CN115595033A - Organic metal phosphonate flame-retardant composition coating, and preparation method and application thereof - Google Patents
Organic metal phosphonate flame-retardant composition coating, and preparation method and application thereof Download PDFInfo
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- CN115595033A CN115595033A CN202211377928.2A CN202211377928A CN115595033A CN 115595033 A CN115595033 A CN 115595033A CN 202211377928 A CN202211377928 A CN 202211377928A CN 115595033 A CN115595033 A CN 115595033A
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- Prior art keywords
- coating
- monomer
- flame
- retardant
- hydroxide
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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 205
- 239000003063 flame retardant Substances 0.000 title claims abstract description 203
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 143
- 239000002184 metal Substances 0.000 title claims abstract description 143
- 239000000203 mixture Substances 0.000 title claims abstract description 131
- 238000000576 coating method Methods 0.000 title claims abstract description 128
- 239000011248 coating agent Substances 0.000 title claims abstract description 125
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims description 104
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 122
- 150000003839 salts Chemical class 0.000 claims abstract description 103
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 57
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 53
- 239000011574 phosphorus Substances 0.000 claims abstract description 53
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 31
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 24
- 238000005507 spraying Methods 0.000 claims description 19
- 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
- 238000007761 roller coating 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
- 239000012299 nitrogen atmosphere Substances 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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 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
- -1 acrylic ester Chemical class 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
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 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
- 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
- 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
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003292 glue Substances 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
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- 238000003756 stirring Methods 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 21
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000010345 tape casting Methods 0.000 description 15
- 238000000502 dialysis Methods 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 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
- 229920000728 polyester Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- CMQAMENQCKNUPB-UHFFFAOYSA-N NC1CCOP(=O)O1 Chemical compound NC1CCOP(=O)O1 CMQAMENQCKNUPB-UHFFFAOYSA-N 0.000 description 1
- HOHPOKYCMNKQJS-UHFFFAOYSA-N [P].[Br] Chemical compound [P].[Br] HOHPOKYCMNKQJS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 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
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity 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)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (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 material comprises the following components in parts by mole: 20-165 parts of acrylate monomers, 35-110 parts of phosphorus-containing flame-retardant monomers 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 adhesion of the coating to the base material; the synergistic effect of phosphorus and metal ions is fully exerted, the flame retardant property of the copolymer coating is further improved, and the fire safety performance of the base material is obviously improved under the condition of lower glue application amount. The flame retardant coating has the advantages of providing an effective flame retardant effect for various flammable base materials, having excellent char forming property compared with common organic phosphorus-containing flame retardant coatings, having far better high-temperature stability and barrier property of a residual metal salt carbon layer than an organic carbon layer, being lasting and effective at high temperature, and having 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 metal phosphonate flame-retardant composition coating, a preparation method and application thereof, and specifically relates to a technical means of an organic metal phosphonate flame-retardant coating capable of being adhered to the surface of a combustible substrate.
Background
In recent years, fire has become one of the main hazards threatening public life safety and social development. Materials such as plastics and wood which are visible everywhere in daily life mostly have the defects of low limiting oxygen index, high heat value and easy ignition. It has been proved that once such material is ignited, the flame spread on its surface is extremely fast, which further promotes the occurrence of fire flashover and causes significant loss of life and property to people.
Constructing a surface coating with a flame-retardant function on the surface of a combustible substrate is an effective means for reducing the fire hazard of the combustible substrate, the method has the advantages of low flame retardant consumption, simple construction, wide applicability and the like, and the surface coating can be applied to the surface of a material in ways of dip coating, spray coating, brush coating, blade coating, roller coating and the like; the flame-retardant coating can be carbonized at flame or high temperature to form a heat-insulating and fireproof protective layer with stable heat, so that the internal base material is prevented from being damaged by the flame.
However, most of the traditional flame retardant coatings in the past are halogen flame retardants, and Chinese patent publication No. CN112553913A discloses a heavy metal-free bromine-phosphorus synergistic aqueous textile flame retardant coating composition containing hyperbranched polymer, wherein the composition comprises a film forming agent, a hydrophobic modified emulsion, a brominated flame retardant, a phosphorus-containing flame retardant, a hyperbranched carbon forming agent and an aqueous coating auxiliary agent, the brominated flame retardant is decabromodiphenylethane, the phosphorus-containing flame retardant is selected from hydrophobically modified wrapped ammonium polyphosphate, and the hydrophobic modified emulsion is selected from organosilicon modified acrylic polyester emulsion and polyurethane modified acrylic polyester emulsion. The flame retardant decabromodiphenylethane is adopted to prepare the flame retardant coating, the coating composition has good water resistance and excellent flame retardant effect, but contains a potentially harmful halogen flame retardant unit, corrosive gas can be decomposed after combustion, and obvious disadvantages are shown under the current market requirements of pursuing halogen-free environmental protection.
The Chinese invention patent with the publication number of CN110527371A provides a sandwich-structured efficient flame-retardant coating, which is characterized in that a bottom conducting layer, a middle temperature-sensitive sensing layer and a top super-hydrophobic conducting layer are sequentially prepared on a flammable base material, wherein the preparation of the bottom conducting layer is to uniformly disperse a metal nano material and an oil-soluble long-chain polymer into an organic solvent together to form a coating A, then the coating A is sprayed on the base material, and the coating A is dried for the first time; the process of spraying and drying is repeated 1-10 times. However, the construction process involves the use of various toxic organic solvents, which easily causes pollution to the environment and influences the human health. In recent years, as national environmental protection policies have become stricter, the use of such conventional flame retardant coatings has been gradually abandoned.
The Chinese patent with publication number CN106632468B discloses a preparation method of amino trimethylene phosphonic acid metal salt flame retardant, wherein the amino trimethylene phosphonic acid metal salt is prepared by the reaction of 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 molar 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 24-48h, filtering, washing and drying the product to obtain the aminotrimethylene phosphonate 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 researches show that the amino trimethylene phosphonic acid metal salt flame retardant has the advantages of good thermal stability, high flame retardant efficiency and high carbon residue rate, but 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 overcome 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, green, environment-friendly, halogen-free, low in toxicity, durable in performance, high in adhesiveness and transparency, can effectively resist high temperature for a long time, can be popularized to the fields of buildings, bridges, pipelines, traffic and the like, and has a wide application prospect.
The purpose of the invention is realized by the following technical scheme: the organic metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 20-165 parts;
phosphorus-containing flame retardant monomer: 35-110 parts;
metal hydroxide: 35-220 parts.
Further, the acrylic ester monomer comprises one or more of acrylic ester substances such as 2- [ [ (butylamino) carbonyl ] oxo ] ethyl 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-styryl phosphonic acid, vinyl phosphonic acid, phosphonic acid-BETA-styryl ester, dimethyl vinyl phosphonate, diethyl vinyl phosphonate and allyl diethyl phosphate.
Further, the metal in the metal hydroxide includes a 1-valent metal hydroxide or a combination of a 1-valent metal hydroxide and several 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 ratio of the acrylate monomer to the phosphorus-containing flame-retardant monomer is 4: 6-6: 4;
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+∑Y n ＝1，∑Y n ≤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 molar part ratio of the acrylate monomer to the phosphorus-containing flame-retardant monomer is within 4: 6-6: 4, but for better effect and easier test, the molar ratio of the acrylate monomer to the phosphorus-containing flame retardant monomer is 1:1.
In addition, the inventors have found through studies that the addition of a high-valent metal hydroxide (excluding 1-valent metal hydroxide) alone as a metal hydroxide makes the coating crosslinking difficult to work with, and therefore, it is necessary to use the high-valent metal hydroxide in combination with 1-valent metal hydroxide, and the molar amount of the high-valent metal hydroxide is usually within 3% of the total molar amount of the metal hydroxides.
And when the high-valence metal hydroxide and the 1-valence metal hydroxide are reused, the polymer crosslinking is promoted, and the high-temperature carbon forming performance is better. If no metal hydroxide is added, the general effect can be achieved only if the molar ratio of the phosphorus-containing flame-retardant monomer is more than 50%, and if the metal hydroxide and the phosphorus-containing flame-retardant monomer are reused, the effect is far better than that of only using the phosphorus-containing flame-retardant monomer.
The second purpose of the invention is to provide a preparation method of the organic phosphonate metal salt flame-retardant composition coating. The second purpose of the invention is realized by the following technical scheme: a method for preparing a coating of an organic phosphonic acid metal salt flame-retardant composition comprises the following steps:
A. mixing a phosphorus-containing flame-retardant monomer, an acrylate 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, azobisisobutyramidine hydrochloride and azobisisobutyronitrile;
C. adding metal hydroxide to obtain the organic phosphonate metal salt flame-retardant composition coating.
Further, the step a specifically includes the following steps:
adding a phosphorus-containing flame-retardant monomer and an acrylate monomer into a solvent under a nitrogen atmosphere, and mixing at a constant temperature;
the temperature of the solvent 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 acrylate monomer and a solvent mixture for the first time, carrying out constant-temperature copolymerization reaction, and adding the initiator for the second time before the reaction is finished to finally obtain an organic phosphonate metal salt flame-retardant composition coating;
the time for adding the initiator for the first time is 30-60 min and less after the phosphorus-containing flame-retardant monomer, the acrylate monomer and the solvent are mixed, the constant-temperature copolymerization reaction is carried out for 3-6 h after the initiator is added for the first time, and the time for adding the initiator for the second time is 0.5-1 h and less before the constant-temperature copolymerization reaction is finished;
the dosage of the initiator is 0.1-1.5 wt% of the total mass of the phosphorus-containing flame-retardant monomer and the acrylate monomer, the dosage of the initiator added for the first time is 80-95 wt% of the total dosage of the initiator, and the dosage of the initiator added for the second time is 5-20 wt% of the total dosage of the initiator.
Further, the step C specifically includes the steps of:
adding metal hydroxide to react at 25-80 deg.c for 0.5-6 hr to obtain the flame retardant organic phosphonate metal salt composition coating.
The third purpose of the invention is to provide the application of the organic phosphonate metal salt flame-retardant composition coating. The third purpose of the invention is realized by the following technical scheme: use of a coating of an organophosphate flame retardant composition on the outer surface of one or more substrates of foam board, plastic, wood, metal;
the organic phosphonate metal salt flame-retardant composition coating is applied to the outer surface of a substrate through one or more of dip coating, spray coating, brush coating, blade coating and roller coating processes and is solidified; applying a thickness of at least 1 micron; preferably 1-3000 microns thick;
the curing condition of the organic phosphonic acid metal salt flame-retardant composition coating is 60-90 ℃ and 0.5-3 h.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) Monomer raw materials in the organic phosphonate metal salt flame-retardant composition coating comprise the following components in parts by mole: 35-110 parts of acrylate monomer, 35-110 parts of phosphorus-containing flame-retardant monomer and 35-110 parts of metal hydroxide; the raw materials are easy to obtain, the halogen is safe, the synthetic process is simple, a highly toxic solvent is not adopted, and the green flame retardant target can be realized;
(2) The copolymerization reaction of the phosphorus-containing flame-retardant monomer and the acrylate film-forming monomer of the organic phosphonate 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 requirement of high adhesive force of the coating to a base material 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 flame retardant property of the copolymer coating can be remarkably improved under the condition of lower glue application 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 buildings, bridges, pipelines, transportation and the like.
Detailed Description
The following examples will assist those skilled in the art in further understanding the 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 and scope of the invention. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between the endpoints and the individual points, and each individual point can be combined with each other to give one or more new numerical ranges, these numerical ranges should be considered as specifically disclosed herein, and the invention is described in detail below with reference to specific examples:
example 1
The organic phosphonate metal salt flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 65 parts of (1);
phosphorus-containing flame retardant monomer: 43 parts of a mixture;
metal hydroxide: and 43 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.043mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, and the temperature was gradually increased to 70 ℃ under a nitrogen atmosphere while stirring was maintained to completely dissolve the PPA. 0.065mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the aqueous PPA solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, the monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the constant temperature reaction is kept for 4h, then 0.016g of KPS is added again, and the reaction is continued for 0.5h.
C. 2.4g of potassium hydroxide were added and stirring was continued at 50 ℃ for 3h, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-K40-co-HEA 60).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate 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 metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 54 parts of a binder;
phosphorus-containing flame retardant monomer: 54 parts of a binder;
metal hydroxide: 53 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.054mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, and the temperature was gradually raised to 70 ℃ under a nitrogen atmosphere while stirring was maintained to completely dissolve the PPA. 0.054mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the aqueous PPA solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, the monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the constant temperature reaction is kept for 4h, then 0.016g of KPS is added again, and the reaction is continued for 0.5h.
C. 3g of potassium hydroxide are added and stirring is continued at 50 ℃ for 3h, and the copolymer solution is taken off. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-K50-co-HEA 50).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate 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 metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 48 parts of a mixture;
phosphorus-containing flame retardant monomer: 60 parts;
metal hydroxide: 60 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.060mol of 1-styrylphosphonic acid (PPA) is weighed, added to 24.5g of distilled water, and gradually heated to 70 ℃ under a nitrogen atmosphere while stirring is maintained to completely dissolve the PPA. 0.048mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the aqueous PPA solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, the monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the constant temperature reaction is kept for 4h, then 0.016g of KPS is added again, and the reaction is continued for 0.5h.
C. 3.4g of potassium hydroxide are added and stirring is continued at 50 ℃ for 3h, and the copolymer solution is taken off. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-K55-co-HEA 45) is obtained.
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate 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 metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 43 parts of a mixture;
phosphorus-containing flame retardant monomer: 65 parts of a binder;
metal hydroxide: and 64 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.065mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, and the temperature was gradually increased to 70 ℃ under a nitrogen atmosphere while stirring was maintained to completely dissolve the PPA. 0.043mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the aqueous PPA solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, the monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the constant temperature reaction is kept for 4h, then 0.016g of KPS is added again, and the reaction is continued for 0.5h.
C. 3.6g of potassium hydroxide were added and stirring was continued at 50 ℃ for 3h, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-K60-co-HEA 40).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate 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 metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 110 parts of a binder;
phosphorus-containing flame retardant monomer: 76 parts of a mixture;
metal hydroxide: and 75 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.076mol of vinylphosphonic acid (VPA) is weighed out into 29g of distilled water, gradually warmed to 80 ℃ under continuous nitrogen introduction and stirring is maintained. 0.11mol of hydroxyethyl acrylate (HEA) was weighed out and slowly added dropwise to the aqueous VPA solution.
B. 0.19g of azodiisobutyramidine hydrochloride (AIBA) is dissolved in 19g of distilled water, and slowly and dropwise added into the monomer solution at a constant speed within 0.5h, after the reaction is kept at a constant temperature for 2h, 0.02g of AIBA is added again, and the reaction is continued for 0.5h.
C. 1.8g of lithium hydroxide were slowly added and stirred vigorously at room temperature for 6h, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (VPA-Li 40-co-HEA 60).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate 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 burn (UL-94) were tested and the results are shown in Table 1.
Example 6
The organic metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 93 parts;
phosphorus-containing flame retardant monomer: 93 parts;
metal hydroxide: 93 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above-mentioned organic phosphonic acid metal salt flame-retardant composition, comprising the steps of:
A. 0.093mol of vinylphosphonic acid (VPA) are weighed out into 29g of distilled water, gradually heated to 80 ℃ under continuous nitrogen introduction and stirring is maintained. 0.093mol of hydroxyethyl acrylate (HEA) was weighed out and slowly added dropwise to the aqueous VPA solution.
B. 0.19g of azodiisobutyramidine hydrochloride (AIBA) is dissolved in 19g of distilled water, and slowly and dropwise added into the monomer solution at a constant speed within 0.5h, after the reaction is kept at a constant temperature for 2h, 0.02g of AIBA is added again, and the reaction is continued for 0.5h.
C. 2.2g of lithium hydroxide were slowly added and stirred vigorously at room temperature for 6h, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (VPA-Li 50-co-HEA 50).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate 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 burn (UL-94) were tested and the results are shown in Table 1.
Example 7
An organic metal phosphonate flame-retardant composition coating, the comonomer raw material of the composition comprises the following components in parts by mole:
acrylate monomer: 84 parts of a mixture;
phosphorus-containing flame retardant monomer: 102 parts of (A);
metal hydroxide: 100 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.102mol of vinylphosphonic acid (VPA) is weighed into 29g of distilled water and gradually heated to 80 ℃ while stirring under continuous nitrogen. 0.084mol of hydroxyethyl acrylate (HEA) was weighed out and slowly added dropwise into the VPA aqueous solution.
B. 0.19g of azodiisobutyramidine hydrochloride (AIBA) is dissolved in 19g of distilled water, and slowly and dropwise added into the monomer solution at a constant speed within 0.5h, after the reaction is kept at a constant temperature for 2h, 0.02g of AIBA is added again, and the reaction is continued for 0.5h.
C. 2.4g of lithium hydroxide were slowly added and stirred vigorously at room temperature for 6h, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (VPA-Li 55-co-HEA 45).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate 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 burn (UL-94) were tested and the results are shown in Table 1.
Example 8
The organic metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 76 parts of a mixture;
phosphorus-containing flame retardant monomer: 110 parts of (A);
metal hydroxide: 109 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.110mol of vinylphosphonic acid (VPA) is weighed into 29g of distilled water and gradually heated to 80 ℃ while stirring under continuous nitrogen. 0.076mol of hydroxyethyl acrylate (HEA) was weighed out and slowly added dropwise to the aqueous VPA solution.
B. 0.19g of azodiisobutyramidine hydrochloride (AIBA) is dissolved in 19g of distilled water, and slowly and dropwise added into the monomer solution at a constant speed within 0.5h, after the reaction is kept at a constant temperature for 2h, 0.02g of AIBA is added again, and the reaction is continued for 0.5h.
C. 2.6g of lithium hydroxide were slowly added and stirred vigorously at room temperature for 6h, 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 phosphonate metal salt flame-retardant polymer coating Poly (VPA-Li 60-co-HEA 40) is obtained.
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate 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 burn (UL-94) were tested and the results are shown in Table 1.
Example 9
The organic metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 54 parts of a binder;
phosphorus-containing flame retardant monomer: 36 parts of (A);
metal hydroxide: 37 parts of the raw materials.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.036mol of 1-styrylphosphonic acid (PPA) was weighed into 25.5g of dimethyl sulfoxide (DMSO), gradually heated to 60 ℃ with continuous nitrogen introduction and stirring for complete dissolution. 0.054mol of 2- [ [ (butylamino) carbonyl ] oxo ] ethyl acrylate (BCOE) monomer is weighed and slowly dropped into the PPA solution.
B. 0.16g of Azobisisobutyronitrile (AIBN) is dissolved in 16g of DMSO, and the monomer solution is slowly dropped into the mixture at a constant speed within 0.5h, and after the constant temperature reaction is kept for 4h, 0.02g of AIBN is added again, and the reaction is continued for 0.5h.
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 to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-Na 40-co-BCOE 60).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate metal salt flame retardant composition coating Poly (PPA-Na 40-co-BCOE 60) and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94) were tested and the results are shown in Table 1.
Example 10
The organic metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 45 parts of (1);
phosphorus-containing flame retardant monomer: 45 parts of (1);
metal hydroxide: 45 parts of the raw materials.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.045mol of 1-styrylphosphonic acid (PPA) is weighed into 25.5g of dimethyl sulfoxide (DMSO), gradually heated to 60 ℃ under continuous nitrogen introduction and stirred until complete dissolution. 0.045mol of 2- [ [ (butylamino) carbonyl ] oxo ] ethyl acrylate (BCOE) monomer is weighed and slowly dripped into the PPA solution.
B. 0.16g of Azobisisobutyronitrile (AIBN) is dissolved in 16g of DMSO, and the monomer solution is slowly dripped into the mixture at a constant speed within 0.5h, after the constant temperature reaction is kept for 4h, 0.02g of AIBN is added again, and the reaction is continued for 0.5h.
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 to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-Na 50-co-BCOE 50).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The organic phosphonate metal salt flame retardant composition coating Poly (PPA-Na 50-co-BCOE 50) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94), and the results are shown in Table 1.
Example 11
The organic metal phosphonate flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 40 parts of a mixture;
phosphorus-containing flame retardant monomer: 50 parts of a mixture;
metal hydroxide: 50 parts of the components.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.050mol of 1-styrylphosphonic acid (PPA) is weighed into 25.5g of dimethyl sulfoxide (DMSO), the temperature was gradually increased to 60 ℃ under continuous nitrogen gas introduction and stirring was maintained to completely dissolve the compound. 0.040mol of 2- [ [ (butylamino) carbonyl ] oxo ] ethyl acrylate (BCOE) monomer is weighed and slowly dropped into the PPA solution.
B. 0.16g of Azobisisobutyronitrile (AIBN) is dissolved in 16g of DMSO, and the monomer solution is slowly dropped into the mixture at a constant speed within 0.5h, and after the constant temperature reaction is kept for 4h, 0.02g of AIBN is added again, and the reaction is continued for 0.5h.
C. 2g of sodium hydroxide are slowly added and the copolymer solution is taken off with vigorous stirring at room temperature for 3h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-Na 55-co-BCOE 45).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The organic phosphonate metal salt flame retardant composition coating Poly (PPA-Na 55-co-BCOE 45) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94), and the results are shown in Table 1.
Example 12
The organic phosphonate metal salt flame-retardant composition coating comprises the following components in parts by mole:
acrylate monomer: 36 parts of (a);
phosphorus-containing flame retardant monomer: 54 parts of a binder;
metal hydroxide: and 55 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.054mol of 1-styrylphosphonic acid (PPA) is weighed into 25.5g of dimethyl sulfoxide (DMSO), gradually heated to 60 ℃ under continuous nitrogen introduction and stirred to be completely dissolved. 0.036mol of 2- [ [ (butylamino) carbonyl ] oxo ] ethyl acrylate (BCOE) monomer is weighed and slowly dropped into the PPA solution.
B. 0.16g of Azobisisobutyronitrile (AIBN) is dissolved in 16g of DMSO, and the monomer solution is slowly dropped into the mixture at a constant speed within 0.5h, and after the constant temperature reaction is kept for 4h, 0.02g of AIBN is added again, and the reaction is continued for 0.5h.
C. 2.2g of sodium hydroxide are slowly added and the copolymer solution is taken off with vigorous stirring at room temperature for 3h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-Na 60-co-BCOE 40).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The organic phosphonate metal salt flame retardant composition coating Poly (PPA-Na 60-co-BCOE 40) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94), and the results are shown in Table 1.
Example 13
An organic phosphonate metal salt flame retardant composition coating, which differs from example 1 in that the comonomer feed of the composition comprises the following components in mole parts:
acrylate monomer: 54 parts of a binder;
phosphorus-containing flame retardant monomer: 54 parts of a binder;
metal hydroxide: 53 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.054mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, the temperature was gradually raised to 70 ℃ under a nitrogen atmosphere and stirring was maintained until PPA was completely dissolved. 0.054mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the aqueous PPA solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, the monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the constant temperature reaction is kept for 4h, then 0.016g of KPS 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 5h, and the copolymer solution was taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the organic phosphonate metal salt flame-retardant polymer coating Poly (PPA-K-Ca 50-co-HEA 50).
In a specific embodiment, there is provided a use of the above-mentioned organic phosphonate metal salt flame-retardant composition coating layer, wherein the organic phosphonate metal salt flame-retardant composition coating layer is applied on the outer surface of the foamed sheet material, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The weight average molecular weight of the organic phosphonate metal salt flame retardant composition coating Poly (PPA-K-Ca 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.
Comparative example 1
An organic phosphonate metal salt flame retardant composition coating, which differs from example 2 in that the comonomer feed of the composition comprises the following components in mole parts:
acrylate monomer: 54 parts of a binder;
phosphorus-containing flame retardant monomer: 54 parts of a binder;
metal hydroxide: 53 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.054mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, the temperature was gradually raised to 70 ℃ under a nitrogen atmosphere and stirring was maintained until PPA was completely dissolved. 0.054mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the aqueous PPA solution.
B. 0.15g of potassium persulfate (KPS) is dissolved in 14g of distilled water, the monomer solution is slowly dripped into the solution at a constant speed within 0.5h, the constant temperature reaction is kept for 4h, then 0.016g of KPS 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 3h, whereupon the copolymer solution precipitated as a white precipitate. Obtaining the solid-liquid mixture paint Poly (PPA-Ca 50-co-HEA 50).
Comparative example 2
An organic phosphonic acid metal salt flame retardant composition coating, which is different from the embodiment 2 in that the comonomer raw material of the composition comprises the following components in molar parts:
acrylate monomer: 54 parts of a binder;
phosphorus-containing flame retardant monomer: 107 parts of;
metal hydroxide: 0 part of (A).
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.108mol of 1-styrylphosphonic acid (PPA) was weighed into 24.5g of distilled water, and the temperature was gradually increased to 70 ℃ under a nitrogen atmosphere while stirring was maintained to completely dissolve the PPA. 0.054mol of hydroxyethyl acrylate (HEA) was slowly added dropwise to the aqueous PPA solution.
B. Dissolving 0.15g of potassium persulfate (KPS) in 14g of distilled water, slowly adding the monomer solution dropwise at a constant speed within 0.5h, keeping constant temperature reaction for 4h, adding 0.016g of KPS again, and continuously reacting for 0.5h to obtain the organic phosphonic acid flame-retardant polymer coating.
In a specific embodiment, there is provided a use of the above organic phosphonic acid metal salt flame retardant polymer coating, wherein the organic phosphonic acid metal salt flame retardant composition coating is applied on the outer surface of the foamed sheet, plastic, wood, metal substrate by dip coating, spray coating, brush coating, knife coating, roller coating process and cured for 0.5-3 h at 60-90 ℃, and the applied thickness is at least 1 micron, preferably 1-3000 microns.
The oxygen index (LOI) and vertical burn (UL-94) of the organophosphonic acid flame retardant polymer coating were tested and the results are shown in Table 1.
Comparative example 3
An organic phosphonate metal salt flame retardant composition coating, which differs from example 2 in that the comonomer feed of the composition comprises the following components in mole parts:
acrylate monomer: 54 parts of a binder;
phosphorus-containing flame retardant monomer: 0 part of (C);
metal hydroxide: 107 parts.
In a specific embodiment, there is provided a method for preparing a coating layer of the above organic phosphonate metal salt flame retardant composition, comprising the steps of:
A. 0.054mol of hydroxyethyl acrylate (HEA) is taken and put into 10g of distilled water, the temperature is gradually raised to 70 ℃ under the nitrogen atmosphere, then 0.07g of potassium persulfate (KPS) is put into the HEA solution for continuous reaction for 4 hours, and finally 6g of potassium hydroxide is added and the stirring is continuously carried out for 3 hours at 50 ℃.
In a specific embodiment, the mixture of hydroxyethyl acrylate and potassium hydroxide is coated on the outer surface of a foam board, plastic, wood or metal substrate by dip coating, spray coating, brush coating, knife coating and roller coating, and is cured for 0.5 to 3 hours at 60 to 90 ℃, the coating is applied to the outer surface of the substrate to a thickness of at least 1 micron, preferably 1 to 3000 microns, and the frost-resistant phenomenon appears after curing.
The coating of hydroxyethyl acrylate and potassium hydroxide mixture was tested for oxygen index (LOI) and vertical burn (UL-94) and the results are shown in Table 1.
TABLE 1 weight average molecular weight of the coating of the organophosphonate flame retardant composition and its Peak Heat Release Rate (PHRR), oxygen index (LOI) and vertical burn (UL-94) test results
As can be obtained from the examples in Table 1, the organic metal phosphonate flame-retardant polymer coating prepared by the invention has extremely high limit oxygen index which can reach UL-94V-2,V-0 grade, the heat release rate in the combustion test process is low, and various flame-retardant test results are far superior to the currently widely used materials such as wood, high polymers and the like, so that the organic metal phosphonate flame-retardant polymer coating serving as the flame-retardant surface coating of the material can effectively protect a bottom base material and improve the overall fire safety of the material. The flame retardant performance of the coating is weakened due to the excessively high content of the acrylate in the polymer coating, the molecular weight of the polymer coating is reduced due to the excessively high content of the phosphorus-containing flame retardant monomer, the polymer coating is not suitable for construction, and the flame retardant benefit is not continuously improved due to the continuously increased dosage of the phosphorus-containing monomer.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. The organic metal phosphonate flame-retardant composition coating is characterized in that the monomer raw materials of the composition comprise the following components in parts by mole:
acrylate monomer: 20-165 parts;
phosphorus-containing flame retardant monomer: 35-110 parts;
metal hydroxide: 35-220 parts.
2. The coating of the organophosphate flame retardant composition of claim 1, wherein the acrylate monomers comprise 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 and the like.
3. The organic phosphonate metal salt flame retardant composition coating of claim 1, wherein said phosphorus-containing flame retardant monomer comprises one or more of 1-styrylphosphonic acid, vinylphosphonic acid, a phosphonic acid-BETA-styryl ester, dimethyl vinylphosphonate, diethyl vinylphosphonate, and allyl diethyl phosphate.
4. The organophosphate flame retardant composition coating of claim 1, wherein the metal in the metal hydroxide comprises a 1-valent metal hydroxide or a combination of a 1-valent metal hydroxide and several 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.
5. The organic phosphonate metal salt flame retardant composition coating of claim 4, wherein the molar part ratio of the acrylate monomer to the phosphorus containing flame retardant monomer is 4: 6-6: 4;
the molar ratio of the 1-valent metal hydroxide to the metal hydroxide isX, the molar ratio of the n-valent metal hydroxide to the metal hydroxide is Y n ，X+∑Y n ＝1，∑Y n ≤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.
6. A method of preparing a coating layer of an organophosphonate flame retardant composition according to any of claims 1 to 5, comprising the steps of:
A. mixing a phosphorus-containing flame-retardant monomer, an acrylate 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, azobisisobutyramidine hydrochloride and azobisisobutyronitrile;
C. adding metal hydroxide to obtain the organic phosphonate metal salt flame-retardant composition coating.
7. The method of claim 6, wherein step A comprises the steps of:
adding a phosphorus-containing flame-retardant monomer and an acrylate monomer into a solvent in a nitrogen atmosphere, and mixing at constant temperature;
the temperature of the solvent 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%.
8. The method for preparing a flame retardant composition coating of metal organophosphate as claimed in claim 6, wherein said step B comprises the following steps:
adding an initiator into a mixture of a phosphorus-containing flame-retardant monomer, an acrylate monomer and a solvent mixture for the first time, carrying out constant-temperature copolymerization reaction, and adding the initiator for the second time before the reaction is finished to finally obtain an organic phosphonate metal salt flame-retardant composition coating;
the time for adding the initiator for the first time is 30-60 min and less after the phosphorus-containing flame-retardant monomer, the acrylate monomer and the solvent are mixed, the constant-temperature copolymerization reaction is carried out for 3-6 h after the initiator is added for the first time, and the time for adding the initiator for the second time is 0.5-1 h and less before the constant-temperature copolymerization reaction is finished;
the dosage of the initiator is 0.1-1.5 wt% of the total mass of the phosphorus-containing flame-retardant monomer and the acrylate monomer, the dosage of the initiator added for the first time is 80-95 wt% of the total dosage of the initiator, and the dosage of the initiator added for the second time is 5-20 wt% of the total dosage of the initiator.
9. The method of claim 6 wherein said step C comprises the steps of:
adding metal hydroxide to react at 25-80 deg.c for 0.5-6 hr to obtain the flame retardant organic phosphonate metal salt composition coating.
10. Use of a coating of an organophosphinic acid metal salt flame retardant composition according to any one of claims 1-5, wherein the organophosphinic acid metal salt flame retardant composition is applied to the outer surface of one or more of a foamed sheet, plastic, wood, metal;
the organic phosphonic acid metal salt flame-retardant composition coating is applied to the outer surface of the base material through one or more of dip coating, spray coating, brush coating, blade coating and roller coating processes and is solidified; applying a thickness of at least 1 micron;
the curing condition of the organic metal phosphonate flame-retardant composition coating is 60-90 ℃ and 0.5-3 h.
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