CN107163478B - Unsaturated resin composition capable of being cured by heat and then by light irradiation, and preparation method and application thereof - Google Patents
Unsaturated resin composition capable of being cured by heat and then by light irradiation, and preparation method and application thereof Download PDFInfo
- Publication number
- CN107163478B CN107163478B CN201710498080.1A CN201710498080A CN107163478B CN 107163478 B CN107163478 B CN 107163478B CN 201710498080 A CN201710498080 A CN 201710498080A CN 107163478 B CN107163478 B CN 107163478B
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- Prior art keywords
- resin composition
- compound
- unsaturated resin
- curing
- unsaturated
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- 239000011342 resin composition Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 44
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 230000009477 glass transition Effects 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000005286 illumination Methods 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 238000001723 curing Methods 0.000 claims description 62
- -1 diene compound Chemical class 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- 229920001187 thermosetting polymer Polymers 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 239000004593 Epoxy Substances 0.000 claims description 17
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 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 15
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 15
- 239000004917 carbon fiber Substances 0.000 claims description 15
- 239000003063 flame retardant Substances 0.000 claims description 15
- 229920003986 novolac Polymers 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 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 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000012778 molding material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 5
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 5
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 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 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 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 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims 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 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 238000003848 UV Light-Curing Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012796 inorganic flame retardant Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 125000001741 organic sulfur group Chemical group 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
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 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
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 239000003292 glue Substances 0.000 description 12
- 229920001400 block copolymer Polymers 0.000 description 11
- 239000004744 fabric Substances 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 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 3
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-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
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-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
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical class OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000037228 dieting effect Effects 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 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
-
- 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
-
- 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
-
- 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
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an unsaturated resin composition capable of being cured by heat and then by light irradiation, a preparation method and application thereof, which are characterized in that: the unsaturated resin composition is obtained by combining a plurality of monomer substances through chemical reaction, wherein the plurality of monomer substances comprise unsaturated resin, epoxy resin, a curing cross-linking agent, a curing accelerator and a photoinitiator, and the mass percentage of the substance components is as follows: 40-80% of unsaturated resin, 5-40% of epoxy resin, 0.5-20% of curing cross-linking agent, 0.01-1% of curing accelerator and 1-5% of photoinitiator; the compound has thermoplastic resin performance, is used as a simple thermoplastic resin and is cured and crosslinked under the condition of epoxy resin, contains unsaturated C ═ C bonds, and can initiate free radicals to perform crosslinking reaction under the conditions of a photoinitiator and UV illumination to obtain a compound with high crosslinking density; the compound has high glass transition temperature, high heat resistance and high strength. The invention has the characteristics and beneficial effects of high heat resistance, high strength, high precision and secondary forming processing capability.
Description
Technical Field
The invention relates to an unsaturated resin composition, in particular to an unsaturated resin composition which can be cured by heat and then irradiated by light, a preparation method and application thereof, and is suitable for places with high strength, high heat resistance and high glass transition temperature. Belongs to the technical field of chemical products.
Background
Currently, photocurable resins and thermosetting resins have been widely used in various fields. The light-cured resin is a resin which is formed by the reaction of a photoinitiator under the condition of UV light to generate free radicals, and then the free radicals initiate oligomer curing and crosslinking. The cured product generally has the advantages of high surface hardness, good chemical resistance, good weather resistance and the like, and is widely applied to the fields of coatings, printing ink, plastics and the like. However, the photocurable resin has the following problems: (1) the glass transition temperature is relatively low, the high-temperature heat resistance is insufficient, and the surface flatness of a solidified substance is low; (2) if the light-cured composition is used for manufacturing a special-shaped product, the precision of the special-shaped product is difficult to ensure. Greatly limiting the application and application fields thereof. Thermosetting resins are superior in glass transition temperature, rigidity, heat resistance, strength, flatness of products, and the like, but have a problem that secondary molding cannot be performed.
Therefore, there is a need to develop a resin composition that is both heat-curable and light-curable.
Disclosure of Invention
An object of the present invention is to provide an unsaturated resin composition that can be cured by heat and light irradiation, in order to solve the problems of relatively low glass transition temperature, insufficient high temperature heat resistance, low surface flatness of the cured product, and inability of secondary molding of the thermosetting resin in the prior art. Has the characteristics of high glass transition temperature, high heat resistance, high strength and high precision and has the capability of secondary forming processing.
The second object of the present invention is to provide a method for producing an unsaturated resin composition which can be cured by heat and then by light irradiation.
The third object of the present invention is to provide an unsaturated resin composition which can be cured by heat and then by light irradiation.
One of the purposes of the invention can be achieved by adopting the following technical scheme:
an unsaturated resin composition curable by heat and then by light irradiation, characterized in that:
the unsaturated resin composition is obtained by combining a plurality of monomer substances through chemical reaction, wherein the plurality of monomer substances comprise unsaturated resin, epoxy resin, a curing cross-linking agent, a curing accelerator and a photoinitiator, and the mass percentage of the substance components is as follows: 40-80% of unsaturated resin, 5-40% of epoxy resin, 0.5-20% of curing cross-linking agent, 0.01-1% of curing accelerator and 1-5% of photoinitiator; dissolving in an organic solvent; the thermoplastic resin has the performance of thermoplastic resin, is used as pure thermoplastic resin and is cured and crosslinked under the condition of epoxy resin, and shows special performance between thermoplastic resin and thermosetting resin; the compound contains unsaturated C ═ C bonds, and under the conditions of a photoinitiator and UV illumination, free radicals are initiated to carry out crosslinking reaction, so that a compound with high crosslinking density is obtained; the compound has high glass transition temperature, high heat resistance and high strength;
the unsaturated resin is represented by the following general formula (I): general formula I
The monomer material comprises a styrene compound and a compound derived therefrom, a diene compound and a compound derived therefrom; the styrene compound and the compound derived from the styrene compound are represented by a general formula II, wherein each R group is independently hydrogen, hydroxyl, amino, carboxyl, alkyl or alkoxy of C1-C9, bromine, phosphorus, DOPO;
general formula II
The diene compounds and compounds derived therefrom are represented by the general formula III, wherein each R1 group independently represents hydrogen, methyl, phenyl, bromine;
general formula III
One of the purposes of the invention can be achieved by adopting the following technical scheme:
further, the unsaturated resin is represented by the following general formula (I): general formula I
The monomer material comprises a styrene compound and a compound derived therefrom, a diene compound and a compound derived therefrom; the styrenic compound and compounds derived therefrom may be represented by general formula II, wherein each R group is independently hydrogen, hydroxy, amino, carboxy, C1-C9 alkyl or alkoxy, bromo, phosphorous, DOPO;
general formula II
The diene compounds and compounds derived therefrom may be represented by formula III, wherein each R1 group independently may represent hydrogen, methyl, phenyl, bromine;
general formula III
One of the purposes of the invention can be achieved by adopting the following technical scheme:
further, the epoxy resin may be one or a combination of two or more of bisphenol a, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac epoxy, cresol novolac epoxy, dicyclopentadiene novolac epoxy, tetramethyl bisphenol F, bisphenol a novolac epoxy, brominated bisphenol a, brominated phenol novolac epoxy, 3-functional phenol, 4-functional phenol, naphthalene-type phenol, or biphenyl-type phenol epoxy; or one or more of bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E and phenol novolac epoxy resin.
Further, the curing agent is one or the combination of more than two of amine curing agent, hydrazide curing agent, Lewis acid-amine complex curing agent, anhydride curing agent and phenolic aldehyde curing agent; the curing accelerator is one or a combination of more than two of imidazole accelerator, peroxide accelerator, azo accelerator, tertiary amine accelerator, phenol accelerator, organic metal salt accelerator and inorganic metal salt accelerator; the photoinitiator is one or the combination of more than two of benzoin derivatives, benzil ketal derivatives, dialkoxyacetophenone, alpha-hydroxyalkyl phenone, alpha-amine alkyl phenone, acyl phosphine oxide, ester ketone compounds, aryl peroxyester compounds, halogenated methyl aryl ketone, organic sulfur-containing compounds and benzoyl formate; or one or more of acylphosphine oxide, alpha-hydroxyalkyl phenone and benzil ketal derivative.
Further, a flame retardant and a surface treatment agent are added into the material components; the flame retardant is a phosphorus flame retardant, a nitrogen flame retardant, a bromine flame retardant or an inorganic flame retardant; the organic phosphorus compound and the nitrogen-containing triazine compound are selected from one or two of brominated epoxy resin, tetrabromophthalamide and inorganic aluminum hydroxide; the surface treating agent comprises a silane coupling agent, a wetting agent or a defoaming agent.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a method for preparing an unsaturated resin composition which can be cured by heat and then by light irradiation, characterized in that: obtained by free radical polymerization, comprising the following steps:
1) adding a polymerization solvent into a reaction kettle under the conditions of normal temperature and normal pressure;
2) adding unsaturated resin, epoxy resin, a curing cross-linking agent, a curing accelerator and a photoinitiator into a reaction kettle according to the mass percentage, wherein the mass percentage of the material components is as follows: 40-80% of unsaturated resin, 5-40% of epoxy resin, 0.5-20% of curing cross-linking agent, 0.01-1% of curing accelerator and 1-5% of photoinitiator; dissolving under the stirring condition of 100-500 r/min to prepare a mixed solution;
3) heating the mixed solution obtained in the step 2) to 60-120 ℃ under an oxygen-free condition, and reacting for 0.5-3 hours to prepare unsaturated resin composition liquid;
4) filtering and solidifying the unsaturated resin composition liquid prepared in the step (3), cleaning and drying to prepare an unsaturated resin composition which can be cured by heat and then UV light irradiation;
the polymerization solvent is one or more of cyclohexane, butanone, cyclohexanone, methanol, toluene and xylene; the mass ratio of the styrene compound to the diene compound is as follows: 30-60 percent, 40-70 percent; the initiator comprises n-butyl lithium and cyclohexanone peroxide which are subjected to anionic polymerization; the addition range of the initiator is controlled to be 0.1-3% by mass; the solvent comprises one or more of butanone, cyclohexanone, toluene, xylene and propylene glycol monomethyl ether; the activating agent comprises tetrahydrofuran, vinyl benzyl mercaptan and dodecyl mercaptan, and the adding amount of the activating agent is 2-5% by mass.
The second purpose of the invention can be achieved by adopting the following technical scheme:
further, the unsaturated resin composition which can be cured by heat and then irradiated by UV light is prepared, and an organic solvent is added according to the functions of adjusting viscosity and dissolving a compound, wherein the organic solvent is not calculated in the components of the thermosetting composition, only has the functions of adjusting viscosity, dissolving a compound and adjusting appearance, and is completely expelled in a heating mode in the production process; the organic solvent is n-butanol, butanone, toluene, xylene, propylene glycol methyl ether acetate; the above solvents are used singly or in combination.
The third purpose of the invention can be achieved by adopting the following technical scheme:
the molecular weight of the prepared unsaturated resin is 4,000-200,000, and the molecule contains groups with large polarity, including hydroxyl or amino, which can be dissolved in an organic solvent; the thermoplastic resin has the performance of thermoplastic resin, is used as pure thermoplastic resin and is cured and crosslinked under the condition of epoxy resin, and shows special performance between thermoplastic resin and thermosetting resin; the compound contains unsaturated C ═ C bonds, and can initiate free radicals to perform crosslinking reaction under the conditions of a photoinitiator and UV illumination to obtain a compound with higher crosslinking density; the compound has high glass transition temperature, high heat resistance and high strength.
The third purpose of the invention can be achieved by adopting the following technical scheme:
further, for the preparation of prepregs and laminates:
1) prepregs, which are obtained by impregnating or coating a reinforcing base material with the above unsaturated resin composition, are used in various fields such as molding materials and reinforcing materials; the reinforced base material is glass fiber, carbon fiber, silicon carbide fiber, asbestos fiber, ultra-high molecular weight polyethylene fiber and aramid fiber; after the reinforcing base material is impregnated or coated by the unsaturated resin composition, in order to drive out the solvent and semi-solidify the unsaturated resin composition, heating the unsaturated resin composition in a drier for 1 to 3 minutes within the temperature range of 100 ℃ and 250 ℃ so as to prepare a prepreg, wherein the content of the unsaturated resin composition in the prepreg is 25 to 95 percent based on 100 parts by mass of the prepreg;
2) the prepreg prepared by the method is subjected to compression molding, the shape and the size of the mold are selected according to the application field, the low-cured material with the required shape and size is prepared by curing for 0.5-2 hours within the range of 100-250 ℃, and then the low-cured material is irradiated and cured for 0.5-60 minutes under the condition that the UV illumination intensity is 100-300uW/cm 2; the molding material is applied to the fields of military industry, aerospace, sports goods and vehicles;
3) laminating the prepreg prepared by the method according to the required thickness requirement, configuring and laminating release films on one surface or the upper surface and the lower surface of the prepreg according to the application, laminating the release films into a sheet under certain temperature, pressure and vacuum conditions, wherein the sheet has secondary molding processing capacity, and after secondary or multiple molding processing, preparing a low-cured substance with required shape and size, and further curing the low-cured substance by UV; the molding material is applied to the fields of military industry, aerospace, sports goods and vehicles; the type and thickness of the release film are not limited; for lamination conditions, the temperature is 100-; for the UV curing conditions: the illumination intensity is 100-300uW/cm2 for 0.5-60 minutes.
The invention has the following outstanding advantages:
1. the unsaturated resin composition which can be cured by heat and then by light can be dissolved in an organic solvent; the thermoplastic resin has the performance of thermoplastic resin, is used as pure thermoplastic resin and is cured and crosslinked under the condition of epoxy resin, and shows special performance between thermoplastic resin and thermosetting resin; the compound contains unsaturated C ═ C bonds, and can initiate free radicals to perform crosslinking reaction under the conditions of a photoinitiator and UV illumination to obtain a compound with high crosslinking density; the compound has high glass transition temperature, high heat resistance and high strength; therefore, the problems that the light-cured resin in the prior art is relatively low in glass-transition temperature, insufficient in high-temperature heat resistance, low in surface flatness of a cured object and incapable of secondary molding processing exist in the heat-cured resin can be solved, and the light-cured resin has the characteristics and the beneficial effects of high glass-transition temperature, high heat resistance, high strength, high precision and secondary molding processing capability.
2. The invention is a kind of unsaturated resin composition that can be thermoset and light-cured at the same time, this composition is heated and carried on solidification of certain proportion and degree first, the post-forming has processing ability of secondary molding after the thermoset, secondary molding or further solidification through UV light irradiation after many times of shaping, the products have high glass transition temperature, high heat-resisting, high strength and high accuracy, the advantage of integrating thermoset and light-curing, the products obtained can be applied to fields such as war industry, aviation and space, sports goods and vehicles, etc.
3. The invention can firstly carry out thermosetting with a certain proportion, has secondary forming processing capability due to relatively low curing proportion, and the product which is formed and further subjected to UV curing has high glass transition temperature, high heat resistance, high strength and high precision, integrates the advantages of thermosetting and photocuring, and endows the secondary forming processing capability. The impact resistance and non-secondary forming processing of the thermosetting resin can be improved, and the curing degree can be further improved through light curing after secondary forming, so that the heat resistance and the glass transition temperature are improved.
The specific implementation mode is as follows:
hereinafter, exemplary embodiments of the present invention will be described in detail, however, these embodiments are merely exemplary, and the present invention is not limited by these examples and proportions.
Specific example 1:
the unsaturated resin composition which can be cured by heat and then by light irradiation according to the present embodiment is prepared as follows:
1) under the conditions of normal temperature and normal pressure, 6000g of the mixture with the mass ratio of 2: adding the cyclohexane and cyclohexanone mixed solvent of 1 into a reaction kettle;
2) 2600g of p-hydroxystyrene, 3400g of butadiene monomer, 100g of n-butyllithium and 150g of vinylbenzylmercaptan are put into a reaction kettle and dissolved under the stirring condition of 500 revolutions per minute;
3) heating the obtained solution to 90 ℃ under an oxygen-free condition, and reacting for 1 hour;
4) and (3) filtering, cleaning and drying the solid prepared in the step (3) to prepare an unsaturated resin composition which can be firstly cured by heat and then cured by UV light irradiation, wherein the unsaturated resin composition is a p-hydroxystyrene-butadiene block copolymer.
The use of example 1 is as follows:
100 parts by mass of the prepared unsaturated resin composition (p-hydroxystyrene-butadiene block copolymer) which can be cured by heat and then by UV light irradiation is added into 200 parts by mass of butanone solvent, stirred for 3 hours at 60 ℃, after the p-hydroxystyrene-butadiene block copolymer is completely dissolved, 18 parts by mass of bisphenol F type epoxy resin, 8 parts by mass of hydrazide curing agent, 0.1 part by mass of imidazole accelerator and 3 parts by mass of acylphosphine oxide are added, and the glue solution is prepared by uniformly stirring. And (3) impregnating the glue solution with carbon fiber cloth with the basis weight of 200g/m2, and baking at 170 ℃ for 3 minutes to remove the solvent to obtain a prepreg with the resin content of 43%. Laminating the obtained 2 prepregs, configuring a release film with the thickness of 35 microns above and below the prepregs, placing the prepregs in a vacuum press with the programmable temperature and pressure control, curing for 1 hour under the conditions of the pressure of 0.5PMa and the temperature of a product of 170 ℃ in a vacuum state to prepare a laminated composite material with the thickness of 0.5mm, performing secondary thermoplastic processing on the laminated composite material, and irradiating and curing for 1 minute under the condition of the UV illumination intensity of 200uW/cm 2.
Specific example 2:
the unsaturated resin composition that can be cured by heat and then by UV light according to the present example is prepared as follows:
1) under the condition of normal pressure, 5500g and the mass ratio of 1: adding the cyclohexane and butanone mixed solvent of 1 into a reaction kettle;
2) 2400g of p-aminostyrene, 2800g of butadiene monomer, 90g of cyclohexanone peroxide and 140g of dodecyl mercaptan are put into a reaction kettle and dissolved under the stirring condition of 300 revolutions per minute;
3) heating the obtained solution to 80 ℃ under an oxygen-free condition, and reacting for 1 hour;
4) filtering, cleaning and drying the solid prepared in the step 3) to prepare an unsaturated resin composition which can be cured by heat and then UV light irradiation, wherein the unsaturated resin composition is a p-aminostyrene-butadiene block copolymer.
The use of example 2 is as follows:
100 parts by mass of the unsaturated resin composition (p-aminostyrene-butadiene block copolymer) which is prepared in the above manner and can be cured by heat curing and then by UV light irradiation is added to 200 parts by mass of the unsaturated resin composition, wherein the mass ratio of the unsaturated resin composition to the p-aminostyrene-butadiene block copolymer is 1: 2, stirring for 3 hours at 65 ℃, adding 25 parts by mass of bisphenol A epoxy resin, 5 parts by mass of phenolic aldehyde curing agent, 0.2 part by mass of imidazole accelerator and 3 parts by mass of alpha-hydroxyalkyl benzophenone after the p-aminostyrene-butadiene block copolymer is completely dissolved, and uniformly stirring to obtain the glue solution. And (3) impregnating the glue solution with carbon fiber cloth with the basis weight of 200g/m2, and baking at 180 ℃ for 2 minutes to remove the solvent to obtain a prepreg with the resin content of 43%. The prepreg 2 obtained was stacked, a release film having a thickness of 35 μm was disposed on the upper and lower sides thereof, and the laminate was cured in a vacuum press having a temperature and pressure controlled and programmable temperature and pressure for 1 hour under a pressure condition of 0.5PMa and a product temperature of 170 ℃ in a vacuum state to obtain a laminate composite having a thickness of 0.5 mm. And then carrying out secondary thermoplastic processing on the laminated composite material, and then irradiating and curing for 0.7 minute under the condition that the UV illumination intensity is 150uW/cm 2.
Specific example 3:
the preparation method of the unsaturated resin composition which can be cured by heat and then by UV light irradiation according to the embodiment is as follows:
1) under the condition of normal pressure, 4000g of the mixed solution is mixed by a mass ratio of 1: adding the cyclohexane and cyclohexanone mixed solvent of 1 into a reaction kettle;
2) putting 1800g of p-carboxystyrene, 2800g of isoprene monomer, 70g of n-butyl lithium and 140g of tetrahydrofuran into a reaction kettle, and dissolving under the stirring condition of 250 revolutions per minute;
3) heating the obtained solution to 80 ℃ under an oxygen-free condition, and reacting for 1 hour;
4) and (4) filtering, cleaning and drying the solid prepared in the step (3) to prepare an unsaturated resin composition which can be cured by heat and then UV light irradiation, wherein the unsaturated resin composition is a p-carboxystyrene-isoprene block copolymer.
The use of example 3 is as follows:
adding 80 parts by mass of the prepared unsaturated resin composition (p-carboxyl styrene-isoprene block copolymer) which can be cured by heat and then irradiated by UV light into 200 parts by mass of toluene solvent, stirring for 3 hours at 70 ℃, adding 20 parts by mass of bisphenol A epoxy resin, 10 parts by mass of phenolic curing agent, 0.5 part by mass of imidazole accelerator and 3 parts by mass of acylphosphine oxide after the p-carboxyl styrene-isoprene block copolymer is completely dissolved, and uniformly stirring to obtain glue solution. And (3) impregnating the glue solution with carbon fiber cloth with the basis weight of 200g/m2, and baking at 165 ℃ for 4 minutes to remove the solvent to obtain a prepreg with the resin content of 43%. The prepreg 2 obtained was stacked, a release film having a thickness of 40 μm was disposed on the upper and lower sides thereof, and the laminate was cured in a vacuum press having a temperature and pressure controllable and programmable under a pressure condition of 0.5PMa and a product temperature of 170 ℃ for 1.5 hours in a vacuum state to obtain a laminate composite having a thickness of 0.5 mm. And then carrying out secondary thermoplastic processing on the laminated composite material, and then irradiating and curing for 2 minutes under the condition of UV illumination intensity of 250uW/cm 2.
Specific example 4:
the preparation method of the unsaturated resin composition which can be cured by heat and then by UV light irradiation according to the embodiment is as follows:
1) under the condition of normal pressure, 5000g of the mixture with the mass ratio of 1: 1 Cyclohexanone: adding a butanone mixed solvent into a reaction kettle;
2) putting 2500g of p-hydroxystyrene, 2500g of 1, 4-diphenyl-1, 3-butadiene monomer, 120g of cyclohexanone peroxide and 180g of tetrahydrofuran into a reaction kettle, and dissolving under the stirring condition of 200 revolutions per minute;
3) heating the obtained solution to 80 ℃ under an oxygen-free condition, and reacting for 1.5 hours;
4) and (3) filtering, cleaning and drying the solid prepared in the step (3) to prepare an unsaturated resin composition which can be firstly cured by heat and then cured by UV light irradiation and is a p-hydroxystyrene-1, 4-diphenyl-1, 3-butadiene block copolymer.
The use of example 3 is as follows;
100 parts by mass of the unsaturated resin composition (p-hydroxystyrene-1, 4-diphenyl-1, 3-butadiene block copolymer) which is prepared and can be cured by heat curing and then UV light irradiation is added into 200 parts by mass of butanone solvent, stirred for 2.5 hours at 70 ℃, after the p-hydroxystyrene-1, 4-diphenyl-1, 3-butadiene block copolymer is completely dissolved, 35 parts by mass of bisphenol A epoxy resin, 10 parts by mass of phenolic curing agent, 0.5 part by mass of imidazole accelerator and 3 parts by mass of acylphosphine oxide are added, and the mixture is uniformly stirred to prepare glue solution. And (3) impregnating the glue solution with carbon fiber cloth with the basis weight of 200g/m2, and baking at 170 ℃ for 3 minutes to remove the solvent to obtain a prepreg with the resin content of 43%. The prepreg 2 obtained was stacked, a release film having a thickness of 35 μm was disposed on the upper and lower sides thereof, and the laminate was cured in a vacuum press having a temperature and pressure controlled and programmable temperature and pressure for 1.5 hours under a pressure condition of 0.3PMa and a product temperature of 170 ℃ in a vacuum state to obtain a laminate composite having a thickness of 0.5 mm. And then carrying out secondary thermoplastic processing on the laminated composite material, and then irradiating and curing for 2 minutes under the condition of UV illumination intensity of 250uW/cm 2.
In the above embodiments:
an unsaturated resin composition which can be cured by heat and then by UV light irradiation, characterized in that: the unsaturated resin composition is obtained by combining a plurality of monomer substances through chemical reaction, wherein the plurality of monomer substances comprise unsaturated resin, epoxy resin, a curing cross-linking agent, a curing accelerator and a photoinitiator, and the mass percentage of the substance components is as follows: 40-80% of unsaturated resin, 5-40% of epoxy resin, 0.5-20% of curing cross-linking agent, 0.01-1% of curing accelerator and 1-5% of photoinitiator; is soluble in organic solvents; the thermoplastic resin has the performance of thermoplastic resin, is used as pure thermoplastic resin and is cured and crosslinked under the condition of epoxy resin, and shows special performance between thermoplastic resin and thermosetting resin; the compound contains unsaturated C ═ C bonds, and can initiate free radicals to perform crosslinking reaction under the conditions of a photoinitiator and UV illumination to obtain a compound with high crosslinking density; the compound has high glass transition temperature, high heat resistance and high strength.
Further, the unsaturated resin is represented by the following general formula (I): general formula I
The monomer material comprises a styrene compound and a compound derived therefrom, a diene compound and a compound derived therefrom; the styrenic compound and compounds derived therefrom may be represented by general formula II, wherein each R group is independently hydrogen, hydroxy, amino, carboxy, C1-C9 alkyl or alkoxy, bromo, phosphorous, DOPO;
general formula II
The diene compounds and compounds derived therefrom may be represented by formula III, wherein each R1 group independently may represent hydrogen, methyl, phenyl, bromine;
general formula III
Further, the epoxy resin may be one or a combination of two or more of bisphenol a, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac epoxy, cresol novolac epoxy, dicyclopentadiene novolac epoxy, tetramethyl bisphenol F, bisphenol a novolac epoxy, brominated bisphenol a, brominated phenol novolac epoxy, 3-functional phenol, 4-functional phenol, naphthalene-type phenol, or biphenyl-type phenol epoxy; preferably, the epoxy resin composition can be one or more of bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E and phenol novolac epoxy resin.
The curing agent may be one or a combination of two or more of an amine curing agent, a hydrazide curing agent, a lewis acid-amine complex curing agent, an acid anhydride curing agent, and a phenol curing agent.
The curing accelerator is one or a combination of more than two of imidazole accelerators, peroxide accelerators, azo accelerators, tertiary amine accelerators, phenol accelerators, organic metal salt accelerators and inorganic metal salt accelerators.
Further, the photoinitiator may be one or a combination of two or more of benzoin derivatives, benzil ketal derivatives, dialkoxyacetophenones, α -hydroxyalkylphenylketones, α -aminoalkylphenones, acylphosphine oxides, esterone compounds, aryl peroxyester compounds, halomethyl arylketones, organic sulfur compounds, and benzoylformate esters. Preferably, one or more than two of acylphosphine oxide, alpha-hydroxyalkyl phenone and benzil ketal derivative are selected.
Further, the substance component can be added with a flame retardant and a surface treatment agent according to the needs. The flame retardant may be a phosphorus flame retardant, a nitrogen flame retardant, a bromine flame retardant, an inorganic flame retardant, or the like. Can be selected from one or two of organic phosphorus compound, triazine compound containing nitrogen, brominated epoxy resin, tetrabromophthalamide and inorganic aluminum hydroxide; the surface treating agent comprises a silane coupling agent, a wetting agent or a defoaming agent.
Comparative example 1:
adding 100 parts by mass of acrylic epoxy resin into 20 parts by mass of isooctyl acrylate, adding 2 parts by mass of acylphosphine oxide, and uniformly stirring to obtain the glue solution. The above dope was impregnated with a carbon fiber cloth having a basis weight of 200g/m2 and a resin content of 43%. And (3) superposing the 2 carbon fiber cloth pieces impregnated with the glue solution in a forming die, and irradiating and curing for 2 minutes under the condition of UV illumination intensity of 250uW/cm 2.
Comparative example 2:
dissolving 30 parts by mass of phenolic resin in 100 parts by mass of butanone solvent, stirring until the resin is completely dissolved, adding 60 parts by mass of bisphenol F type epoxy resin and 1 part by mass of imidazole accelerator, and uniformly stirring to prepare glue solution. Then, the glue solution is soaked in carbon fiber cloth with the basis weight of 200g/m2, and the prepreg is baked at 160 ℃ for 5 minutes to remove the solvent, so that the prepreg with the resin content of 45% is prepared. The prepreg 2 obtained was stacked in a molding die, placed in a vacuum press with programmable temperature and pressure control, and cured for 1.5 hours under a pressure condition of 0.5PMa and a product temperature of 170 ℃ in a vacuum state to prepare a molded product with a thickness of 0.5 mm.
The following table is the data for each example:
comparative example 1 and comparative example 2 are different in that comparative example 1 is a photocurable resin-carbon fiber composite material and comparative example 2 is a thermosetting resin-carbon fiber composite material. From the results of the above table, comparative example 2 is superior to comparative example 1 in glass transition temperature, heat resistance, and flexural strength, and comparative example 1 is superior to comparative example 2 in tensile modulus and impact strength.
As can be seen from comparison of comparative example 1 and embodiment 1, the difference between the two is that comparative example 1 is a photocurable resin-carbon fiber composite material, and embodiment 1 is a carbon fiber composite material of the unsaturated resin composition described above. From the above results, the glass transition temperature, heat resistance, flexural strength, tensile modulus, impact strength, and the like of example 1 were significantly improved as compared with those of comparative example 1.
Comparative example 2 and specific example 1 are different in that comparative example 2 is a thermosetting resin-carbon fiber composite material, and specific example 1 is a carbon fiber composite material of an unsaturated resin composition. From the above table, the glass transition temperature, heat resistance, flexural strength, tensile modulus, impact strength, etc. of example 1 are greatly improved as compared with those of comparative example 2. Meanwhile, the plate after thermosetting has secondary hot forming capability.
As described above, the unsaturated resin composition of the present invention is a composite material having improved impact resistance and non-moldability of a thermosetting resin, improved heat resistance and product accuracy of a photocurable resin, and high strength, high glass transition temperature and high heat resistance, as compared with a general thermosetting composition. Can be widely applied to the fields of military industry, aerospace, sports goods, vehicles and the like.
The above examples are not intended to limit the content of the composition of the present invention, and all the minor modifications, equivalent changes and modifications made to the above examples according to the technical spirit or composition components or contents of the present invention are within the technical scope of the present invention.
Claims (8)
1. An unsaturated resin composition curable by heat and then by light irradiation, characterized in that:
the unsaturated resin composition is obtained by combining a plurality of monomer substances through chemical reaction, wherein the plurality of monomer substances comprise unsaturated resin, epoxy resin, a curing cross-linking agent, a curing accelerator and a photoinitiator, and the mass percentage of the substance components is as follows: 40-80% of unsaturated resin, 5-40% of epoxy resin, 0.5-20% of curing cross-linking agent, 0.01-1% of curing accelerator and 1-5% of photoinitiator; dissolving in an organic solvent; the thermoplastic resin has the performance of thermoplastic resin, is used as pure thermoplastic resin and is cured and crosslinked under the condition of epoxy resin, and shows special performance between thermoplastic resin and thermosetting resin; the compound contains unsaturated C ═ C bonds, and under the conditions of a photoinitiator and UV illumination, free radicals are initiated to carry out crosslinking reaction, so that a compound with high crosslinking density is obtained; the compound has high glass transition temperature, high heat resistance and high strength;
the unsaturated resin is represented by the following general formula (I): general formula I
The unsaturated resin-forming monomer material comprises a styrenic compound and a compound derived therefrom, a diene compound and a compound derived therefrom; the styrene compound and the compound derived from the styrene compound are represented by a general formula II, wherein each R group is independently hydrogen, hydroxyl, amino, carboxyl, alkyl or alkoxy of C1-C9, bromine, phosphorus, DOPO;
general formula II
The diene compounds and compounds derived therefrom are represented by the general formula III, wherein each R1 group independently represents hydrogen, methyl, phenyl, bromine;
general formula III
2. The unsaturated resin composition curable by heat and light irradiation according to claim 1, wherein: the epoxy resin is one or the combination of more than two of bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac epoxy compound, cresol novolac epoxy compound, dicyclopentadiene novolac epoxy compound, tetramethyl bisphenol F, bisphenol A novolac epoxy compound, brominated bisphenol A, brominated phenol novolac epoxy compound, 3 functional phenol, 4 functional phenol, naphthalene type phenol or biphenyl type phenol epoxy resin.
3. The unsaturated resin composition curable by heat and light irradiation according to claim 1, wherein: the curing crosslinking agent is one or the combination of more than two of an amine curing agent, a hydrazide curing agent, a Lewis acid-amine complex curing agent, an anhydride curing agent and a phenolic aldehyde curing agent; the curing accelerator is one or a combination of more than two of imidazole accelerator, peroxide accelerator, azo accelerator, tertiary amine accelerator, phenol accelerator, organic metal salt accelerator and inorganic metal salt accelerator; the photoinitiator is one or the combination of more than two of benzoin derivatives, benzil ketal derivatives, dialkoxyacetophenone, alpha-hydroxyalkyl phenone, alpha-amine alkyl phenone, acyl phosphine oxide, ester ketone compounds, aryl peroxyester compounds, halogenated methyl aryl ketone, organic sulfur-containing compounds and benzoyl formate.
4. The unsaturated resin composition curable by heat and light irradiation according to claim 1, wherein: the material components are also added with a flame retardant and a surface treating agent; the flame retardant is a phosphorus flame retardant, a nitrogen flame retardant, a bromine flame retardant or an inorganic flame retardant; the surface treating agent comprises a silane coupling agent, a wetting agent or a defoaming agent.
5. The method for producing a thermosetting and then light-curing unsaturated resin composition according to claim 1, wherein: obtained by free radical polymerization, comprising the following steps:
1) adding a polymerization solvent into a reaction kettle under the conditions of normal temperature and normal pressure;
2) adding unsaturated resin, epoxy resin, a curing cross-linking agent, a curing accelerator and a photoinitiator into a reaction kettle according to the mass percentage, wherein the mass percentage of the material components is as follows: 40-80% of unsaturated resin, 5-40% of epoxy resin, 0.5-20% of curing cross-linking agent, 0.01-1% of curing accelerator and 1-5% of photoinitiator; dissolving under the stirring condition of 100-500 r/min to prepare a mixed solution;
3) heating the mixed solution obtained in the step 2) to 60-120 ℃ under an oxygen-free condition, and reacting for 0.5-3 hours to prepare unsaturated resin composition liquid;
4) filtering and solidifying the unsaturated resin composition liquid prepared in the step (3), cleaning and drying to prepare an unsaturated resin composition which can be cured by heat and then UV light irradiation;
the polymerization solvent is one or more of cyclohexane, butanone, cyclohexanone, methanol, toluene and xylene; the mass ratio of the styrene compound to the diene compound is as follows: 30-60 percent, 40-70 percent; the photoinitiator comprises cyclohexanone peroxide; the addition range of the photoinitiator is controlled to be 0.1-3% by mass; the catalyst also comprises an activating agent, wherein the activating agent comprises tetrahydrofuran, vinyl benzyl mercaptan and dodecyl mercaptan, and the adding amount of the activating agent is 2-5% by mass.
6. The method for producing the unsaturated resin composition curable by heat-first and then light-irradiation according to claim 5, wherein: the unsaturated resin composition which can be firstly cured by heat and then cured by UV light irradiation is prepared, and an organic solvent is added according to the functions of adjusting viscosity and dissolving compounds, wherein the organic solvent is not calculated in the components of the thermosetting composition and only has the functions of adjusting viscosity, dissolving compounds and adjusting appearance, and is completely expelled in a heating mode in the production process; the organic solvent is n-butanol, butanone, toluene, xylene, propylene glycol methyl ether acetate; the above solvents are used singly or in combination.
7. Use of the thermosetting and then light-curing unsaturated resin composition according to claim 1, wherein: the molecular weight of the prepared unsaturated resin is 4,000-200,000, and the molecule contains a group with large polarity, specifically a hydroxyl group or an amino group, which can be dissolved in an organic solvent; the thermoplastic resin has the performance of thermoplastic resin, is used as pure thermoplastic resin and is cured and crosslinked under the condition of epoxy resin, and shows special performance between thermoplastic resin and thermosetting resin; the compound contains unsaturated C ═ C bonds, and can initiate free radicals to perform crosslinking reaction under the conditions of a photoinitiator and UV illumination to obtain a compound with higher crosslinking density; the compound has high glass transition temperature, high heat resistance and high strength.
8. Use of the heat-curable, re-radiation-curable unsaturated resin composition according to claim 7, characterized in that: for the preparation of prepregs and laminates:
1) a prepreg which is obtained by impregnating or coating a reinforcing base material with the above unsaturated resin composition and is used in the fields of various molding materials and reinforcing materials; the reinforced base material is glass fiber, carbon fiber, silicon carbide fiber, asbestos fiber, ultra-high molecular weight polyethylene fiber and aramid fiber; after the reinforcing base material is impregnated or coated by the unsaturated resin composition, in order to drive out the solvent and semi-solidify the unsaturated resin composition, heating the unsaturated resin composition in a drier for 1 to 3 minutes within the temperature range of 100 ℃ and 250 ℃ so as to prepare a prepreg, wherein the content of the unsaturated resin composition in the prepreg is 25 to 95 percent based on 100 parts by mass of the prepreg;
2) the prepreg prepared by the method is subjected to compression molding, the shape and the size of the mold are selected according to the application field, the low-cured material with the required shape and size is prepared by curing for 0.5-2 hours within the range of 100-250 ℃, and then the low-cured material is irradiated and cured for 0.5-60 minutes under the condition that the UV illumination intensity is 100-300uW/cm 2; the molding material is applied to the fields of military industry, aerospace, sports goods and vehicles;
3) laminating the prepreg prepared by the method according to the required thickness requirement, configuring and laminating release films on one surface or the upper surface and the lower surface of the prepreg according to the application, laminating the release films into a sheet under certain temperature, pressure and vacuum conditions, wherein the sheet has secondary molding processing capacity, and after secondary or multiple molding processing, preparing a low-cured substance with required shape and size, and further curing the low-cured substance by UV; the molding material is applied to the fields of military industry, aerospace, sports goods and vehicles; the type and thickness of the release film are not limited; for lamination conditions, the temperature is 100-; for the UV curing conditions: the illumination intensity is 100-300uW/cm2 for 0.5-60 minutes.
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| CN111116879B (en) * | 2019-12-09 | 2021-03-09 | 广东盈骅新材料科技有限公司 | Unsaturated polyester resin and preparation method and application thereof |
| CN115612142B (en) * | 2022-12-20 | 2023-05-23 | 中国电子科技集团公司第四十六研究所 | Method for preparing prepreg by ultraviolet curing and thermal curing composite technology |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849460A (en) * | 1994-07-27 | 1998-12-15 | Hitachi, Ltd. | Photosensitive resin composition and method for using the same in manufacture of circuit boards |
| JP2002080525A (en) * | 2000-06-27 | 2002-03-19 | Showa Highpolymer Co Ltd | Thermosetting or photo-setting resin |
| CN1408764A (en) * | 2001-09-27 | 2003-04-09 | 山荣化学株式会社 | Light solidified and heat solidified resin composition and method for producing printed circuit board |
| CN102127386A (en) * | 2010-12-29 | 2011-07-20 | 东莞市新懿电子材料技术有限公司 | Light-curing and heat-curing conductive adhesive and preparation method |
| CN102439089A (en) * | 2010-06-28 | 2012-05-02 | 株式会社艾迪科 | Curable resin composition |
| CN102533146A (en) * | 2010-12-06 | 2012-07-04 | 第一毛织株式会社 | Adhesive film for semiconductor device |
| CN102690611A (en) * | 2011-12-27 | 2012-09-26 | 3M中国有限公司 | Adhesive tape composition and adhesive tape prepared by same |
| CN103992439A (en) * | 2014-04-30 | 2014-08-20 | 中国科学院化学研究所 | Light-cured unsaturated polyester material applied to three-dimensional printing rapid molding and preparation method thereof |
| CN104031304A (en) * | 2014-04-30 | 2014-09-10 | 中国科学院化学研究所 | Ultraviolet light crosslinked polymer material used for 3D printing, and preparation method and application thereof |
| CN105418893A (en) * | 2016-01-08 | 2016-03-23 | 中国林业科学研究院林产化学工业研究所 | Preparation method of thermosetting resin composition and cured product thereof |
-
2017
- 2017-06-27 CN CN201710498080.1A patent/CN107163478B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849460A (en) * | 1994-07-27 | 1998-12-15 | Hitachi, Ltd. | Photosensitive resin composition and method for using the same in manufacture of circuit boards |
| JP2002080525A (en) * | 2000-06-27 | 2002-03-19 | Showa Highpolymer Co Ltd | Thermosetting or photo-setting resin |
| CN1408764A (en) * | 2001-09-27 | 2003-04-09 | 山荣化学株式会社 | Light solidified and heat solidified resin composition and method for producing printed circuit board |
| CN102439089A (en) * | 2010-06-28 | 2012-05-02 | 株式会社艾迪科 | Curable resin composition |
| CN102533146A (en) * | 2010-12-06 | 2012-07-04 | 第一毛织株式会社 | Adhesive film for semiconductor device |
| CN102127386A (en) * | 2010-12-29 | 2011-07-20 | 东莞市新懿电子材料技术有限公司 | Light-curing and heat-curing conductive adhesive and preparation method |
| CN102690611A (en) * | 2011-12-27 | 2012-09-26 | 3M中国有限公司 | Adhesive tape composition and adhesive tape prepared by same |
| CN103992439A (en) * | 2014-04-30 | 2014-08-20 | 中国科学院化学研究所 | Light-cured unsaturated polyester material applied to three-dimensional printing rapid molding and preparation method thereof |
| CN104031304A (en) * | 2014-04-30 | 2014-09-10 | 中国科学院化学研究所 | Ultraviolet light crosslinked polymer material used for 3D printing, and preparation method and application thereof |
| CN105418893A (en) * | 2016-01-08 | 2016-03-23 | 中国林业科学研究院林产化学工业研究所 | Preparation method of thermosetting resin composition and cured product thereof |
Non-Patent Citations (3)
| Title |
|---|
| Morphology and mechanical properties of dual-curable epoxyacrylate hybrid composites;Su, Yu-Chieh，等;《JOURNAL OF APPLIED POLYMER SCIENCE》;20150415;第132卷(第15期);B014-73页 * |
| 光敏橡胶;角田隆弘，等;《橡胶译丛》;19810302;第77-82页 * |
| 含光敏基团线形梳状/星形梳状高支化聚丁二烯研究;张宇;《中国博士学位论文全文数据库 工程科技Ⅰ辑 》;20150715(第07期);第41820篇 * |
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