CN115595033B - Organic phosphonic acid metal salt flame-retardant composition coating, preparation method and application - Google Patents
Organic phosphonic acid metal salt flame-retardant composition coating, preparation method and application Download PDFInfo
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- CN115595033B CN115595033B CN202211377928.2A CN202211377928A CN115595033B CN 115595033 B CN115595033 B CN 115595033B CN 202211377928 A CN202211377928 A CN 202211377928A CN 115595033 B CN115595033 B CN 115595033B
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- coating
- flame retardant
- monomer
- phosphonic acid
- metal salt
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- 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 196
- 239000003063 flame retardant Substances 0.000 title claims abstract description 193
- 238000000576 coating method Methods 0.000 title claims abstract description 173
- 239000011248 coating agent Substances 0.000 title claims abstract description 157
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 133
- 239000002184 metal Substances 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 106
- 150000003839 salts Chemical class 0.000 title claims abstract description 98
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 120
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 59
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 52
- 239000011574 phosphorus Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 42
- -1 acrylic ester Chemical class 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 29
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000005507 spraying Methods 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003618 dip coating Methods 0.000 claims description 18
- 239000004033 plastic Substances 0.000 claims description 18
- 238000010345 tape casting Methods 0.000 claims description 18
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 125000006309 butyl amino group Chemical group 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 238000007761 roller coating Methods 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 claims description 2
- CQCXMYUCNSJSKG-UHFFFAOYSA-N 1-dimethoxyphosphorylethene Chemical compound COP(=O)(OC)C=C CQCXMYUCNSJSKG-UHFFFAOYSA-N 0.000 claims description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- GZNJJEODYYLYSA-UHFFFAOYSA-N diethyl prop-2-enyl phosphate Chemical compound CCOP(=O)(OCC)OCC=C GZNJJEODYYLYSA-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 58
- 238000003756 stirring Methods 0.000 description 28
- 239000012153 distilled water Substances 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 238000000502 dialysis Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000010276 construction Methods 0.000 description 5
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- SKRKROTYQLXALL-UHFFFAOYSA-N [P]Br Chemical compound [P]Br SKRKROTYQLXALL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an organic phosphonic acid metal salt flame-retardant composition coating, a preparation method and application thereof, and relates to the field of flame-retardant chemical material preparation, wherein the monomer raw materials comprise the following components in parts by mole: 20-165 parts of acrylic ester monomer, 35-110 parts of phosphorus-containing flame-retardant monomer and 35-220 parts of metal hydroxide; the invention has simple synthesis process, stable polymerization and higher yield, and the selected raw materials are green and nontoxic, thereby meeting the requirement of high adhesive force of the coating on the substrate; the synergistic effect of phosphorus and metal ions is fully exerted, the flame retardant property of the copolymer coating is further improved, and the safety performance to the base material fire is obviously improved under the condition of lower sizing amount. The flame retardant coating has the advantages that an effective flame retardant effect is provided for various inflammable base materials, the flame retardant coating is superior to common organic phosphorus flame retardant coatings in char formation, the high-temperature stability and barrier property of the residual metal salt carbon layer are far superior to those of the organic carbon layer, the flame retardant coating is durable and effective at high temperature, and the flame retardant coating has extremely high commercial value.
Description
Technical Field
The invention relates to the field of preparation of flame-retardant chemical materials, in particular to an organic phosphonic acid metal salt flame-retardant composition coating, a preparation method and application thereof, and in particular relates to a technical means of an organic phosphonic acid metal salt flame-retardant coating which can be attached to the surface of a flammable substrate.
Background
In recent years, fire has become one of the major hazards threatening public life safety and social development. Materials such as plastics and wood which are visible everywhere in daily life have the defects of low limiting oxygen index, high heat value and easy ignition. It is proved that once the material is ignited, the flame spreads very fast on the surface, so that the occurrence of fire is promoted, and the important loss of life and property is caused for people.
Constructing a surface coating with a flame retardant function on the surface of a flammable substrate is an effective means for reducing the fire hazard of the flammable substrate, and the method has the advantages of low consumption of flame retardant, simple construction, wide applicability and the like, and can be applied to the surface of the material in a manner of dip coating, spray coating, brush coating, knife coating, roller coating and the like; the flame-retardant coating can be carbonized to form a heat-stable heat-insulating fireproof protective layer under flame or high temperature, so that internal base materials are prevented from being affected by flame.
However, most of the traditional flame retardant coating before adopts halogen flame retardant, chinese patent publication No. CN112553913A discloses a heavy metal-free bromophosphorus synergistic aqueous textile flame retardant coating composition containing hyperbranched polymer, wherein the composition comprises film forming agent, hydrophobic modified emulsion, brominated flame retardant, phosphorus-containing flame retardant, hyperbranched carbon forming agent and aqueous coating auxiliary agent, the brominated flame retardant is decabromodiphenyl ethane, the phosphorus-containing flame retardant is selected from hydrophobic modified wrapped ammonium polyphosphate, and the hydrophobic modified emulsion is selected from organosilicon modified acrylic acid polyester emulsion and polyurethane modified acrylic acid polyester emulsion. The flame retardant coating is prepared by adopting the decabromodiphenylethane as the flame retardant, and the coating composition has good water resistance and excellent flame retardant effect, but contains a halogen flame retardant unit with potential hazard, and can decompose corrosive gas after combustion, thus the coating composition has obvious disadvantages under the current market requirement of pursuing halogen-free environment protection.
The Chinese patent of the invention with the publication number of CN110527371A proposes a sandwich-structured high-efficiency flame-retardant coating, which is prepared by sequentially preparing a bottom conducting layer, a middle temperature-sensitive sensing layer and a top super-hydrophobic conducting layer on a flammable substrate, wherein the bottom conducting layer is prepared by uniformly dispersing a metal nano material and an oil-soluble long-chain polymer together in an organic solvent to form a coating A, then spraying the coating A on the substrate, and drying for the first time; the spraying and drying process is repeated 1 to 10 times. However, the construction process involves the use of various toxic organic solvents, which is easy to pollute the environment and influence the health of human bodies. In recent years, as the national environmental protection policy becomes more stringent, people begin to gradually abandon the use of such traditional flame retardant coatings.
The Chinese patent publication No. CN106632468B discloses a preparation method of an amino trimethylene phosphonic acid metal salt flame retardant, wherein the amino trimethylene phosphonic acid metal salt is prepared by reacting amino trimethylene phosphonic acid and metal chloride, and the specific steps are as follows: amino trimethylene phosphonic acid and metal chloride are mixed according to a mole ratio of 1:1, adding the mixture into a reaction vessel with stirring, adding water with the amount of 20-50 times of the metal chloride, uniformly stirring, adjusting the pH value to 1-3, heating to 100-130 ℃, reacting for 24-48 hours, filtering the product, washing with water, and drying to obtain the amino trimethylene phosphonic acid metal salt flame retardant. The amino trimethylene phosphonic acid metal salt flame retardant is prepared by taking amino trimethylene phosphonic acid and metal chloride as raw materials, and is found to have the advantages of good thermal stability, high flame retardant efficiency and high carbon residue rate, however, the flame retardant does not have the coating characteristic and is only suitable for being used as an additive flame retardant.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a novel organic phosphonic acid metal salt flame-retardant coating system which is simple to prepare, environment-friendly, halogen-free, low-toxicity, durable in performance, high in adhesiveness, high in transparency and capable of effectively resisting high temperature for a long time, and the novel organic phosphonic acid metal salt flame-retardant coating system can be popularized to the fields of buildings, bridges, pipelines, traffic and the like, and has a wide application prospect.
The first object of the invention is realized by the following technical scheme: the organic phosphonic acid metal salt flame-retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 20-165 parts;
Phosphorus-containing flame retardant monomer: 35-110 parts;
metal hydroxide: 35-220 parts.
Further, the acrylic monomer comprises one or more acrylic substances such as ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycidyl acrylate and the like.
Further, the phosphorus-containing flame retardant monomer comprises one or more of 1-styrylphosphonic acid, vinylphosphonic acid, phosphonic acid-beta-styryl ester, dimethyl vinylphosphonate, diethyl vinylphosphonate and allyl diethyl phosphate.
Further, the metal in the metal hydroxide comprises a 1-valent metal hydroxide or a combination of a 1-valent metal hydroxide and a plurality of n-valent metal hydroxides; n is a positive integer greater than 1;
The metal hydroxide comprises one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, copper hydroxide, barium hydroxide, zinc hydroxide and nickel hydroxide;
the molar ratio of the metal hydroxide to the phosphorus-containing flame retardant monomer is less than or equal to 2:1.
Further, the molar part ratio of the acrylic monomer to the phosphorus-containing flame-retardant monomer is 4: 6-6: 4, a step of;
The molar ratio of the 1-valence metal hydroxide to the metal hydroxide is X, and the molar ratio of the n-valence metal hydroxide to the metal hydroxide is Y n,X+∑Yn＝1,∑Yn -3%;
the molar ratio of the metal hydroxide to the phosphorus-containing flame-retardant monomer is less than or equal to Wherein n is a positive integer greater than 1.
Wherein the mol part ratio range of the acrylic monomer to the phosphorus-containing flame-retardant monomer is 4: 6-6: 4, but for better effect and more convenient test, the molar ratio of the acrylic monomer to the phosphorus-containing flame-retardant monomer is generally 1:1.
In addition, the inventors have also found that the addition of a high-valence metal hydroxide (other than 1-valence metal hydroxide) alone as a metal hydroxide results in difficulty in the construction of crosslinking of the coating, and therefore it is necessary to use the high-valence metal hydroxide in cooperation with 1-valence metal hydroxide, and the molar amount of the high-valence metal hydroxide is usually within 3% of the total molar amount of the metal hydroxide.
And under the condition that the high-valence metal hydroxide is multiplexed with the 1-valence metal hydroxide, the crosslinking of the polymer is promoted, and the high-temperature carbonization performance is better. If the metal hydroxide is not added, the molar ratio of the phosphorus-containing flame-retardant monomer is more than 50 percent, and if the metal hydroxide and the phosphorus-containing flame-retardant monomer are multiplexed, the effect is far better than that of the phosphorus-containing flame-retardant monomer.
The invention also aims to provide a preparation method of the organic phosphonic acid metal salt flame-retardant composition coating. The second purpose of the invention is realized by the following technical scheme: a preparation method of an organic phosphonic acid metal salt flame retardant composition coating comprises the following steps:
A. Mixing a phosphorus-containing flame-retardant monomer, an acrylic ester monomer and a solvent; the solvent comprises one or more of water, ethanol, propanol, butanol, ethyl acetate or dimethyl sulfoxide;
B. Adding an initiator to the mixture; the initiator comprises one or more of potassium persulfate, ammonium persulfate, azobisisobutyrimidine hydrochloride and azobisisobutyronitrile;
C. And adding metal hydroxide to obtain the organic phosphonic acid metal salt flame-retardant composition coating.
Further, the step A specifically includes the following steps:
adding a phosphorus-containing flame-retardant monomer and an acrylic ester monomer into a solvent under the atmosphere of nitrogen, and mixing at constant temperature;
The solvent temperature and the constant temperature are 60-80 ℃, and the total concentration of the phosphorus-containing flame-retardant monomer and the acrylic ester monomer solution is 10-35 wt%.
Further, the step B specifically includes the following steps:
adding an initiator into a mixture of a phosphorus-containing flame-retardant monomer, an acrylic ester monomer and a solvent mixture for the first time, carrying out a constant-temperature copolymerization reaction, and adding the initiator for the second time before the reaction is finished to finally obtain the organic phosphonic acid metal salt flame-retardant composition coating;
the first time of adding the initiator is 30-60 min after mixing the phosphorus-containing flame-retardant monomer, the acrylic ester monomer and the solvent, the first time of adding the initiator is 3-6 h after the constant temperature copolymerization reaction, and the second time of adding the initiator is 0.5-1 h before the end of the constant temperature copolymerization reaction;
The initiator is 0.1-1.5 wt% of the total mass of the phosphorus-containing flame-retardant monomer and the acrylic ester monomer, the input of the initiator is 80-95 wt% of the total amount of the initiator in the first time, and the input of the initiator is 5-20 wt% of the total amount of the initiator in the second time.
Further, the step C specifically includes the following steps:
Adding metal hydroxide to react for 0.5-6 h at 25-80 ℃ to obtain the organic phosphonic acid metal salt flame-retardant composition coating.
The invention aims at providing an application of an organic phosphonic acid metal salt flame-retardant composition coating. The third object of the invention is realized by the following technical scheme: the application of the organic phosphonic acid metal salt flame retardant composition coating on the outer surface of one or more substrates in foam boards, plastics, wood and metals;
The organic phosphonic acid metal salt flame retardant composition coating is applied to the outer surface of the substrate and cured by one or more of dip coating, spray coating, brush coating, knife coating and roller coating processes; applying a thickness of at least 1 micron; preferably 1-3000 microns in thickness;
The curing condition of the organic phosphonic acid metal salt flame retardant composition coating is 60-90 ℃ for 0.5-3 h.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) The monomer raw materials in the organic phosphonic acid metal salt flame retardant composition coating comprise the following components in parts by mole: 35-110 parts of acrylic ester monomer, 35-110 parts of phosphorus-containing flame-retardant monomer and 35-110 parts of metal hydroxide; raw materials are easy to obtain, safe and halogen-free, the synthesis process is simple, and a high-toxicity solvent is not adopted, so that the green flame-retardant aim can be realized;
(2) The phosphorus-containing flame-retardant monomer of the organic phosphonic acid metal salt flame-retardant composition coating has the advantages of simple synthesis process, stable polymerization and higher yield, and the selected raw materials are green and nontoxic, so that the high adhesive force requirement of the coating on a substrate is met; the synergistic effect of phosphorus and metal ions is fully exerted, and the flame retardant property of the copolymer coating is further improved, so that the copolymer coating can meet the remarkable improvement of the fire safety performance of a base material under the condition of lower sizing amount;
(3) The organic phosphonic acid metal salt flame-retardant composition coating material is simple to use, has wide applicability, and is suitable for large-scale use in the fields of construction, bridges, pipelines, traffic and the like.
Detailed Description
The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, and should be considered as specifically disclosed herein, the invention is described in detail below in connection with the specific embodiments:
Example 1
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
Acrylic ester monomer: 65 parts;
Phosphorus-containing flame retardant monomer: 43 parts;
Metal hydroxide: 43 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.043mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, gradually warmed to 70℃under nitrogen atmosphere and kept stirring to dissolve PPA completely. 0.065mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the PPA aqueous solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the solution is reacted for 4h at constant temperature, then 0.016gKPS is added again, and the reaction is continued for 0.5h.
C. 2.4g of potassium hydroxide was added and stirring was continued at 50℃for 3 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-K40-co-HEA 60) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-K40-co-HEA 60) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 2
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 54 parts;
phosphorus-containing flame retardant monomer: 54 parts;
Metal hydroxide: 53 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.054mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, gradually warmed to 70℃under nitrogen atmosphere and kept stirring to dissolve PPA completely. 0.054mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the PPA aqueous solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the solution is reacted for 4h at constant temperature, then 0.016gKPS is added again, and the reaction is continued for 0.5h.
C. 3g of potassium hydroxide was added and stirring was continued at 50℃for 3 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-K50-co-HEA 50) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-K50-co-HEA 50) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 3
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 48 parts;
Phosphorus-containing flame retardant monomer: 60 parts;
Metal hydroxide: 60 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.060mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, gradually heated to 70℃under nitrogen atmosphere and kept stirring to dissolve PPA completely. 0.048mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the PPA aqueous solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the solution is reacted for 4h at constant temperature, then 0.016gKPS is added again, and the reaction is continued for 0.5h.
C. 3.4g of potassium hydroxide was added and stirring was continued at 50℃for 3 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-K55-co-HEA 45) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-K55-co-HEA 45) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 4
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 43 parts;
Phosphorus-containing flame retardant monomer: 65 parts;
metal hydroxide: 64 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.065mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, gradually heated to 70℃under nitrogen atmosphere and kept stirring to dissolve PPA completely. 0.043mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the PPA aqueous solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the solution is reacted for 4h at constant temperature, then 0.016gKPS is added again, and the reaction is continued for 0.5h.
C. 3.6g of potassium hydroxide was added and stirring was continued at 50℃for 3 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-K60-co-HEA 40) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-K60-co-HEA 40) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 5
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 110 parts;
Phosphorus-containing flame retardant monomer: 76 parts;
Metal hydroxide: 75 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.076mol of vinylphosphonic acid (VPA) was weighed into 29g of distilled water, and gradually warmed to 80℃with continued nitrogen introduction and maintained under stirring. 0.11mol of hydroxyethyl acrylate (HEA) is weighed and slowly added dropwise to the aqueous VPA solution.
B. 0.19g of azobisisobutyrimidine hydrochloride (AIBA) was dissolved in 19g of distilled water, and the monomer solution was slowly dropped into the solution at a constant speed over 0.5h, and after keeping the constant temperature for 2h, 0.02gAIBA was added again, and the reaction was continued for 0.5h.
C. 1.8g of lithium hydroxide was slowly added and stirred vigorously at room temperature for 6 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (VPA-Li 40-co-HEA 60) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (VPA-Li 40-co-HEA 60) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 6
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 93 parts;
Phosphorus-containing flame retardant monomer: 93 parts;
Metal hydroxide: 93 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.093mol of vinylphosphonic acid (VPA) is weighed into 29g of distilled water, and gradually heated to 80℃with continuous nitrogen introduction and stirring. 0.093mol of hydroxyethyl acrylate (HEA) was weighed and slowly added dropwise to the aqueous VPA solution.
B. 0.19g of azobisisobutyrimidine hydrochloride (AIBA) was dissolved in 19g of distilled water, and the monomer solution was slowly dropped into the solution at a constant speed over 0.5h, and after keeping the constant temperature for 2h, 0.02gAIBA was added again, and the reaction was continued for 0.5h.
C. 2.2g of lithium hydroxide was slowly added and stirred vigorously at room temperature for 6 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (VPA-Li 50-co-HEA 50) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (VPA-Li 50-co-HEA 50) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 7
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 84 parts;
Phosphorus-containing flame retardant monomer: 102 parts;
metal hydroxide: 100 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.102mol of vinylphosphonic acid (VPA) was weighed into 29g of distilled water, and gradually warmed to 80℃with continuous nitrogen introduction and kept stirring. 0.084mol of hydroxyethyl acrylate (HEA) was weighed and slowly added dropwise to the aqueous VPA solution.
B. 0.19g of azobisisobutyrimidine hydrochloride (AIBA) was dissolved in 19g of distilled water, and the monomer solution was slowly dropped into the solution at a constant speed over 0.5h, and after keeping the constant temperature for 2h, 0.02gAIBA was added again, and the reaction was continued for 0.5h.
C. 2.4g of lithium hydroxide was slowly added and stirred vigorously at room temperature for 6 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (VPA-Li 55-co-HEA 45) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (VPA-Li 55-co-HEA 45) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested and the test results are shown in Table 1.
Example 8
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 76 parts;
Phosphorus-containing flame retardant monomer: 110 parts;
Metal hydroxide: 109 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.110mol of vinylphosphonic acid (VPA) was weighed into 29g of distilled water, and gradually warmed to 80℃with continuous nitrogen introduction and kept stirring. 0.076mol of hydroxyethyl acrylate (HEA) was weighed and slowly added dropwise to the aqueous VPA solution.
B. 0.19g of azobisisobutyrimidine hydrochloride (AIBA) was dissolved in 19g of distilled water, and the monomer solution was slowly dropped into the solution at a constant speed over 0.5h, and after keeping the constant temperature for 2h, 0.02gAIBA was added again, and the reaction was continued for 0.5h.
C. 2.6g of lithium hydroxide was slowly added and stirred vigorously at room temperature for 6 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (VPA-Li 60-co-HEA 40) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (VPA-Li 60-co-HEA 40) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested and the test results are shown in Table 1.
Example 9
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 54 parts;
phosphorus-containing flame retardant monomer: 36 parts;
metal hydroxide: 37 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.036mol of 1-styrylphosphonic acid (PPA) was weighed into 25.5g of dimethyl sulfoxide (DMSO), and gradually warmed to 60℃under continuous nitrogen and kept stirring to dissolve completely. 0.054mol of ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate (BCOE) monomer was weighed and slowly added dropwise to the PPA solution.
B. 0.16g of Azobisisobutyronitrile (AIBN) was dissolved in 16gDMSO and the monomer solution was slowly dropped at a constant speed over 0.5 hours, and after keeping the constant temperature for 4 hours, 0.02g of AIBN was added again to continue the reaction for 0.5 hours.
C. 1.5g of sodium hydroxide was slowly added and the copolymer solution was taken out with vigorous stirring at room temperature for 3 hours. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-Na 40-co-BCOE) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-Na 40-co-BCOE) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 10
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
Acrylic ester monomer: 45 parts;
phosphorus-containing flame retardant monomer: 45 parts;
metal hydroxide: 45 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.045mol of 1-styrylphosphonic acid (PPA) was weighed into 25.5g of dimethyl sulfoxide (DMSO), and gradually warmed to 60℃under continuous nitrogen and kept stirring to dissolve completely. 0.045mol of ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate (BCOE) monomer was weighed and slowly dropped into the PPA solution.
B. 0.16g of Azobisisobutyronitrile (AIBN) was dissolved in 16gDMSO and the monomer solution was slowly dropped at a constant speed over 0.5 hours, and after keeping the constant temperature for 4 hours, 0.02g of AIBN was added again to continue the reaction for 0.5 hours.
C. 1.8g of sodium hydroxide was slowly added and the copolymer solution was taken out with vigorous stirring at room temperature for 3 hours. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-Na 50-co-BCOE) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-Na 50-co-BCOE) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 11
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 40 parts;
Phosphorus-containing flame retardant monomer: 50 parts;
Metal hydroxide: 50 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.050mol of 1-styrylphosphonic acid (PPA) was weighed into 25.5g of dimethyl sulfoxide (DMSO), and gradually warmed to 60℃with continuous nitrogen and kept stirring to dissolve completely. 0.040mol of ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate (BCOE) monomer was weighed and slowly dropped into the PPA solution.
B. 0.16g of Azobisisobutyronitrile (AIBN) was dissolved in 16gDMSO and the monomer solution was slowly dropped at a constant speed over 0.5 hours, and after keeping the constant temperature for 4 hours, 0.02g of AIBN was added again to continue the reaction for 0.5 hours.
C. 2g of sodium hydroxide was slowly added and the copolymer solution was taken out with vigorous stirring at room temperature for 3 h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-Na 55-co-BCOE) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-Na 55-co-BCOE) 45 and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 12
The organic phosphonic acid metal salt flame retardant composition coating comprises the following components in parts by mole:
acrylic ester monomer: 36 parts;
phosphorus-containing flame retardant monomer: 54 parts;
metal hydroxide: 55 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.054mol of 1-styrylphosphonic acid (PPA) was weighed into 25.5g of dimethyl sulfoxide (DMSO), and gradually warmed to 60℃with continuous nitrogen and kept stirring to dissolve completely. 0.036mol of ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate (BCOE) monomer was weighed and slowly dropped into the PPA solution.
B. 0.16g of Azobisisobutyronitrile (AIBN) was dissolved in 16gDMSO and the monomer solution was slowly dropped at a constant speed over 0.5 hours, and after keeping the constant temperature for 4 hours, 0.02g of AIBN was added again to continue the reaction for 0.5 hours.
C. 2.2g of sodium hydroxide was slowly added and the copolymer solution was taken out with vigorous stirring at room temperature for 3 h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-Na 60-co-BCOE 40) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-Na 60-co-BCOE) and its heat release rate Peak (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Example 13
The organic phosphonic acid metal salt flame retardant composition coating differs from example 1 in that the comonomer starting materials of the composition comprise the following components in parts by mole:
acrylic ester monomer: 54 parts;
phosphorus-containing flame retardant monomer: 54 parts;
Metal hydroxide: 53 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.054mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, gradually warmed to 70℃under nitrogen atmosphere and kept stirring to dissolve PPA completely. 0.054mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the PPA aqueous solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the solution is reacted for 4h at constant temperature, then 0.016gKPS is added again, and the reaction is continued for 0.5h.
C. 2.9g of potassium hydroxide and 0.1g of calcium hydroxide were added and stirring was continued at 50℃for 5 hours, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, so that the organic phosphonic acid metal salt flame-retardant polymer coating Poly (PPA-K-Ca 50-co-HEA 50) is obtained.
In a specific embodiment, there is provided the use of a coating of the above-described metal organophosphonate flame retardant composition, applied to the outer surface of a foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating processes and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The weight average molecular weight of the organic phosphonic acid metal salt flame retardant composition coating Poly (PPA-K-Ca 50-co-HEA 50) and its Peak Heat Release Rate (PHRR), oxygen index (LOI) and vertical burning (UL-94) were tested, and the test results are shown in Table 1.
Comparative example 1
The organic phosphonic acid metal salt flame retardant composition coating differs from example 2 in that the comonomer starting materials of the composition comprise the following components in parts by mole:
acrylic ester monomer: 54 parts;
phosphorus-containing flame retardant monomer: 54 parts;
Metal hydroxide: 53 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.054mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, gradually warmed to 70℃under nitrogen atmosphere and kept stirring to dissolve PPA completely. 0.054mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the PPA aqueous solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the solution is reacted for 4h at constant temperature, then 0.016gKPS is added again, and the reaction is continued for 0.5h.
C. 3g of calcium hydroxide were added and stirring was continued at 50℃for 3 hours, the copolymer solution precipitating a white precipitate. The solid-liquid mixture coating Poly (PPA-Ca 50-co-HEA 50) is obtained.
Comparative example 2
The organic phosphonic acid metal salt flame retardant composition coating differs from example 2 in that the comonomer starting materials of the composition comprise the following components in parts by mole:
acrylic ester monomer: 54 parts;
phosphorus-containing flame retardant monomer: 107 parts;
Metal hydroxide: 0 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.108mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, gradually warmed to 70℃under nitrogen atmosphere and kept stirring to dissolve PPA completely. 0.054mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the PPA aqueous solution.
B. dissolving 0.15g of potassium persulfate (KPS) in 14g of distilled water, slowly dripping the solution into the solution within 0.5h at a constant speed, keeping the constant temperature for reaction for 4h, then pouring the solution into the solution again for 0.016gKPS h, and continuing the reaction for 0.5h to obtain the organic phosphonic acid flame-retardant polymer coating.
In a specific embodiment, there is provided the use of an organic phosphonic acid flame retardant polymer coating as described above, wherein the organic phosphonic acid metal salt flame retardant composition coating is applied to the outer surface of a foam board, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roll coating process and cured at 60-90 ℃ for 0.5-3 hours, with a thickness of at least 1 micrometer, preferably a thickness of 1-3000 micrometers.
The organic phosphonic acid flame retardant polymer coating was tested for oxygen index (LOI) and vertical burn (UL-94) and the test results are shown in table 1.
Comparative example 3
The organic phosphonic acid metal salt flame retardant composition coating differs from example 2 in that the comonomer starting materials of the composition comprise the following components in parts by mole:
acrylic ester monomer: 54 parts;
Phosphorus-containing flame retardant monomer: 0 parts;
Metal hydroxide: 107 parts.
In a specific embodiment, a method for preparing a coating of the organic phosphonic acid metal salt flame retardant composition is provided, which comprises the following steps:
A. 0.054mol of hydroxyethyl acrylate (HEA) was taken, put into 10g of distilled water, gradually warmed up to 70℃under nitrogen atmosphere, then 0.07g of potassium persulfate (KPS) was put into HEA solution for continuous reaction for 4 hours, finally 6g of potassium hydroxide was added and stirring was continued for 3 hours at 50 ℃.
In a specific embodiment, the mixture coating of hydroxyethyl acrylate and potassium hydroxide is applied to the outer surface of a foam board, plastic, wood and metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes, and is cured for 0.5-3 hours at 60-90 ℃, wherein the application thickness is at least 1 micron, preferably 1-3000 microns, and the anti-frosting phenomenon of the cured coating occurs.
The hydroxyethyl acrylate and potassium hydroxide mixture coating was tested for oxygen index (LOI) and vertical burn (UL-94) and the test results are shown in Table 1.
TABLE 1 weight average molecular weight of coating layer of organic phosphonate flame retardant composition and heat release rate Peak (PHRR), oxygen index (LOI) and vertical Combustion (UL-94) test results table
As can be obtained from the examples in Table 1, the organic phosphonic acid metal salt flame retardant polymer coating prepared by the invention has extremely high limiting oxygen index, can reach UL-94V-2, V-0 grade, has low heat release rate in the combustion test process, and has various flame retardant test results far superior to the materials such as wood, high polymer and the like which are widely used at present, so that the organic phosphonic acid metal salt flame retardant polymer coating can be used as a flame retardant surface coating of the material to effectively protect a bottom substrate and improve the overall fire safety of the material. Wherein, too high acrylic ester content in the polymer coating can lead to the decay of the flame retardant property of the coating, too high phosphorus-containing flame retardant monomer can bring about the reduction of the molecular weight of the polymer coating, is not suitable for construction, and the continuously increased phosphorus-containing monomer dosage can not bring about the continuously improved flame retardant benefit.
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the application. The embodiments of the application and the features of the embodiments may be combined with each other arbitrarily without conflict.
Claims (9)
1. The organic phosphonic acid metal salt flame retardant composition coating is characterized in that monomer raw materials of the composition comprise the following components in parts by mole:
acrylic ester monomer: 20-165 parts;
phosphorus-containing flame retardant monomer: 35-110 parts;
Metal hydroxide: 35-220 parts;
The metal hydroxide comprises a 1-valent metal hydroxide or a combination of a 1-valent metal hydroxide and a number of n-valent metal hydroxides; n is a positive integer greater than 1; the molar amount of the n-valent metal hydroxide is less than or equal to 3% of the molar total amount of the metal hydroxide;
The phosphorus-containing flame retardant monomer comprises one or more of 1-styryl phosphonic acid, vinyl phosphonic acid, phosphonic acid-beta-styryl ester, dimethyl vinylphosphonate, diethyl vinylphosphonate and allyl diethyl phosphate.
2. The metal organophosphonate flame retardant composition coating of claim 1, wherein the acrylic monomer comprises one or more of ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycidyl acrylate.
3. The coating of the organic phosphonic acid metal salt flame retardant composition of claim 1 wherein,
The metal hydroxide comprises one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, copper hydroxide, barium hydroxide, zinc hydroxide and nickel hydroxide;
the molar ratio of the metal hydroxide to the phosphorus-containing flame retardant monomer is less than or equal to 2:1.
4. The metal organophosphonate flame retardant composition coating of claim 3, wherein the molar fraction ratio of the acrylic monomer to the phosphorous flame retardant monomer is 4: 6-6: 4, a step of;
The molar ratio of the 1-valence metal hydroxide to the metal hydroxide is X, and the molar ratio of the n-valence metal hydroxide to the metal hydroxide is Y n,X+∑Yn＝1,∑Yn -3%;
the molar ratio of the metal hydroxide to the phosphorus-containing flame-retardant monomer is less than or equal to Wherein n is a positive integer greater than 1.
5. A method of preparing a coating of the metal organophosphonate flame retardant composition according to any one of claims 1-4, comprising the steps of:
A. Mixing a phosphorus-containing flame-retardant monomer, an acrylic ester monomer and a solvent; the solvent comprises one or more of water, ethanol, propanol, butanol, ethyl acetate or dimethyl sulfoxide;
B. Adding an initiator to the mixture; the initiator comprises one or more of potassium persulfate, ammonium persulfate, azobisisobutyrimidine hydrochloride and azobisisobutyronitrile;
C. And adding metal hydroxide to obtain the organic phosphonic acid metal salt flame-retardant composition coating.
6. The method for preparing a coating of an organic phosphonic acid metal salt flame retardant composition according to claim 5, wherein the step A specifically comprises the following steps:
adding a phosphorus-containing flame-retardant monomer and an acrylic ester monomer into a solvent under the atmosphere of nitrogen, and mixing at constant temperature;
The solvent temperature and the constant temperature are 60-80 ℃, and the total concentration of the phosphorus-containing flame-retardant monomer and the acrylic ester monomer solution is 10-35 wt%.
7. The method for preparing a coating of an organic phosphonic acid metal salt flame retardant composition according to claim 5, wherein the step B specifically comprises the following steps:
adding an initiator into a mixture of a phosphorus-containing flame-retardant monomer, an acrylic ester monomer and a solvent mixture for the first time, carrying out a constant-temperature copolymerization reaction, and adding the initiator for the second time before the reaction is finished to finally obtain the organic phosphonic acid metal salt flame-retardant composition coating;
the first time of adding the initiator is 30-60 min after mixing the phosphorus-containing flame-retardant monomer, the acrylic ester monomer and the solvent, the first time of adding the initiator is 3-6 h of constant temperature copolymerization reaction, and the second time of adding the initiator is 0.5-1 h before the end of the constant temperature copolymerization reaction;
The initiator is 0.1-1.5 wt% of the total mass of the phosphorus-containing flame-retardant monomer and the acrylic ester monomer, the input of the initiator is 80-95 wt% of the total amount of the initiator in the first time, and the input of the initiator is 5-20 wt% of the total amount of the initiator in the second time.
8. The method for preparing a coating of an organic phosphonic acid metal salt flame retardant composition according to claim 5, wherein the step C specifically comprises the following steps:
Adding metal hydroxide to react for 0.5-6 h at 25-80 ℃ to obtain the organic phosphonic acid metal salt flame-retardant composition coating.
9. Use of a coating of an organophosphonate metal salt flame retardant composition according to any one of claims 1 to 4, wherein the use of the organophosphonate metal salt flame retardant composition coating is on the outer surface of one or more substrates of foam board, plastic, wood, metal;
The organic phosphonic acid metal salt flame retardant composition coating is applied to the outer surface of the substrate and cured by one or more of dip coating, spray coating, brush coating, knife coating and roller coating processes; applying a thickness of at least 1 micron;
The curing condition of the organic phosphonic acid metal salt flame retardant composition coating is 60-90 ℃ for 0.5-3 h.
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