CN113880882A - Phosphorus-nitrogen light-cured flame-retardant acrylic resin, flame-retardant coating prepared from same and application of flame-retardant coating - Google Patents
Phosphorus-nitrogen light-cured flame-retardant acrylic resin, flame-retardant coating prepared from same and application of flame-retardant coating Download PDFInfo
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- CN113880882A CN113880882A CN202111209684.2A CN202111209684A CN113880882A CN 113880882 A CN113880882 A CN 113880882A CN 202111209684 A CN202111209684 A CN 202111209684A CN 113880882 A CN113880882 A CN 113880882A
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- phosphorus
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- nitrogen
- retardant
- acrylic resin
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 120
- 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 title claims abstract description 119
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 65
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 65
- 238000000016 photochemical curing Methods 0.000 claims abstract description 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- -1 nitrogen-containing triazine ring compound Chemical class 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 6
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 238000001723 curing Methods 0.000 claims description 33
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 19
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 17
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000012456 homogeneous solution Substances 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 239000002023 wood Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 5
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 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 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 3
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 claims description 2
- NPCUWXDZFXSRLT-UHFFFAOYSA-N chromium;2-ethylhexanoic acid Chemical compound [Cr].CCCCC(CC)C(O)=O NPCUWXDZFXSRLT-UHFFFAOYSA-N 0.000 claims description 2
- QZUFYZAIYPHVTL-UHFFFAOYSA-L diacetyloxy(butyl)tin Chemical compound CCCC[Sn](OC(C)=O)OC(C)=O QZUFYZAIYPHVTL-UHFFFAOYSA-L 0.000 claims description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229960003505 mequinol Drugs 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229960003742 phenol Drugs 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000006221 furniture coating Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/06—Triglycidylisocyanurates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a phosphorus-nitrogen photocuring flame-retardant acrylic resin, a flame-retardant coating prepared from the same and application of the flame-retardant acrylic resin, wherein a phosphorus source of the resin is provided by phosphate with active phosphorus hydrogen bonds, and a nitrogen source is provided by a nitrogen-containing triazine ring compound;the molar ratio of the phosphorus element of the phosphate to the nitrogen element of the nitrogen-containing triazine ring compound is 1:1, and the structure of the phosphorus-nitrogen photocuring flame-retardant acrylic resin is shown as a general formula (1):
Description
Technical Field
The invention relates to the technical field of chemical coating processing, in particular to a phosphorus-nitrogen photocuring flame-retardant acrylic resin, a flame-retardant coating prepared from the same and application of the flame-retardant coating.
Background
The Ultraviolet (UV) curing coating has the advantages of high curing speed, energy conservation, room temperature curing, no Volatile Organic Compound (VOC) and the like, is widely applied to PVC floors, shadow masks, food packages, wood floors, cabinet panels and the like, and has wide application prospect. With the development of economy, the decoration of wooden furniture also gradually becomes the focus of attention, and especially can be said to be of great importance in the decoration of home. The types of ground decoration materials in the market are also greatly enriched, and the ground materials commonly used at present comprise PVC (polyvinyl chloride) floors, wood floors, plastic floors and the like. The biggest defect of the floor and the wooden furniture is flammability, which is very easy to cause fire and flame spread. Therefore, the flame retardant coating of the invention is imminent.
Among the flame retardant coatings of the prior art in recent years, patent publication No. CN 107586507A discloses a flame retardant wooden furniture coating which has not an important moisture resistance function, although it can improve the corrosion resistance of the coating on wood and has the performances of fire and insect prevention, heat insulation, skid resistance and flame retardance. Patent publication No. CN 108753081A discloses a flame retardant floor coating, which solves the problem of poor adhesion between the carbonized layer and the substrate, improves the strength and toughness of the coating, and improves the fire-retardant property of the coating, but does not provide the floor with wear resistance.
The coating for floor and wooden furniture in the current market is not only expensive, but also has some defects, such as poor flame retardant property, insufficient adhesive force of the coating, poor wear resistance, easy layer formation and falling, and the like, and can not meet the use requirement.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a phosphorus-nitrogen-containing uv-curable flame retardant coating for indoor furniture and floors, which has the advantages of low cost, simple process, strong adhesion and mechanical properties, low viscosity, good wear resistance, excellent flame retardancy, heat resistance, moisture resistance, etc. Another purpose is to provide a preparation method of the phosphorus-nitrogen-containing ultraviolet curing flame-retardant coating.
The technical scheme of the invention is as follows:
a phosphorus-nitrogen light-cured flame-retardant acrylic resin, wherein a phosphorus source of the resin is provided by phosphate with active phosphorus hydrogen bonds, and a nitrogen source is provided by a nitrogen-containing triazine ring compound; the molar ratio of the phosphorus element of the phosphate to the nitrogen element of the nitrogen-containing triazine ring compound is 1: 1.
Preferably, the structure of the phosphorus-nitrogen photocuring flame-retardant acrylic resin is shown as a general formula (1):
in the general formula (1), R represents
One kind of (1).
A preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin comprises the following steps:
adding tris (2-hydroxyethyl) isocyanurate, itaconic anhydride and a polymerization inhibitor into an organic solvent at one time, and reacting for 3-5 h at 80-110 ℃;
adding a phosphorus-containing flame retardant monomer, and continuously reacting for 6-10 h at 80-110 ℃;
and finally, adding a catalyst and a glycidyl methacrylate monomer, heating to 110-130 ℃, reacting until the acid value is unchanged, stopping the reaction, removing the solvent by rotary evaporation, and drying in vacuum to obtain the transparent phosphorus-nitrogen photocuring flame-retardant acrylic resin.
In a preferable scheme, the polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, p-methoxyphenol, hydroquinone methyl ether, p-hydroxyanisole and 2-tert-butylhydroquinone; the phosphorus-containing flame retardant monomer is one or more of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dimethyl phosphite, diethyl phosphite and diphenyl phosphite; the organic solvent is one or more of 1, 4-dioxane, N-dimethylformamide, toluene, dimethyl sulfoxide, N-dimethylacetamide and N-methyl-pyrrolidone; the catalyst is one or more of tetrabutylammonium bromide, triphenylphosphine, chromium 2-ethylhexanoate, butyltin dilaurate, stannous octoate and butyltin diacetate;
the amount of the polymerization inhibitor is 0.05-0.2% of the total mass of the tris (2-hydroxyethyl) isocyanurate and the itaconic anhydride; the dosage of the catalyst is 0.5-3% of the total mass of the tris (2-hydroxyethyl) isocyanurate, the itaconic anhydride, the phosphorus-containing flame retardant monomer and the glycidyl methacrylate monomer.
In a preferable scheme, the molar ratio of the tris (2-hydroxyethyl) isocyanurate to the itaconic anhydride is 1: 2.8-3.2; the dosage of the organic solvent is such that the concentration of the tris (2-hydroxyethyl) isocyanurate and the itaconic anhydride is 1.0-2.0 g/mL; the molar ratio of the phosphorus-containing flame retardant monomer to tris (2-hydroxyethyl) isocyanurate is 2.8-3.2: 1; the molar ratio of the using amount of the glycidyl methacrylate monomer to the tris (2-hydroxyethyl) isocyanurate is 2.8-3.2: 1.
The phosphor-nitrogen-containing ultraviolet-curing flame-retardant coating contains the phosphor-nitrogen-containing ultraviolet-curing flame-retardant acrylic resin;
the phosphorus-nitrogen-containing ultraviolet curing flame-retardant coating comprises the following components in parts by weight:
preferably, the photosensitive resin is one of urethane acrylate, bisphenol a epoxy acrylate, polyester acrylate, epoxy soybean oil acrylate and novolac epoxy acrylate.
Preferably, the reactive diluent is one or more of neopentyl glycol diacrylate (NPGDA), hydroxyethyl methacrylate (HEMA), 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA); the photoinitiator is one of 1173, CBP, 184 and MBF; the auxiliary agent is defoaming agent BYK-011 and/or leveling agent BYK-3565.
A preparation method of the phosphorus and nitrogen containing ultraviolet curing flame retardant coating comprises the following steps:
mixing 50-70 parts of photosensitive resin, 0-10 parts of reactive diluent, 1-5 parts of photoinitiator, 20-50 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin and 0.1-0.5 part of auxiliary agent, and then stirring at the rotating speed of 1500-2500r/min for 5-10min to obtain a homogeneous solution, namely the phosphorus-nitrogen ultraviolet photocuring flame-retardant coating.
The application of the phosphorus and nitrogen containing ultraviolet curing flame retardant coating is to form a film on a plastic floor and a wood floor by using a roller coating method, wherein the thickness of the film is controlled to be 7-11 g/square meter and is 500mJ/cm2Ultraviolet curing under the energy of (3) to obtain a paint film.
The beneficial technical effects of the invention are as follows:
the phosphorus-nitrogen photocuring flame-retardant acrylic resin takes a tris (2-hydroxyethyl) isocyanurate monomer, an itaconic anhydride monomer, a phosphorus-containing flame retardant monomer and a glycidyl methacrylate monomer as raw materials, and is prepared into a trifunctional acrylic resin by a simple and efficient one-pot method; the phosphorus-nitrogen photocuring flame-retardant acrylic resin has a flexible and rigid structure, and the flexible structure enables the coating to have low viscosity and good performance, and can be directly applied to photocuring coatings; the rigid benzene ring and triazine ring structure enables the prepared coating to have excellent wear resistance; in addition, the phosphorus-nitrogen light-cured flame-retardant acrylic resin has higher functionality, so that the crosslinking density of the coating can be increased, and the pencil hardness and the heat resistance of the coating are improved; meanwhile, due to the existence of a hydrophobic structure in the phosphorus-nitrogen photocuring flame-retardant acrylic resin, the coating has certain moisture resistance; the phosphorus-nitrogen photocuring flame-retardant acrylic resin has a large amount of phosphorus sources and nitrogen sources, and the phosphorus-nitrogen cooperation can well improve the inflammability of the coating; the phosphorus-nitrogen photocuring flame-retardant acrylic resin has a similar hyperbranched three-dimensional structure, so that the interior of the acrylic resin has a large number of cavities and free volumes, and when the phosphorus-nitrogen photocuring flame-retardant acrylic resin is added into the phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating, the shrinkage of a system can be effectively reduced, and the internal stress is reduced; the addition of the phosphorus-nitrogen light-cured flame-retardant acrylic resin can not only enhance the cohesive force of the coating; and the curing shrinkage of the whole system can be effectively reduced, so that the adhesive force between the coating and the wood board can be improved.
The method for synthesizing the phosphorus-nitrogen photocuring flame-retardant acrylic resin has the advantages of simple process, low cost, green monomers and capability of being synthesized in large quantities.
The phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating prepared by the invention has the characteristics of excellent flame retardant property, resistance to heat and humidity, wear resistance, low shrinkage, low internal stress, strong adhesive force, high pencil hardness, low viscosity and the like. The paint film is obtained by adopting a UV curing mode, and a solvent is not required to be added in the system, so that the resource is saved, and the paint film is green and environment-friendly.
Drawings
FIG. 1 is an infrared spectrum of a phosphorus-nitrogen photocuring flame-retardant acrylic resin obtained in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the phosphorus-nitrogen photocuring flame-retardant acrylic resin obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
A phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating is prepared by the following steps:
70 parts of urethane acrylate, 5 parts of active diluent PETA, 3 parts of photoinitiator 1173, 30 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin, 0.3 part of defoamer BYK-011 and 0.4 part of flatting agent BYK-3565 are mixed and stirred for 5min at the rotating speed of 1800r/min to obtain a homogeneous solution, so that the phosphorus-nitrogen ultraviolet curing flame-retardant coating is obtained.
The preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin comprises the following steps:
26.1g (0.1mol) of tris (2-hydroxyethyl) isocyanurate, 33.7g (0.3mol) of itaconic anhydride, 0.1 wt% of p-hydroxybenzene plus phenol and 40mL of 1, 4-dioxane were added in one portion to the flask and reacted at 95 ℃ for 4 hours; then 64.8g (0.3mol) of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 32mL of 1, 4-dioxane solution are added into the reactor dropwise within 0.5h, and the reaction is continued for 8h at 95 ℃; then 42.3g (0.3mol) of glycidyl methacrylate and 262mL of 1, 4-dioxane are added into a flask and reacted at 115 ℃ until the acid value of the system is unchanged, after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, and the transparent phosphorus-nitrogen light-cured flame-retardant acrylic resin is obtained after vacuum drying.
The infrared absorption spectrum is shown in figure 1, and the nuclear magnetic resonance hydrogen spectrum is shown in figure 2.
As can be seen from FIG. 1, 918cm-1，1115cm-1And 1229cm-1Characteristic absorption peaks of P-O-Ph, P-Ph and P ═ O appear, 810cm-1And 1630cm-1The peak of unsaturated double bond of the acrylic resin appeared, and 910cm-1The characteristic absorption peaks of the left and right epoxy groups disappear. 3400cm-1And characteristic absorption peaks of hydroxyl generated by ring opening of epoxy groups appear on the left and right. The successful synthesis of the phosphorus-nitrogen light-cured flame-retardant acrylic resin is proved.
As can be seen from FIG. 2, 3.44 to 3.89ppm are proton signal peaks of methylene connected with an ester group, 4.69 to 4.80ppm are proton signal peaks of hydroxyl generated by ring opening of an epoxy group, 5.03 to 6.10ppm are proton signal peaks of unsaturated double bonds on glycidyl methacrylate, and 7.19 to 8.31ppm are proton signal peaks of benzene rings on 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which proves successful synthesis of the phosphorus-nitrogen photocuring flame-retardant acrylic resin.
Example 2
A phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating is prepared by the following steps:
70 parts of urethane acrylate, 5 parts of active diluent PETA, 3 parts of photoinitiator 1173, 30 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin, 0.3 part of defoamer BYK-011 and 0.4 part of flatting agent BYK-3565 are mixed and stirred for 8min at the rotating speed of 1500r/min to obtain a homogeneous solution, so that the phosphorus-nitrogen ultraviolet curing flame-retardant coating is obtained.
The preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin comprises the following steps:
26.1g (0.1mol) of tris (2-hydroxyethyl) isocyanurate, 31.5g (0.28mol) of itaconic anhydride, 0.05% by weight of p-hydroxybenzene plus phenol and 60mL of toluene were put into a flask in one portion and reacted at 110 ℃ for 3 hours; then 30.8g (0.28mol) of dimethyl phosphite and 32mL of toluene solution are added into the reactor dropwise in 0.5h, and the reaction is continued for 6h at 100 ℃; and adding 45.1g (0.32mol) of glycidyl methacrylate and 43mL of toluene into the flask, reacting at 115 ℃ until the acid value of the system is unchanged, concentrating the reaction solution by rotary evaporation after the reaction is finished, and drying in vacuum to obtain the transparent phosphorus-nitrogen light-cured flame-retardant acrylic resin.
Example 3
A phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating is prepared by the following steps:
70 parts of aromatic difunctional urethane acrylate, 5 parts of active diluent PETA, 3 parts of photoinitiator 1173, 30 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin, 0.3 part of defoaming agent BYK-011 and 0.4 part of flatting agent BYK-3565 are mixed and stirred for 5min at the rotating speed of 2500r/min to obtain a homogeneous solution, so that the phosphorus-nitrogen ultraviolet curing flame-retardant coating is obtained.
The preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin comprises the following steps:
26.1g (0.1mol) of tris (2-hydroxyethyl) isocyanurate, 35.9g (0.32mol) of itaconic anhydride, 0.2 wt% hydroquinone and 30mL of N, N-dimethylformamide were added in one portion to the flask and reacted at 110 ℃ for 5 hours; then 65.6g (0.28mol) of diphenyl phosphite and 35mL of N, N-dimethylformamide solution are added into the reactor dropwise within 0.5h, and the reaction is continued for 10h at 110 ℃; and adding 39.5g (0.28mol) of glycidyl methacrylate and 150mL of N, N-dimethylformamide into the flask, reacting at 115 ℃ until the acid value of the system is unchanged, concentrating the reaction solution by rotary evaporation after the reaction is finished, and drying in vacuum to obtain the transparent phosphorus-nitrogen photocuring flame-retardant acrylic resin.
Example 4
A phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating is prepared by the following steps:
mixing 80 parts of novolac epoxy acrylate, 10 parts of an active diluent HDDA, 5 parts of a photoinitiator 1173, 20 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin, 0.5 part of a defoaming agent BYK-011 and 0.5 part of a leveling agent BYK-3565, and stirring at the rotating speed of 2200r/min for 5min to obtain a homogeneous solution, thereby obtaining the phosphorus-nitrogen ultraviolet curing flame-retardant coating.
The preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin comprises the following steps:
26.1g (0.1mol) of tris (2-hydroxyethyl) isocyanurate, 35.9g (0.32mol) of itaconic anhydride, 0.1 wt% of p-hydroxybenzene plus phenol and 40mL of 1, 4-dioxane were added in one portion to the flask and reacted at 95 ℃ for 4 hours; then 64.8g (0.3mol) of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 32mL of 1, 4-dioxane solution are added into the reactor dropwise within 0.5h, and the reaction is continued for 8h at 95 ℃; then 42.3g (0.3mol) of glycidyl methacrylate and 262mL of 1, 4-dioxane are added into a flask and reacted at 115 ℃ until the acid value of the system is unchanged, after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, and the transparent phosphorus-nitrogen light-cured flame-retardant acrylic resin is obtained after vacuum drying.
Example 5
A phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating is prepared by the following steps:
70 parts of epoxidized soybean oil acrylate, 5 parts of a reactive diluent HEMA, 4 parts of a photoinitiator 184, 30 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin, 0.3 part of a defoaming agent BYK-011 and 0.3 part of a leveling agent BYK-3565 are mixed and stirred for 5min at the rotating speed of 2000r/min to obtain a homogeneous solution, so that the phosphorus-nitrogen ultraviolet curing flame-retardant coating is obtained.
The preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin comprises the following steps:
26.1g (0.1mol) of tris (2-hydroxyethyl) isocyanurate, 33.7g (0.3mol) of itaconic anhydride, 0.1 wt% of p-hydroxybenzene plus phenol and 40mL of 1, 4-dioxane were added in one portion to the flask and reacted at 95 ℃ for 4 hours; then 64.8g (0.3mol) of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 32mL of 1, 4-dioxane solution are added into the reactor dropwise within 0.5h, and the reaction is continued for 8h at 95 ℃; then 42.3g (0.3mol) of glycidyl methacrylate and 262mL of 1, 4-dioxane are added into a flask and reacted at 115 ℃ until the acid value of the system is unchanged, after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, and the transparent phosphorus-nitrogen light-cured flame-retardant acrylic resin is obtained after vacuum drying.
Example 6
A phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating is prepared by the following steps:
60 parts of bisphenol A type epoxy acrylate, 0 part of active diluent HDDA, 3 parts of photoinitiator CBP, 40 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin, 0.2 part of defoaming agent BYK-011 and 0.3 part of leveling agent BYK-3565 are mixed and stirred at the rotating speed of 1800r/min for 6min to obtain a homogeneous solution, so that the phosphorus-nitrogen ultraviolet curing flame-retardant coating is obtained.
The preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin comprises the following steps:
26.1g (0.1mol) of tris (2-hydroxyethyl) isocyanurate, 33.7g (0.3mol) of itaconic anhydride, 0.1 wt% of p-hydroxybenzene plus phenol and 40mL of 1, 4-dioxane were added in one portion to the flask and reacted at 95 ℃ for 4 hours; then 64.8g (0.3mol) of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 32mL of 1, 4-dioxane solution are added into the reactor dropwise within 0.5h, and the reaction is continued for 8h at 95 ℃; then 42.3g (0.3mol) of glycidyl methacrylate and 262mL of 1, 4-dioxane are added into a flask and reacted at 115 ℃ until the acid value of the system is unchanged, after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, and the transparent phosphorus-nitrogen light-cured flame-retardant acrylic resin is obtained after vacuum drying.
Example 7
A phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating is prepared by the following steps:
mixing 50 parts of polyester acrylate, 0 part of NPGDA (reactive diluent), 3 parts of CBP (photoinitiator), 50 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin, 0.1 part of defoaming agent BYK-011 and 0.2 part of flatting agent BYK-3565, and stirring at the rotating speed of 1500r/min for 5min to obtain a homogeneous solution, thereby obtaining the phosphorus-nitrogen ultraviolet curing flame-retardant coating.
The preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin comprises the following steps:
26.1g (0.1mol) of tris (2-hydroxyethyl) isocyanurate, 33.7g (0.3mol) of itaconic anhydride, 0.1 wt% of p-hydroxybenzene plus phenol and 40mL of 1, 4-dioxane were added in one portion to the flask and reacted at 95 ℃ for 4 hours; then 64.8g (0.3mol) of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 32mL of 1, 4-dioxane solution are added into the reactor dropwise within 0.5h, and the reaction is continued for 8h at 95 ℃; then 42.3g (0.3mol) of glycidyl methacrylate and 262mL of 1, 4-dioxane are added into a flask and reacted at 115 ℃ until the acid value of the system is unchanged, after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, and the transparent phosphorus-nitrogen light-cured flame-retardant acrylic resin is obtained after vacuum drying.
Comparative example 1:
the same procedure as in example 1 was conducted except that the phosphorus-nitrogen photocuring flame-retardant acrylic resin was not added, thereby obtaining the photocurable coating of comparative example 1.
Comparative example 2:
the same procedure as in example 2 was carried out except that the phosphorus-nitrogen photocuring flame-retardant acrylic resin was not added, thereby obtaining the photocurable coating of comparative example 2.
Comparative example 3:
the same procedure as in example 3 was conducted except that the phosphorus-nitrogen photocuring flame-retardant acrylic resin was not added, thereby obtaining the photocurable coating of comparative example 3.
Comparative example 4:
the same procedure as in example 5 was conducted except that the phosphorus-nitrogen photocuring flame-retardant acrylic resin was not added, thereby obtaining the photocurable coating of comparative example 4.
Film coating Performance test
The UV light containing phosphorus and nitrogen prepared in examples 1-3The cured flame-retardant coating is formed into a film on a plastic floor by a roll coating method, and the phosphorus-nitrogen-containing ultraviolet-curable flame-retardant coating prepared in examples 4 to 7 is formed into a film on a tung wood board furniture by a roll coating method, wherein the thickness is controlled to be 8 g/square meter. At 500mJ/cm2The ultraviolet curing is carried out under the energy of (1) to obtain a paint film, and the performance test results are shown in Table 1.
TABLE 1
Note: the pencil hardness was measured in GB/T6739-. X: indicating a completely frosted surface, the light transmission drops severely: and (delta): the number of scratches which are not ground but have a surface of more than 1cm is more than 30: o: the number of surface > 1cm of scar strips is between 5 and 30: □: the number of the surface-1 cm scratches is less than 5, and the moisture and heat resistance is measured according to GB/T1740-2007.
As can be seen from table 1, in the examples 1 to 7, compared with the coating film properties, mechanical properties, processability, wear resistance, flame retardancy and the like of the comparative examples 1 to 4, the multifunctional phosphorus-nitrogen photocuring flame-retardant acrylic resin can increase the crosslinking density of the coating, and contains rigid triazine ring and benzene ring structures, so that the pencil hardness, wear resistance, wet heat resistance and tensile strength of the coating are improved. In addition, the phosphorus-nitrogen light-cured flame-retardant acrylic resin contains a flexible glycidyl methacrylate structure, so that the viscosity of the resin can be reduced. Meanwhile, the phosphorus-nitrogen light-cured flame-retardant acrylic resin can enhance the cohesive force of the coating; on the other hand, the curing shrinkage of the whole system can be effectively reduced, so that the adhesive force between the coating and the base material is improved. Compared with comparative examples 1-3, the limiting oxygen index and the vertical burning grade of examples 1-7 are greatly improved, mainly because the phosphorus-nitrogen photocuring flame-retardant acrylic resin plays a good phosphorus-nitrogen synergistic effect. As shown above, the phosphorus-nitrogen light-cured flame-retardant acrylic resin can provide excellent flame-retardant performance, improve the rigidity and mechanical properties of the coating, resist wear and humidity, and reduce the viscosity of the composite resin.
Claims (10)
1. A phosphorus-nitrogen photocuring flame-retardant acrylic resin is characterized in that a phosphorus source of the resin is provided by phosphate with active phosphorus hydrogen bonds, and a nitrogen source is provided by a nitrogen-containing triazine ring compound; the molar ratio of the phosphorus element of the phosphate to the nitrogen element of the nitrogen-containing triazine ring compound is 1: 1.
2. The phosphorus-nitrogen photocuring flame-retardant acrylic resin as claimed in claim 1, wherein the structure of the phosphorus-nitrogen photocuring flame-retardant acrylic resin is represented by the general formula (1):
in the general formula (1), R represents
One kind of (1).
3. The preparation method of the phosphorus-nitrogen photocuring flame-retardant acrylic resin as claimed in claim 1, which is characterized by comprising the following steps:
adding tris (2-hydroxyethyl) isocyanurate, itaconic anhydride and a polymerization inhibitor into an organic solvent at one time, and reacting for 3-5 h at 80-110 ℃;
adding a phosphorus-containing flame retardant monomer, and continuously reacting for 6-10 h at 80-110 ℃;
and finally, adding a catalyst and a glycidyl methacrylate monomer, heating to 110-130 ℃, reacting until the acid value is unchanged, stopping the reaction, removing the solvent by rotary evaporation, and drying in vacuum to obtain the transparent phosphorus-nitrogen photocuring flame-retardant acrylic resin.
4. The preparation method according to claim 3, wherein the polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, p-methoxyphenol, hydroquinone methyl ether, p-hydroxyanisole, 2-tert-butylhydroquinone; the phosphorus-containing flame retardant monomer is one or more of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dimethyl phosphite, diethyl phosphite and diphenyl phosphite; the organic solvent is one or more of 1, 4-dioxane, N-dimethylformamide, toluene, dimethyl sulfoxide, N-dimethylacetamide and N-methyl-pyrrolidone; the catalyst is one or more of tetrabutylammonium bromide, triphenylphosphine, chromium 2-ethylhexanoate, butyltin dilaurate, stannous octoate and butyltin diacetate;
the amount of the polymerization inhibitor is 0.05-0.2% of the total mass of the tris (2-hydroxyethyl) isocyanurate and the itaconic anhydride; the dosage of the catalyst is 0.5-3% of the total mass of the tris (2-hydroxyethyl) isocyanurate, the itaconic anhydride, the phosphorus-containing flame retardant monomer and the glycidyl methacrylate monomer.
5. The preparation method according to claim 3, wherein the molar ratio of the tris (2-hydroxyethyl) isocyanurate to the itaconic anhydride is 1: 2.8-3.2; the dosage of the organic solvent is such that the concentration of the tris (2-hydroxyethyl) isocyanurate and the itaconic anhydride is 1.0-2.0 g/mL; the molar ratio of the phosphorus-containing flame retardant monomer to tris (2-hydroxyethyl) isocyanurate is 2.8-3.2: 1; the molar ratio of the using amount of the glycidyl methacrylate monomer to the tris (2-hydroxyethyl) isocyanurate is 2.8-3.2: 1.
6. A phosphorus-nitrogen-containing ultraviolet-curable flame-retardant coating, which is characterized by comprising the phosphorus-nitrogen-containing ultraviolet-curable flame-retardant acrylic resin according to any one of claims 1 to 2;
the phosphorus-nitrogen-containing ultraviolet curing flame-retardant coating comprises the following components in parts by weight:
7. the phosphorus-nitrogen-containing ultraviolet-curable flame-retardant coating according to claim 6, wherein the photosensitive resin is one of urethane acrylate, bisphenol A epoxy acrylate, polyester acrylate, epoxy soybean oil acrylate, and novolac epoxy acrylate.
8. The UV-curable flame retardant coating material with phosphorus and nitrogen content according to claim 6, wherein the reactive diluent is one or more selected from neopentyl glycol diacrylate (NPGDA), hydroxyethyl methacrylate (HEMA), 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA); the photoinitiator is one of 1173, CBP, 184 and MBF; the auxiliary agent is defoaming agent BYK-011 and/or leveling agent BYK-3565.
9. A preparation method of the phosphorus-nitrogen-containing ultraviolet-curing flame-retardant coating as claimed in claim 6, characterized in that the preparation method comprises the following steps:
mixing 50-70 parts of photosensitive resin, 0-10 parts of reactive diluent, 1-5 parts of photoinitiator, 20-50 parts of phosphorus-nitrogen photocuring flame-retardant acrylic resin and 0.1-0.5 part of auxiliary agent, and then stirring at the rotating speed of 1500-2500r/min for 5-10min to obtain a homogeneous solution, namely the phosphorus-nitrogen ultraviolet photocuring flame-retardant coating.
10. The use of the UV-curable flame-retardant coating containing phosphorus and nitrogen according to claim 6, wherein the coating is prepared by mixing the componentsThe roller coating method for the phosphorus-nitrogen-containing ultraviolet curing flame-retardant coating is used for forming a film on a plastic floor and a wood floor, the thickness is controlled to be 7-11 g/square meter and is 500mJ/cm2Ultraviolet curing under the energy of (3) to obtain a paint film.
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| CN115926183A (en) * | 2022-12-15 | 2023-04-07 | 常州回天新材料有限公司 | Phosphorus-nitrogen hyperbranched flame-retardant resin and preparation method and application thereof |
| CN117877803A (en) * | 2024-03-08 | 2024-04-12 | 天津市华夏电缆有限公司 | Smoke-suppressing flame-retardant cable |
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| CN115247046A (en) * | 2022-06-02 | 2022-10-28 | 上海库弗新材料有限公司 | High-transmittance LED/UV ultraviolet curing flame-retardant adhesive and preparation method thereof |
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| CN117877803A (en) * | 2024-03-08 | 2024-04-12 | 天津市华夏电缆有限公司 | Smoke-suppressing flame-retardant cable |
| CN117877803B (en) * | 2024-03-08 | 2024-05-14 | 天津市华夏电缆有限公司 | Smoke-suppressing flame-retardant cable |
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