethyl Bisphenol F, bisphenol-A phenolic epoxide, bromination
Bisphenol-A, brominated phenol novalac epoxy, 3 function phenols, 4 function phenols, naphthalene type phenols or biphenyl type phenols epoxy resin
In one or two or more kinds of combinations；Preferably, it can be bisphenol-A, Bisphenol F, bis-phenol M, bis-phenol P, bis-phenol E, phenol novolac ring
One or two or more kinds of combinations in oxygen tree fat.
4. according to claim 1 or 2 can first heat cure, the unsaturated resin composition of light irradiation solidification again, its feature
It is：The curing agent can be amine curing agent, hydrazides class curing agent, lewis acid-amine complex class curing agent, anhydrides
One or two or more kinds of combinations of curing agent, phenolic curing agent；The curing accelerator is imidazoles accelerator, peroxide
Class accelerator, azo accelerator, tertiary amines accelerator, phenol accelerant, organic metal salt accelerator, inorganic metal salt promote
One or two or more kinds of combinations in agent；The light trigger can be benzoin derivatives, benzil ketals derivative, dioxane
Epoxide acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide, esterification assimilation compound, aryl peroxy esters chemical combination
One or two or more kinds of combinations in thing, halogenated methyl arone, sulfur-containing organic compound, benzoyl formiate.Preferably, select
Acylphosphine oxide, alpha-hydroxyalkyl benzophenone, one or two or more kinds of combinations of benzil ketals derivative.
5. according to claim 1 or 2 can first heat cure, the unsaturated resin composition of light irradiation solidification again, its feature
It is：Material composition can also be added as needed on fire retardant, surface conditioning agent.The fire retardant, can be phosphorus flame retardant,
Nitrogenated flame retardant, bromide fire retardant, inorganic flame retardant etc..May be selected from organic phosphorus compound, nitrogenous triaizine compounds, bromination
Epoxy resin, tetrabromo-phthalic diformamide and one kind or two kinds of matched combineds in inorganic aluminium hydroxide；At the surface
Managing agent includes silane coupler, size or defoamer.
6. can first heat cure, the preparation method of the unsaturated resin composition of light irradiation solidification again, it is characterised in that：Pass through freedom
Base polymerization is obtained, and specifically includes following steps：
1) under normal temperature and pressure conditionses, polymer solvent is added in reactor；
2) unsaturated-resin, epoxy resin, cure-crosslinking agent, curing accelerator and light trigger are added by weight/mass percentage composition
In reactor, the weight/mass percentage composition of the material composition is：Unsaturated-resin 40-80%, epoxy resin 5-40%, solidification are handed over
Join agent 0.5-20%, curing accelerator 0.01-1% and light trigger 1-5%；Carried out under 100-500 revs/min of stirring condition
Dissolving, is made mixed solution；
3) by step 2) obtained mixed solution under anaerobic, be heated to 60-120 DEG C, react 0.5-3 hours, insatiable hunger processed
With resin combination liquid；
4) unsaturated resin composition liquid made from step (3) is filtered, solidified, then cleaned, dried, be made
Can first through heat cure, again UV light irradiations solidification unsaturated resin composition.
7. it is according to claim 1 can first heat cure, the preparation method of the unsaturated resin composition of light irradiation solidification again,
It is characterized in that：The polymer solvent can be one kind or several of hexamethylene, butanone, cyclohexanone, methanol, toluene, dimethylbenzene etc.
Kind；Described styrene compound and the mass ratio of alkadiene compound are：30-60%:40-70%；The initiator
The including but not limited to various lithium alkylides of anionic polymerisation such as n-BuLi, organic peroxide such as cyclohexanone peroxide；It is described
Initiator adds mass ratio of the scope control in 0.1%-3%；The solvent includes but is not limited to butanone, cyclohexanone, toluene, two
The one or more of toluene, propylene glycol monomethyl ether；The activator includes but is not limited to such as tetrahydrofuran, vinylbenzyl mercaptan, ten
Dialkyl group mercaptan, the addition of activator is 2-5% mass ratio.
8. it is according to claim 6 can first heat cure, the preparation method of the unsaturated resin composition of light irradiation solidification again,
It is characterized in that：Prepare it is described can first through heat cure, the unsaturated resin composition of UV light irradiations solidification again, always according to regulation
Viscosity, the function of dissolved compound, add organic solvent, and organic solvent is not calculated in thermoset composition composition, only served
Viscosity, dissolved compound and the function of adjusting outward appearance are adjusted, is all driven out of by way of heating in process of production；It is organic
Solvent；It is n-butanol, butanone, toluene, dimethylbenzene, propylene glycol monomethyl ether, propylene glycol methyl ether acetate etc..Above-mentioned solvent is used alone
One or two kinds of two or more is used in mixed way.
9. can first heat cure, the purposes of the unsaturated resin composition of light irradiation solidification again, it is characterised in that：Obtained unsaturation
Molecular resin amount, containing the group that polarized is big, including hydroxyl or amino, is dissolvable in water organic in 4,000-200,000, molecule
Solvent；With thermoplastic resin performance, used as simple thermoplastic resin and certain journey is carried out under the conditions of epoxy resin
The solidification crosslinking of degree, shows the property between thermoplastic and thermosetting resin；Containing unsaturated C=C keys, it can draw in light
Send out under agent, UV illumination conditions, trigger free radical to carry out cross-linking reaction, obtain the higher compound of crosslink density；The compound is high
Glass transition temperature, high-fire resistance, high intensity.
10. it is according to claim 9 can first heat cure, the purposes of the unsaturated resin composition of light irradiation solidification again, its
It is characterised by：For preparing prepreg and laminate：
1) prepreg, refers to that enhancing base materials are impregnated or coated with above-mentioned unsaturated resin composition to be formed, can be in various moulds
Used in the fields such as pressure material, supporting material.The enhancing base materials can be glass fibre, carbon fiber, silicon carbide fibre, asbestos
Fiber, superhigh molecular weight polyethylene fibers, aramid fiber etc.；Unsaturated resin composition above-mentioned enhancing base materials are impregnated or
After coating, in order to drive solvent out of and unsaturated resin composition is reached semi-solid preparation, it will usually in 100-250 DEG C of temperature range
It is interior, heat 1-3 minutes, so that prepreg is made, counted by 100 mass parts of prepreg, unsaturated-resin in drier
The content in prepreg of composition is preferably 25-95%；
2) by prepreg made from the above method, compression molding, mold shape, die size are selected according to application field
Select, solidify 0.5-2 hours in the range of 100-250 DEG C of selection, shape, the low solidfied material of size required for being made, then in UV light
It is 100-300uW/cm according to intensity2Irradiation solidification 0.5-60 minutes；Moulding material can be applicable to military project, Aero-Space, physical culture use
Product, vehicular field；
3) thickness requirement of prepreg made from the above method as required is laminated, and according to purposes in its one side or
Upper and lower surface configures and is laminated mould release membrance, is molded into sheet material in certain temperature, pressure, vacuum condition laminated, sheet material has
Post-forming process ability, is carried out after secondary or multiple processing and forming, shape, the low solidfied material of size required for being made, then UV
Further solidification.Moulding material can be applied to the fields such as military project, Aero-Space, sports goods, vehicle；Release film type used
Do not limited with thickness；For lamination, temperature is 100-350 DEG C, pressure be 0.1-10PMa, vacuum 0-100 millimetress of mercury,
Heat time is 0.5-5 hours；For UV conditions of cure：Intensity of illumination 100-300uW/cm2Irradiation solidification 0.5-60 minutes.
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Cited By (2)
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| WO2021114553A1 (en) * | 2019-12-09 | 2021-06-17 | 广东盈骅新材料科技有限公司 | Unsaturated polyester resin, and preparation method therefor and use thereof |
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