CA3028431A1 - Flame-retardant, waterproof water-based core-shell acrylate resin coating and preparation method of paint - Google Patents
Flame-retardant, waterproof water-based core-shell acrylate resin coating and preparation method of paint Download PDFInfo
- Publication number
- CA3028431A1 CA3028431A1 CA3028431A CA3028431A CA3028431A1 CA 3028431 A1 CA3028431 A1 CA 3028431A1 CA 3028431 A CA3028431 A CA 3028431A CA 3028431 A CA3028431 A CA 3028431A CA 3028431 A1 CA3028431 A1 CA 3028431A1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000000576 coating method Methods 0.000 title claims abstract description 94
- 239000003973 paint Substances 0.000 title claims abstract description 82
- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- 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 66
- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 40
- 239000011258 core-shell material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000005871 repellent Substances 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 230000002940 repellent Effects 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 19
- 230000035484 reaction time Effects 0.000 claims abstract description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012792 core layer Substances 0.000 claims abstract description 16
- 238000004945 emulsification Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000007792 addition Methods 0.000 claims description 21
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- SCESWTHQFQXGMV-UHFFFAOYSA-N ethenylphosphane Chemical compound PC=C SCESWTHQFQXGMV-UHFFFAOYSA-N 0.000 claims description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 15
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 14
- OSASVXMJTNOKOY-UHFFFAOYSA-N chlorobutanol Chemical compound CC(C)(O)C(Cl)(Cl)Cl OSASVXMJTNOKOY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 7
- LKLWLDOUZJEHDY-UHFFFAOYSA-N 7-hydroxy-2-oxochromene-3-carboxylic acid Chemical compound C1=C(O)C=C2OC(=O)C(C(=O)O)=CC2=C1 LKLWLDOUZJEHDY-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 7
- 244000060011 Cocos nucifera Species 0.000 claims description 7
- LMFWXTZEFKLNSB-UHFFFAOYSA-N OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.P.P Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.P.P LMFWXTZEFKLNSB-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229960004926 chlorobutanol Drugs 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 claims description 6
- CRZVCXRSZLYXAL-UHFFFAOYSA-N 2-[1-(dimethylamino)propan-2-yl-methylamino]ethanol Chemical compound CN(C)CC(C)N(C)CCO CRZVCXRSZLYXAL-UHFFFAOYSA-N 0.000 claims description 5
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- QUIMTLZDMCNYGY-UHFFFAOYSA-N 2,4-dichloro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1Cl QUIMTLZDMCNYGY-UHFFFAOYSA-N 0.000 claims description 4
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- CMQAMENQCKNUPB-UHFFFAOYSA-N NC1CCOP(=O)O1 Chemical compound NC1CCOP(=O)O1 CMQAMENQCKNUPB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011527 polyurethane coating Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- RDUAXDDQRLRHQZ-UHFFFAOYSA-N 2-hydroxypropane-1,1,1-tricarboxylic acid Chemical compound CC(O)C(C(O)=O)(C(O)=O)C(O)=O RDUAXDDQRLRHQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002023 wood Substances 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 239000010985 leather Substances 0.000 abstract 1
- 229920000178 Acrylic resin Polymers 0.000 description 10
- FUOOLUPWFVMBKG-UHFFFAOYSA-N 2-Aminoisobutyric acid Chemical compound CC(C)(N)C(O)=O FUOOLUPWFVMBKG-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 241000758789 Juglans Species 0.000 description 4
- 235000009496 Juglans regia Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000020234 walnut Nutrition 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DCULKBZETKTADO-UHFFFAOYSA-N 5,5-dimethylhex-3-en-1-ol Chemical group CC(C)(C)C=CCCO DCULKBZETKTADO-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- -1 graphene modified acrylate Chemical class 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AJYLWDRNNNHBEV-UHFFFAOYSA-N 2-hydrazinylbutanoic acid Chemical compound CCC(NN)C(O)=O AJYLWDRNNNHBEV-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000010073 coating (rubber) Methods 0.000 description 1
- 238000009500 colour coating Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- BXLLINKJZLDGOX-UHFFFAOYSA-N dimethoxyphosphorylmethanamine Chemical compound COP(=O)(CN)OC BXLLINKJZLDGOX-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- 238000004078 waterproofing 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- 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
- C09D5/185—Intumescent paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant, waterproof and water-based core-shell type acrylate resin coating and a preparation method of the paint. The following weight ratio raw materials are added to the reaction container: water 55-75 parts, emulsifier 0.2-2.2 parts, acrylic acid 0.6 ¨3.0 parts, warmed to 50 ° C, stirred for 30 min, added A monomer, emulsification time is 30 ¨ 60min;
warmed to 70 ° C began to pass the reflux water, heated to 75 °
C after the insulation, adding initiator A0.2 ~ 0.6 weight The dropwise addition time lasts for 1~2h, and the reaction is carried out for 2~5h after the addition, to obtain the core layer emulsion; the B
monomer is added dropwise to the obtained core layer emulsion, 0.3~0.6 parts by weight of the initiator A and the step (1) 4.4 parts by weight of the obtained flame retardant, the dropping time lasts for 1~4h, after the addition is completed, the reaction is stirred at 75~85 °C for 2 hours, then the crosslinking agent is added 0.5-1.0 parts by weight, and the reaction time is 75~85 °C. 2h, cooling to 50 ° C, adding 0.3 parts by weight of emulsifier and 0.7 parts of water repellent obtained in step (2), reaction time 30min, adding ammonia to adjust pH to 7~8, to obtain the flame retardant, waterproof water-based core shell type acrylate resin coatings and paints for interior and exterior wall coatings, metal finishing and anti-corrosion, wood-based paints and as leather finishes.
warmed to 70 ° C began to pass the reflux water, heated to 75 °
C after the insulation, adding initiator A0.2 ~ 0.6 weight The dropwise addition time lasts for 1~2h, and the reaction is carried out for 2~5h after the addition, to obtain the core layer emulsion; the B
monomer is added dropwise to the obtained core layer emulsion, 0.3~0.6 parts by weight of the initiator A and the step (1) 4.4 parts by weight of the obtained flame retardant, the dropping time lasts for 1~4h, after the addition is completed, the reaction is stirred at 75~85 °C for 2 hours, then the crosslinking agent is added 0.5-1.0 parts by weight, and the reaction time is 75~85 °C. 2h, cooling to 50 ° C, adding 0.3 parts by weight of emulsifier and 0.7 parts of water repellent obtained in step (2), reaction time 30min, adding ammonia to adjust pH to 7~8, to obtain the flame retardant, waterproof water-based core shell type acrylate resin coatings and paints for interior and exterior wall coatings, metal finishing and anti-corrosion, wood-based paints and as leather finishes.
Description
Flame-retardant, waterproof water-based core-shell acrylate resin coating and preparation method of paint Technical field [0001] The present invention relates to a method for preparing an aqueous core-shell type acrylate-based resin, particularly a flame-retardant, water-repellent aqueous core-shell type acrylate resin coating and a method for preparing a paint.
The arts of Background
The arts of Background
[0002] Paint, the traditional name in China for paint.The so-called paint is a continuous film that is applied to the surface of the object to be protected or decorated and can form a firm adhesion with the object to be coated, usually based on resin, oil or emulsion, with or without adding pigments, fillers, and additions. A
viscous liquid prepared with an organic solvent or water.
viscous liquid prepared with an organic solvent or water.
[0003] In the 60 years since the founding of the People's Republic of China, along with the development of various industries in the national economy, the supporting paint industry has gradually developed from an extremely unobtrusive small industry into an important industry in all fields of the national economy.After several generations of hard work and pioneering efforts, China has become the world's second largest paint producer and consumer, and has entered the mainstream of the world's coatings industry.
[0004] The service life of the paint is determined according to different products. The liquid marble texture product is based on the modified silicone resin emulsion, and the special color coating technology is used to coat the various color paints into colloidal water-based colored particles. It is uniformly and stably suspended in a specific aqueous dispersion, and the color of the various colored particles remains unchanged, and the colored pigment does not precipitate in water.Then the service life of this exterior wall paint is about 15 years.
[0005] Water-based paints and powder coatings have become a climate, especially architectural paints based on water-based paints have accounted for about 38%
of the total coatings in China. Because the chemical properties of water-based paints and oil-based paints are fundamentally different, and the properties of water-based paints and oil-based paints are also very different, it is unscientific to define water-based paints as a major branch of the paint industry. .
of the total coatings in China. Because the chemical properties of water-based paints and oil-based paints are fundamentally different, and the properties of water-based paints and oil-based paints are also very different, it is unscientific to define water-based paints as a major branch of the paint industry. .
[0006] There are many methods for classifying paints, and there are usually several classification methods:
(1)) According to the form of the product, it can be divided into: liquid paint, powder paint, high solid paint.
(1)) According to the form of the product, it can be divided into: liquid paint, powder paint, high solid paint.
[0007] (2) Dispersing medium used as a coating material: a solvent-based coating; an aqueous coating (emulsion-based coating, water-soluble coating).
[0008] (3) According to the use can be divided into architectural coatings, can coatings, automotive coatings, aircraft coatings, home appliance coatings, wood coatings, bridge coatings, plastic coatings, paper coatings, marine coatings, wind power coatings, nuclear power coatings, pipelines Coatings, steel structural coatings, rubber coatings, aviation coatings, etc.
[0009] (4) According to its performance, it can be divided into: anti-corrosion coating, anti-rust coating, insulating coating, high temperature coating, anti-aging coating, acid and alkali coating, chemical resistant coating.
[0010] (5)) According to whether there is color, it can be divided into:
varnish, color paint.
varnish, color paint.
[0011] (6) according to the construction process, can be divided into: sealer, putty, primer, primer, topcoat, varnish.
[0012] (7) According to the construction method, it can be divided into brush coating, spray coating, roller coating, dip coating, electrophoretic coating and the like.
[0013] (8) According to the function can be divided into non-stick coating, Teflon coating, decorative coating, anti-corrosion coating, conductive coating, anti-rust coating, high temperature coating, temperature coating, thermal insulation coating, fire retardant coating, waterproof coating, etc. .
[0014] (9) Household paint can be divided into interior wall paint, exterior wall paint, wood paint, metal paint, floor paint.
[0015] (10) according to the film properties (anti-corrosion paint, insulating paint, conductive paint, heat-resistant paint ...) (11) According to film-forming substances (natural resin paint, phenolic paint, alkyd paint, amino paint, nitro paint, epoxy paint, chlorinated rubber paint, acrylic paint, polyurethane paint) , silicone resin paint, fluorocarbon resin paint, silicone paint, vinyl paint etc.) (12) According to the type of base material: can be divided into organic coatings, inorganic coatings, organic-inorganic composite coatings. Organic coatings are classified into organic solvent-based coatings and organic water-based (including water-based and water-soluble) coatings because of the different solvents they use.
Common coatings in life are generally organic coatings. The inorganic coating refers to a coating produced by using an inorganic polymer material as a base material, and includes a water-soluble silicate system, a silica sol system, a silicone, and an inorganic polymer system. Organic-inorganic composite coatings have two composite forms. One is that the organic and inorganic materials are used together as a base material to form a composite coating; the other is that organic and inorganic coatings are combined in the decoration construction.
Common coatings in life are generally organic coatings. The inorganic coating refers to a coating produced by using an inorganic polymer material as a base material, and includes a water-soluble silicate system, a silica sol system, a silicone, and an inorganic polymer system. Organic-inorganic composite coatings have two composite forms. One is that the organic and inorganic materials are used together as a base material to form a composite coating; the other is that organic and inorganic coatings are combined in the decoration construction.
[0016] According to the decorative effect classification: can be divided into:
1. The surface smooth and smooth plane paint (commonly known as flat coating), which is the most common construction method; 2. The surface is sand-like decorative effect of the sand wall coating, such as real stone paint; 3. a multi-layer paint that forms a three-dimensional decorative effect of concave and convex patterns, such as relief.
1. The surface smooth and smooth plane paint (commonly known as flat coating), which is the most common construction method; 2. The surface is sand-like decorative effect of the sand wall coating, such as real stone paint; 3. a multi-layer paint that forms a three-dimensional decorative effect of concave and convex patterns, such as relief.
[0017] Classified according to the use parts on the building: divided into interior wall paint, exterior wall paint, floor paint, door and window paint and ceiling paint.
[0018] According to the function classification: can be divided into ordinary coatings and special functional architectural coatings (such as fire retardant coatings, waterproof coatings, mildew coatings, road marking paints, etc.).
[0019] According to the use of color effects classification: such as metal paint, natural paint (or known as: solid paint), transparent varnish.
[0020] 201610645798.4 The invention relates to the field of production and preparation of polymer products, in particular to an acrylic resin flame retardant coating, 12-18 parts amino resin, 3-6 parts ethyl acrylate, 3-5 parts of butyl acrylate, 2-10 parts melamine, 1-2 parts defoamer, 2-6 parts of pigment and filler, 2-3 parts of acrylic acid, 60 to 70 parts by weight of an anionic aqueous resin containing a carboxyl group, 5 to 10 parts by weight of a water-resistant pigment, 7 to 8 parts by weight of an auxiliary agent, 1 to 2 parts by weight of an interfacial adhesion promoter, 4-8 parts of charcoal agent, 10-20 parts by weight of deionized water;
interface adhesion promoter is formed by reacting metal organic compounds, polyisocyanates and hydroxyl groups-containing oligomers. The acrylic resin coating of the present invention has excellent interfacial adhesion with the substrate and has a good flame retarding effect.
interface adhesion promoter is formed by reacting metal organic compounds, polyisocyanates and hydroxyl groups-containing oligomers. The acrylic resin coating of the present invention has excellent interfacial adhesion with the substrate and has a good flame retarding effect.
[0021] flame retardant, antibacterial, waterproof graphene modified acrylate resin coating preparation method 201610331925.3 discloses a flame retardant, antibacterial, waterproof graphene modified acrylate resin coating preparation method, the walnut peel is peeled off, washed with water, set Dry in an oven at 40-70 C to constant weight, crush and pass 80-100 mesh sieve to obtain walnut green skin powder, weigh walnut powder and water, add allyl trimethyl ammonium chloride, 4-Methyl methoxyacetoacetate is boiled under reflux at 80-100 C, filtered and decoctioned, concentrated under reduced pressure at 60-70 C, until the concentrated liquid reaches a concentration of 15%-20%. The constant weight can be obtained, and the walnut green skin extract concentrate is obtained and used in the acrylate resin, and the obtained acrylate resin has antibacterial, flame retardant and water repellency.
Summary of the invention
Summary of the invention
[0022] The present invention relates to a flame-retardant, water-repellent aqueous core-shell type acrylate resin coating and a method for preparing a paint. The main idea of the invention is to modify the intumescent flame retardant and the water repellent with a vinyl monomer, can be grafted into the acrylic resin, specifically with vinyl phosphine as a bridge, with the aid of 2-aminoisobutyric acid to react the intumescent flame retardant into the acrylic resin, while using acrylic acid, hydroxyethyl acrylate The water repellent is grafted into the acrylic resin under the action of aminotrimethylene phosphonic acid and tetramethylethylenediamine, and the flame retardant and water-repellent water-based core-shell acrylate resin coating is obtained by the action of a self-made crosslinking agent. And paint.
[0023] A flame-retardant, water-repellent water-based core-shell type acrylate resin coating and a preparation method of the paint, the preparation method is as follows:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacting at 90-120 C for 3-5h, cooling to 70-80 C, reaction for 2-5h, then heating up To 90-100 C, adding 1-2mol diethanolamine, chlorobutanol 0.3mo1, 0.3mo1 vinyl phosphine and 1.6-aminoisobutyric acid 1.6g, the reaction time is 2-6h, the flame retardant is obtained;
(2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g of water, and gradually The temperature was raised to 85 C, and 22 g of coconut fatty acid, 16 g of diethanolamide, 3.9 g of trimethylolpropane, 4.4 g of aminotrimethylene phosphonate and 0.7 g of tetramethylethylenediamine were added in that order, and the mixture was uniformly heated to 70 C. Stir until completely dissolved, and react for 2h to obtain the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel:
water 55-75 parts, emulsifier 0.2-2.2 parts, acrylic acid 0.6-3.0 parts, heating to 50 C, stirring for 30 min, adding A monomer, the emulsification time is 30-60min;
warming up to 70 C to start reflux water, warming up to 75 C, heat preservation, adding initiator A0.2-0.6 parts by weight, the dropping time lasts for 1-2h, after the addition, the reaction is 2-5h, Core layer emulsion The monomer A is prepared by mixing 3-8 parts by weight of butyl acrylate, 2-6 parts by weight of methyl methacrylate, and 3-3.5 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.3-0.6 parts by weight of initiator A
and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time lasts for 1 to 4 hours. After the completion of the dropwise addition, the reaction was stirred at 75-85 C
for 2 h, then 0.5-1.0 parts by weight of the cross-linking agent was added, the reaction time was maintained at 75-85 C for 1-2 h, the temperature was lowered to 50 C, 0.3 parts by weight of the emulsifier was added, and the step (2) The obtained water repellent agent is 0.7 parts, the reaction time is 30 min, and the pH value is adjusted to 7-8 by adding ammonia water to obtain the flame retardant, water-repellent water-based core-shell type acrylate resin coating and paint;
The B monomer is prepared by mixing 4 to 8 parts by weight of butyl acrylate, 3 to 6 parts by weight of methyl methacrylate, and 3 to 5 parts by weight of ethyl acrylate.
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacting at 90-120 C for 3-5h, cooling to 70-80 C, reaction for 2-5h, then heating up To 90-100 C, adding 1-2mol diethanolamine, chlorobutanol 0.3mo1, 0.3mo1 vinyl phosphine and 1.6-aminoisobutyric acid 1.6g, the reaction time is 2-6h, the flame retardant is obtained;
(2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g of water, and gradually The temperature was raised to 85 C, and 22 g of coconut fatty acid, 16 g of diethanolamide, 3.9 g of trimethylolpropane, 4.4 g of aminotrimethylene phosphonate and 0.7 g of tetramethylethylenediamine were added in that order, and the mixture was uniformly heated to 70 C. Stir until completely dissolved, and react for 2h to obtain the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel:
water 55-75 parts, emulsifier 0.2-2.2 parts, acrylic acid 0.6-3.0 parts, heating to 50 C, stirring for 30 min, adding A monomer, the emulsification time is 30-60min;
warming up to 70 C to start reflux water, warming up to 75 C, heat preservation, adding initiator A0.2-0.6 parts by weight, the dropping time lasts for 1-2h, after the addition, the reaction is 2-5h, Core layer emulsion The monomer A is prepared by mixing 3-8 parts by weight of butyl acrylate, 2-6 parts by weight of methyl methacrylate, and 3-3.5 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.3-0.6 parts by weight of initiator A
and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time lasts for 1 to 4 hours. After the completion of the dropwise addition, the reaction was stirred at 75-85 C
for 2 h, then 0.5-1.0 parts by weight of the cross-linking agent was added, the reaction time was maintained at 75-85 C for 1-2 h, the temperature was lowered to 50 C, 0.3 parts by weight of the emulsifier was added, and the step (2) The obtained water repellent agent is 0.7 parts, the reaction time is 30 min, and the pH value is adjusted to 7-8 by adding ammonia water to obtain the flame retardant, water-repellent water-based core-shell type acrylate resin coating and paint;
The B monomer is prepared by mixing 4 to 8 parts by weight of butyl acrylate, 3 to 6 parts by weight of methyl methacrylate, and 3 to 5 parts by weight of ethyl acrylate.
[0024] The catalyst A is any one of 2,4-dichloronitrobenzene, p-nitroaniline, hydroxylamine sulfate, and hydroxylamine chloride.
[0025] The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is any one of diethyl vinylphosphonate and vinylphosphonic acid. The initiator A is any one of ammonium persulfate and potassium persulfate; the crosslinking agent is prepared by adding 4.6g of hydroxyethylidene diphosphonic acid and 3.5g of 2-hydroxypropanetricarboxylic acid to In a three-necked flask, 6.2 g of pentaerythritol and 4.1g of trimethylolpropane were added at 90 C, the reaction was incubated for 2 to 4 hours, and then 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the reaction was carried out at 110 C for 3-4 h. The crosslinking agent is obtained.
The advantages of the present invention are:
(1) selecting 2,4-dichloronitrobenzene, p-nitroaniline, hydroxylamine sulfate, and hydroxylamine chloride as catalysts for intumescent flame retardants; having the advantages of non-toxicity and high efficiency;
(2) The flame retardant is an intumescent flame retardant with good carbon residue and expansion, which promotes the dense carbon layer on the surface of the acrylic resin, and has a thermal non-thermal body at the same time, which reduces the external heat. The tendency to continue burning.
[0027] (3) The intumescent flame retardant and the water repellent are modified with a vinyl monomer, and can be grafted into an acrylic resin, specifically, a vinyl phosphine as a bridge in 2-aminoisobutyric acid. With the assistance of the reaction, the intumescent flame retardant is reacted into the acrylic resin, and the water repellent is grafted into the acrylic resin by using acrylic acid and hydroxyethyl acrylate under the action of aminotrimethylene phosphonic acid and tetramethylethylenediamine. Under the action of self-made cross-linking agent, a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint are obtained.
[0028] (4) The initiators which were not specifically described in the step (3) of the preparation of the acrylic resin and the step (4) were all dissolved in 5 g of water.
Embodiments Example 1 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 90 C for 3h, cooled to 70 C, reacted for 2h, then heated to 90 C, added 1 mol of diethanolamine , 0.3 mol of chlorobutanol, 0.3 mol of vinyl phosphine and 1.6 g of 2-aminoisobutyric acid, the reaction time is 2 h, to obtain the flame retardant;
(2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g of water, and gradually The temperature was raised to 85 C, and 22 g of coconut fatty acid, 16 g of diethanolamide, 3.9 g of trimethylolpropane, 4.4 g of aminotrimethylene phosphonate and 0.7 g of tetramethylethylenediamine were added in that order, and the mixture was uniformly heated to 70 C. Stir until completely dissolved, and react for 2h to obtain the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel: 55 parts of water, 0.2 parts of emulsifier, 0.6 parts of acrylic acid, heating to 50 C, stirring for 30 min, adding A monomer, emulsification time is 30 min; heating to 70 C The mixture was refluxed, heated to 75 C, and then incubated. The initiator A
was added dropwise with 0.2 parts by weight (dissolved with 5 parts by weight of water), and the addition time was 1 h. After the completion of the dropwise addition, the reaction was carried out for 2 hours to obtain a core layer emulsion;
The monomer A is prepared by mixing 3 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.3 parts by weight of initiator A
(dissolved with 5 parts by weight of water) and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), dropwise The time lasts for 1 hour. After the completion of the dropwise addition, the reaction is stirred at 75 C for 2 h, then 0.5 parts by weight of the crosslinking agent is added, the reaction time is kept at 75 C for 1 h, the temperature is lowered to 50 C, 0.3 parts by weight of the emulsifier is added, and the water obtained by the step (2) is obtained. 0.7 parts, the reaction time is 30min, and the pH value is adjusted to 7-8 by adding ammonia water to obtain the flame retardant and waterproof water-based core-shell type acrylate resin coating and paint;
The B monomer was prepared by mixing 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate.
[0030] Its catalyst A is 2,4-dichloronitrobenzene.
[0031] The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is diethyl vinylphosphonate; the initiator A is ammonium persulfate. The cross-linking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and trimethylolpropane at 90 C. 4.1 g, the incubation reaction was carried out for 2 h, and further 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the mixture was reacted at 110 C for 3 h to obtain the crosslinking agent.
Example 2 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 120 C for 5h, cooled to 80 C, reacted for 5h, then heated to 100 C, added 2mo1 of diethanolamine , 0.3 mol of chlorobutanol, 0.3 mol of vinyl phosphine and 1.6 g of 2-aminoisobutyric acid, the reaction time is 6 h, to obtain the flame retardant;
(2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g of water, and gradually The temperature was raised to 85 C, and 22 g of coconut fatty acid, 16 g of diethanolamide, 3.9 g of trimethylolpropane, 4.4g of aminotrimethylene phosphonate and 0.7 g of tetramethylethylenediamine were added in that order, and the mixture was uniformly heated to 70 C. Stir until completely dissolved, and react for 2h to obtain the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel: 75 parts of water, 2.2 parts of emulsifier, 3.0 parts of acrylic acid, heating to 50 C, stirring for 30 min, adding A monomer, emulsification time is 60 min; heating to 70 C The reflux water was started, the temperature was raised to 75 C, and the temperature was maintained. The initiator A was added dropwise in an amount of 0.6 parts by weight, the dropping time was continued for 2 hours, and the reaction was carried out for 5 hours after the dropwise addition to obtain a core layer emulsion;
The A monomer is prepared by mixing 8 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate and 3.5 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.6 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time is continued for 4 hours, after the dropwise addition The reaction was stirred at 85 C for 2 h, then 1.0 part by weight of cross-linking agent was added, the reaction time was kept at 85 C for 2 h, the temperature was lowered to 50 C, 0.3 parts by weight of emulsifier and 0.7 parts of water-repellent agent obtained in step (2) were added, and the reaction time was 30 min. The pH of the ammonia water is adjusted to 7-8, and the flame retardant and waterproof water-based core-shell type acrylate resin coating and paint are obtained;
The B monomer was prepared by mixing 8 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate, and 5 parts by weight of ethyl acrylate.
[0033] Its catalyst A is p-nitroaniline.
[0034] The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is vinylphosphonic acid; the initiator A is potassium persulfate; The cross-linking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 C. After the reaction was kept for 4 hours, 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was further added, and the mixture was reacted at 110 C for 4 hours to obtain the crosslinking agent.
Example 3 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 105 C for 4h, cooled to 75 C, reacted for 3.5h, then heated to 95 C, added 1.5mo1 Diethanolamine, chlorobutanol 0.3 mol, 0.3 mol of vinyl phosphine and 1.6 g of aminoaminobutyric acid were reacted for 4 h to obtain the flame retardant.
[0036] (2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethyl hydroxyethyl propylene diamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g. Water, gradually warmed to 85 C, followed by the addition of 22g coconut fatty acid, 16g diethanolamide, trimethylolpropane 6.9g, aminotrimethylene phosphonic acid 4.4g and tetramethylethylenediamine 0.7g, mixed evenly, heated to At 70 C, stirring until completely dissolved, the reaction for 2 h, that is, the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel: 65 parts of water, 1.2 parts of emulsifier, 1.8 parts of acrylic acid, heating to 50 C, stirring for 30 min, adding A monomer, emulsification time is 45 mm; heating to 70 C The water was refluxed, the temperature was raised to 75 C, and the temperature was maintained. The initiator A was added dropwise in an amount of 0.4 parts by weight, and the dropping time was continued for 1.5 hours. After the dropwise addition, the reaction was carried out for 2.5 hours to obtain a core layer emulsion;
The monomer A is prepared by mixing: 5.5 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, and 3.3 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.45 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropwise addition time is 2.5 hours, and the addition is completed. After the incubation at 80 C for 2 h, add 0.75 parts by weight of cross-linking agent, heat the reaction at 80 C for 1.5 h, reduce the temperature to 50 C, add 0.3 parts by weight of emulsifier and 0.7 parts of water-repellent agent obtained in step (2), reaction time 30 min. Adding ammonia water to adjust the pH
value to 7-8, and obtaining the flame retardant, waterproof and water-based core-shell type acrylate resin coating and paint;
The B monomer was prepared by mixing 6 parts by weight of butyl acrylate, 4.5 parts by weight of methyl methacrylate, and 4 parts by weight of ethyl acrylate.
[0037] Its catalyst A is hydroxylamine sulfate.
0038] The emulsifier is a mixture of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; vinyl phosphine is diethyl vinylphosphonate; initiator A is ammonium persulfate The crosslinking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and trimethylolpropane at 90 C. 4.1 g, the reaction was kept for 3 hours, and then 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the mixture was reacted at 110 C for 3.5 hours to obtain the crosslinking agent.
Example 4 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and -y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 90 C for 5h, cooled to 80 C, reacted for 5h, then heated to 100 C, added 2mo1 of diethanolamine 0.3 g of chlorobutanol, 0.3 mol of vinylphosphine and 1.6 g of 2-aminoisobutyric acid were reacted for 3 hours to obtain the flame retardant.
[0040] (2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylene diamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g. Water, gradually warmed to 85 C, followed by the addition of 22g coconut fatty acid, 16g diethanolamide, trimethylolpropane 6.9g, aminotrimethylene phosphonic acid 4.4g and tetramethylethylenediamine 0.7g, mixed evenly, heated to At 70 C, stirring until completely dissolved, the reaction for 2 h, the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel: 60 parts of water, 1 part of emulsifier, 2 parts of acrylic acid, heating to 50 C, stirring for 30 mm, adding A monomer, emulsification time is 45 min; heating to 70 C Start the reflux water, heat up to 75 C and then keep warm, add 0.2 parts by weight of the initiator, the dropping time lasts for 1 h, and after the addition, the reaction is carried out for 2 h to obtain a core layer emulsion;
The A monomer is prepared by mixing 3 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate and 3.5 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.6 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time is continued for 4 hours, after the dropwise addition The reaction was stirred at 85 C for 2 h, then 1.0 part by weight of cross-linking agent was added, the reaction time was kept at 85 C for 2 h, the temperature was lowered to 50 C, 0.3 parts by weight of emulsifier and 0.7 parts of water-repellent agent obtained in step (2) were added, and the reaction time was 30 min. The pH of the ammonia water is adjusted to 7-8, and the flame retardant and waterproof water-based core-shell type acrylate resin coating and paint are obtained;
The B monomer is obtained by mixing 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, and 5 parts by weight of ethyl acrylate.
[0041] Its catalyst A is hydroxylamine chloride.The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is diethyl vinylphosphonate; the initiator A is ammonium persulfate; The cross-linking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 C.
The reaction was kept for 2 hours, and then 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the mixture was reacted at 110 C for 4 hours to obtain the crosslinking agent.
Example 5 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 120 C for 3h, cooled to 70 C, reacted for 2h, then heated to 90 C, added 1 mol of diethanolamine 0.3 g of chlorobutanol, 0.3 mol of vinylphosphine and 1.6 g of 2-aminoisobutyric acid were reacted for 2 hours to obtain the flame retardant.
[0043] (2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g. Water, gradually warmed to 85 C, followed by the addition of 22g coconut fatty acid, 16g diethanolamide, trimethylolpropane 6.9g, aminotrimethylene phosphonic acid 4.4g and tetramethylethylenediamine 0.7g, mixed evenly, heated to The water repellent was obtained by stirring at 70 C until completely dissolved and reacting for 2 h.
[0044] (3) The following weight ratio of raw materials were added to the reaction vessel: water 55 parts, emulsifier 2.2 parts, acrylic acid 3.0 parts, the temperature was raised to 50 C, stirred for 30 min, A monomer was added, the emulsification time was 60 min; At 70 C, the reflux water was started, the temperature was raised to 75 C, and the temperature was maintained. The initiator A was added dropwise in an amount of 0.6 parts by weight, the dropping time was continued for 2 hours, and the reaction was carried out for 5 hours after the dropwise addition to obtain a core layer emulsion;
The monomer A is prepared by mixing 8 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.3 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time is continued for 1 hour, after the dropwise addition The reaction was stirred at 75 C for 2 h, then 0.5 parts by weight of cross-linking agent was added, the reaction time was kept at 75 C for 1 h, the temperature was lowered to 50 C, 0.3 parts by weight of emulsifier and 0.7 parts of water-repellent agent obtained in step (2) were added, and the reaction time was 30 min. The pH of the ammonia water is adjusted to 7-8, and the flame retardant and waterproof water-based core-shell type acrylate resin coating and paint are obtained;
The B monomer is obtained by mixing 5 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, and 4 parts by weight of ethyl acrylate.
[0045] Its catalyst A is p-nitroaniline.The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is diethyl vinylphosphonate; the initiator A is potassium persulfate; The cross-linking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 C.
The reaction was kept for 3 hours, and then 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the mixture was reacted at 110 C for 3 hours to obtain the crosslinking agent.
[0046] The flame retardancy is measured by the oxygen index and the flaming burning time, wherein the flame retardancy and the light resistance are both measured by the performance of the acrylate resin coating film and the expansion property is to heat the muffle furnace to 500 C The crucible containing 1 g (with an error of not more than 0.1 g) was placed in a muffle furnace and heated for 10 min, and the expansion ratio and the residual carbon ratio (only the flame retardant was measured) were measured.
Table 1 Test Performance Example 1 Example 2 Example 3 Example 4 Example 5 Oxygen Index/% 28.4 28.7 29.4 29.2 28.8 Flaming burning time 3.2 3.5 3.8 4.2 3.9 /s Residual carbon rate 66.2 68.4 69.8 68.7 68.8 of flame retardant /%
Flame retardant 67.9 66.4 68.3 68.9 68.5 expansion ratio Water resistanceNo waterNo waterNo waterNo waterNo water (0.3Mpa) 30min leakage leakage leakage leakage leakage It can be seen from Table 1 that the polyurethane coating and the adhesive are superior to the performance of the invention patent mentioned in the background art in terms of oxygen index, flaming burning time and water repellency. Due to space limitations, the applicant has 201610331925.3 Both Example 1 and Example 2 of 201610645798.4 were tested for oxygen index and flaming burn time. The oxygen index was found to be 26.2 and 22.9, respectively, and the flaming burn time was 19.8 and 16.8, respectively.
Table 2 Test Performance (No Catalyst A) Example Example 1 Example 2 Example 3 Example 4 Oxygen
The advantages of the present invention are:
(1) selecting 2,4-dichloronitrobenzene, p-nitroaniline, hydroxylamine sulfate, and hydroxylamine chloride as catalysts for intumescent flame retardants; having the advantages of non-toxicity and high efficiency;
(2) The flame retardant is an intumescent flame retardant with good carbon residue and expansion, which promotes the dense carbon layer on the surface of the acrylic resin, and has a thermal non-thermal body at the same time, which reduces the external heat. The tendency to continue burning.
[0027] (3) The intumescent flame retardant and the water repellent are modified with a vinyl monomer, and can be grafted into an acrylic resin, specifically, a vinyl phosphine as a bridge in 2-aminoisobutyric acid. With the assistance of the reaction, the intumescent flame retardant is reacted into the acrylic resin, and the water repellent is grafted into the acrylic resin by using acrylic acid and hydroxyethyl acrylate under the action of aminotrimethylene phosphonic acid and tetramethylethylenediamine. Under the action of self-made cross-linking agent, a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint are obtained.
[0028] (4) The initiators which were not specifically described in the step (3) of the preparation of the acrylic resin and the step (4) were all dissolved in 5 g of water.
Embodiments Example 1 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 90 C for 3h, cooled to 70 C, reacted for 2h, then heated to 90 C, added 1 mol of diethanolamine , 0.3 mol of chlorobutanol, 0.3 mol of vinyl phosphine and 1.6 g of 2-aminoisobutyric acid, the reaction time is 2 h, to obtain the flame retardant;
(2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g of water, and gradually The temperature was raised to 85 C, and 22 g of coconut fatty acid, 16 g of diethanolamide, 3.9 g of trimethylolpropane, 4.4 g of aminotrimethylene phosphonate and 0.7 g of tetramethylethylenediamine were added in that order, and the mixture was uniformly heated to 70 C. Stir until completely dissolved, and react for 2h to obtain the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel: 55 parts of water, 0.2 parts of emulsifier, 0.6 parts of acrylic acid, heating to 50 C, stirring for 30 min, adding A monomer, emulsification time is 30 min; heating to 70 C The mixture was refluxed, heated to 75 C, and then incubated. The initiator A
was added dropwise with 0.2 parts by weight (dissolved with 5 parts by weight of water), and the addition time was 1 h. After the completion of the dropwise addition, the reaction was carried out for 2 hours to obtain a core layer emulsion;
The monomer A is prepared by mixing 3 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.3 parts by weight of initiator A
(dissolved with 5 parts by weight of water) and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), dropwise The time lasts for 1 hour. After the completion of the dropwise addition, the reaction is stirred at 75 C for 2 h, then 0.5 parts by weight of the crosslinking agent is added, the reaction time is kept at 75 C for 1 h, the temperature is lowered to 50 C, 0.3 parts by weight of the emulsifier is added, and the water obtained by the step (2) is obtained. 0.7 parts, the reaction time is 30min, and the pH value is adjusted to 7-8 by adding ammonia water to obtain the flame retardant and waterproof water-based core-shell type acrylate resin coating and paint;
The B monomer was prepared by mixing 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate.
[0030] Its catalyst A is 2,4-dichloronitrobenzene.
[0031] The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is diethyl vinylphosphonate; the initiator A is ammonium persulfate. The cross-linking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and trimethylolpropane at 90 C. 4.1 g, the incubation reaction was carried out for 2 h, and further 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the mixture was reacted at 110 C for 3 h to obtain the crosslinking agent.
Example 2 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 120 C for 5h, cooled to 80 C, reacted for 5h, then heated to 100 C, added 2mo1 of diethanolamine , 0.3 mol of chlorobutanol, 0.3 mol of vinyl phosphine and 1.6 g of 2-aminoisobutyric acid, the reaction time is 6 h, to obtain the flame retardant;
(2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g of water, and gradually The temperature was raised to 85 C, and 22 g of coconut fatty acid, 16 g of diethanolamide, 3.9 g of trimethylolpropane, 4.4g of aminotrimethylene phosphonate and 0.7 g of tetramethylethylenediamine were added in that order, and the mixture was uniformly heated to 70 C. Stir until completely dissolved, and react for 2h to obtain the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel: 75 parts of water, 2.2 parts of emulsifier, 3.0 parts of acrylic acid, heating to 50 C, stirring for 30 min, adding A monomer, emulsification time is 60 min; heating to 70 C The reflux water was started, the temperature was raised to 75 C, and the temperature was maintained. The initiator A was added dropwise in an amount of 0.6 parts by weight, the dropping time was continued for 2 hours, and the reaction was carried out for 5 hours after the dropwise addition to obtain a core layer emulsion;
The A monomer is prepared by mixing 8 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate and 3.5 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.6 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time is continued for 4 hours, after the dropwise addition The reaction was stirred at 85 C for 2 h, then 1.0 part by weight of cross-linking agent was added, the reaction time was kept at 85 C for 2 h, the temperature was lowered to 50 C, 0.3 parts by weight of emulsifier and 0.7 parts of water-repellent agent obtained in step (2) were added, and the reaction time was 30 min. The pH of the ammonia water is adjusted to 7-8, and the flame retardant and waterproof water-based core-shell type acrylate resin coating and paint are obtained;
The B monomer was prepared by mixing 8 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate, and 5 parts by weight of ethyl acrylate.
[0033] Its catalyst A is p-nitroaniline.
[0034] The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is vinylphosphonic acid; the initiator A is potassium persulfate; The cross-linking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 C. After the reaction was kept for 4 hours, 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was further added, and the mixture was reacted at 110 C for 4 hours to obtain the crosslinking agent.
Example 3 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 105 C for 4h, cooled to 75 C, reacted for 3.5h, then heated to 95 C, added 1.5mo1 Diethanolamine, chlorobutanol 0.3 mol, 0.3 mol of vinyl phosphine and 1.6 g of aminoaminobutyric acid were reacted for 4 h to obtain the flame retardant.
[0036] (2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethyl hydroxyethyl propylene diamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g. Water, gradually warmed to 85 C, followed by the addition of 22g coconut fatty acid, 16g diethanolamide, trimethylolpropane 6.9g, aminotrimethylene phosphonic acid 4.4g and tetramethylethylenediamine 0.7g, mixed evenly, heated to At 70 C, stirring until completely dissolved, the reaction for 2 h, that is, the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel: 65 parts of water, 1.2 parts of emulsifier, 1.8 parts of acrylic acid, heating to 50 C, stirring for 30 min, adding A monomer, emulsification time is 45 mm; heating to 70 C The water was refluxed, the temperature was raised to 75 C, and the temperature was maintained. The initiator A was added dropwise in an amount of 0.4 parts by weight, and the dropping time was continued for 1.5 hours. After the dropwise addition, the reaction was carried out for 2.5 hours to obtain a core layer emulsion;
The monomer A is prepared by mixing: 5.5 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, and 3.3 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.45 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropwise addition time is 2.5 hours, and the addition is completed. After the incubation at 80 C for 2 h, add 0.75 parts by weight of cross-linking agent, heat the reaction at 80 C for 1.5 h, reduce the temperature to 50 C, add 0.3 parts by weight of emulsifier and 0.7 parts of water-repellent agent obtained in step (2), reaction time 30 min. Adding ammonia water to adjust the pH
value to 7-8, and obtaining the flame retardant, waterproof and water-based core-shell type acrylate resin coating and paint;
The B monomer was prepared by mixing 6 parts by weight of butyl acrylate, 4.5 parts by weight of methyl methacrylate, and 4 parts by weight of ethyl acrylate.
[0037] Its catalyst A is hydroxylamine sulfate.
0038] The emulsifier is a mixture of sodium dodecylbenzenesulfonate and fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; vinyl phosphine is diethyl vinylphosphonate; initiator A is ammonium persulfate The crosslinking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and trimethylolpropane at 90 C. 4.1 g, the reaction was kept for 3 hours, and then 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the mixture was reacted at 110 C for 3.5 hours to obtain the crosslinking agent.
Example 4 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and -y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 90 C for 5h, cooled to 80 C, reacted for 5h, then heated to 100 C, added 2mo1 of diethanolamine 0.3 g of chlorobutanol, 0.3 mol of vinylphosphine and 1.6 g of 2-aminoisobutyric acid were reacted for 3 hours to obtain the flame retardant.
[0040] (2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylene diamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g. Water, gradually warmed to 85 C, followed by the addition of 22g coconut fatty acid, 16g diethanolamide, trimethylolpropane 6.9g, aminotrimethylene phosphonic acid 4.4g and tetramethylethylenediamine 0.7g, mixed evenly, heated to At 70 C, stirring until completely dissolved, the reaction for 2 h, the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel: 60 parts of water, 1 part of emulsifier, 2 parts of acrylic acid, heating to 50 C, stirring for 30 mm, adding A monomer, emulsification time is 45 min; heating to 70 C Start the reflux water, heat up to 75 C and then keep warm, add 0.2 parts by weight of the initiator, the dropping time lasts for 1 h, and after the addition, the reaction is carried out for 2 h to obtain a core layer emulsion;
The A monomer is prepared by mixing 3 parts by weight of butyl acrylate, 6 parts by weight of methyl methacrylate and 3.5 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.6 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time is continued for 4 hours, after the dropwise addition The reaction was stirred at 85 C for 2 h, then 1.0 part by weight of cross-linking agent was added, the reaction time was kept at 85 C for 2 h, the temperature was lowered to 50 C, 0.3 parts by weight of emulsifier and 0.7 parts of water-repellent agent obtained in step (2) were added, and the reaction time was 30 min. The pH of the ammonia water is adjusted to 7-8, and the flame retardant and waterproof water-based core-shell type acrylate resin coating and paint are obtained;
The B monomer is obtained by mixing 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, and 5 parts by weight of ethyl acrylate.
[0041] Its catalyst A is hydroxylamine chloride.The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is diethyl vinylphosphonate; the initiator A is ammonium persulfate; The cross-linking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 C.
The reaction was kept for 2 hours, and then 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the mixture was reacted at 110 C for 4 hours to obtain the crosslinking agent.
Example 5 A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and y-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacted at 120 C for 3h, cooled to 70 C, reacted for 2h, then heated to 90 C, added 1 mol of diethanolamine 0.3 g of chlorobutanol, 0.3 mol of vinylphosphine and 1.6 g of 2-aminoisobutyric acid were reacted for 2 hours to obtain the flame retardant.
[0043] (2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g. Water, gradually warmed to 85 C, followed by the addition of 22g coconut fatty acid, 16g diethanolamide, trimethylolpropane 6.9g, aminotrimethylene phosphonic acid 4.4g and tetramethylethylenediamine 0.7g, mixed evenly, heated to The water repellent was obtained by stirring at 70 C until completely dissolved and reacting for 2 h.
[0044] (3) The following weight ratio of raw materials were added to the reaction vessel: water 55 parts, emulsifier 2.2 parts, acrylic acid 3.0 parts, the temperature was raised to 50 C, stirred for 30 min, A monomer was added, the emulsification time was 60 min; At 70 C, the reflux water was started, the temperature was raised to 75 C, and the temperature was maintained. The initiator A was added dropwise in an amount of 0.6 parts by weight, the dropping time was continued for 2 hours, and the reaction was carried out for 5 hours after the dropwise addition to obtain a core layer emulsion;
The monomer A is prepared by mixing 8 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, and 3 parts by weight of ethyl acrylate;
(4) simultaneously adding B monomer, 0.3 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time is continued for 1 hour, after the dropwise addition The reaction was stirred at 75 C for 2 h, then 0.5 parts by weight of cross-linking agent was added, the reaction time was kept at 75 C for 1 h, the temperature was lowered to 50 C, 0.3 parts by weight of emulsifier and 0.7 parts of water-repellent agent obtained in step (2) were added, and the reaction time was 30 min. The pH of the ammonia water is adjusted to 7-8, and the flame retardant and waterproof water-based core-shell type acrylate resin coating and paint are obtained;
The B monomer is obtained by mixing 5 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, and 4 parts by weight of ethyl acrylate.
[0045] Its catalyst A is p-nitroaniline.The emulsifier is a mixture of sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether in a weight ratio of 4:1; the vinyl phosphine is diethyl vinylphosphonate; the initiator A is potassium persulfate; The cross-linking agent is prepared by adding 4.6 g of hydroxyethylidene diphosphonic acid and 3.5 g of 2-hydroxypropanetricarboxylic acid to a three-necked flask, and adding 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane at 90 C.
The reaction was kept for 3 hours, and then 1.1 g of 7-hydroxycoumarin-3-carboxylic acid was added, and the mixture was reacted at 110 C for 3 hours to obtain the crosslinking agent.
[0046] The flame retardancy is measured by the oxygen index and the flaming burning time, wherein the flame retardancy and the light resistance are both measured by the performance of the acrylate resin coating film and the expansion property is to heat the muffle furnace to 500 C The crucible containing 1 g (with an error of not more than 0.1 g) was placed in a muffle furnace and heated for 10 min, and the expansion ratio and the residual carbon ratio (only the flame retardant was measured) were measured.
Table 1 Test Performance Example 1 Example 2 Example 3 Example 4 Example 5 Oxygen Index/% 28.4 28.7 29.4 29.2 28.8 Flaming burning time 3.2 3.5 3.8 4.2 3.9 /s Residual carbon rate 66.2 68.4 69.8 68.7 68.8 of flame retardant /%
Flame retardant 67.9 66.4 68.3 68.9 68.5 expansion ratio Water resistanceNo waterNo waterNo waterNo waterNo water (0.3Mpa) 30min leakage leakage leakage leakage leakage It can be seen from Table 1 that the polyurethane coating and the adhesive are superior to the performance of the invention patent mentioned in the background art in terms of oxygen index, flaming burning time and water repellency. Due to space limitations, the applicant has 201610331925.3 Both Example 1 and Example 2 of 201610645798.4 were tested for oxygen index and flaming burn time. The oxygen index was found to be 26.2 and 22.9, respectively, and the flaming burn time was 19.8 and 16.8, respectively.
Table 2 Test Performance (No Catalyst A) Example Example 1 Example 2 Example 3 Example 4 Oxygen
26.3 25.8 25.9 24.7 26.6 Index/%
Flaming burning time 13.6 15.2 14.9 16.8 19.8 Is _ Residual carbon rate 58.6 52.3 53.9 54.2 57.8 of flame retardant /%
_ Flame retardant 52.9 51.8 53.5 56.3 54.9 expansion ratio As can be seen from Table 2, the oxygen index, the flaming burning time, the residual carbon ratio, and the expansion ratio of the catalyst A were not decreased.
Table 3 Test performance (catalyst A, without 2-aminoisobutyric acid) Example 1 Example 2 Example 3 Example 4 Example 5 Oxygen Index/% 27.6 26.9 26.7 25.9 27.7 Flaming burning 8.8 11.6 13.2 8.9 11.6 time / s Residual carbon rate of flame61.2 59.6 58.7 58.6 60.3 retardant /%
Flame retardant 61.3 58.8 59.7 58.9 56.8 expansion ratio As can be seen from Table 3, 2-aminoisobutyric acid improves various indexes of flame retardancy.
[0050]
Table 4 Test performance (no crosslinker added) Example 1 Example 2 Example 3 Example 4 Example 5 Water resistanceLeaking No water Leaking Leaking Leaking water (0.3Mpa) 30min water leakage water water As can be seen from Table 4, most of the data obtained without the cross-linking agent leaked.
Table 5 Test performance (without waterproofing agent) Example 1 Example 2 Example 3 Example 4 Example 5 Waterproof Leaking Leaking Leaking Leaking water Leaking water (0.3Mpa) 30min, water water water It can be seen from Table 5 that the water-repellent agent is not added and the resulting material leaks.
[0052]
Table 6 Test performance (plus water repellent, no aminotrimethylphosphonic acid or tetramethylethylenediamine) Example 1 Example 2 Example 3 Example 4 Example 5 Waterproof (0.3Mpa).
Leaking No water Leaking No water 30min,no aminotrimethyl Leaking water water leakage water leakage phosphonic acid Waterproof (0.3Mpa) for No wate Leaking Leaking No waterNo water 30min without leakage water water leakage leakage tetramethylethylenediamine As can be seen from Table 6, the obtained material partially leaked without the addition of aminotrimethylene phosphonic acid or tetramethylethylenediamine.
Flaming burning time 13.6 15.2 14.9 16.8 19.8 Is _ Residual carbon rate 58.6 52.3 53.9 54.2 57.8 of flame retardant /%
_ Flame retardant 52.9 51.8 53.5 56.3 54.9 expansion ratio As can be seen from Table 2, the oxygen index, the flaming burning time, the residual carbon ratio, and the expansion ratio of the catalyst A were not decreased.
Table 3 Test performance (catalyst A, without 2-aminoisobutyric acid) Example 1 Example 2 Example 3 Example 4 Example 5 Oxygen Index/% 27.6 26.9 26.7 25.9 27.7 Flaming burning 8.8 11.6 13.2 8.9 11.6 time / s Residual carbon rate of flame61.2 59.6 58.7 58.6 60.3 retardant /%
Flame retardant 61.3 58.8 59.7 58.9 56.8 expansion ratio As can be seen from Table 3, 2-aminoisobutyric acid improves various indexes of flame retardancy.
[0050]
Table 4 Test performance (no crosslinker added) Example 1 Example 2 Example 3 Example 4 Example 5 Water resistanceLeaking No water Leaking Leaking Leaking water (0.3Mpa) 30min water leakage water water As can be seen from Table 4, most of the data obtained without the cross-linking agent leaked.
Table 5 Test performance (without waterproofing agent) Example 1 Example 2 Example 3 Example 4 Example 5 Waterproof Leaking Leaking Leaking Leaking water Leaking water (0.3Mpa) 30min, water water water It can be seen from Table 5 that the water-repellent agent is not added and the resulting material leaks.
[0052]
Table 6 Test performance (plus water repellent, no aminotrimethylphosphonic acid or tetramethylethylenediamine) Example 1 Example 2 Example 3 Example 4 Example 5 Waterproof (0.3Mpa).
Leaking No water Leaking No water 30min,no aminotrimethyl Leaking water water leakage water leakage phosphonic acid Waterproof (0.3Mpa) for No wate Leaking Leaking No waterNo water 30min without leakage water water leakage leakage tetramethylethylenediamine As can be seen from Table 6, the obtained material partially leaked without the addition of aminotrimethylene phosphonic acid or tetramethylethylenediamine.
Claims (6)
1. A method for preparing a flame-retardant, water-repellent water-based core-shell acrylate resin coating and paint, which is prepared by:
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and .gamma.-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacting at 90-120 ° C for 3~5h, cooling to 70-80 °C, reaction for 2~5h, then heating up To 90~100 ° C, adding 1~2mol diethanolamine, chlorobutanol 0.3mol, 0.3mol vinyl phosphine and 1.6-aminoisobutyric acid 1.6g, the reaction time is 2~6h, the flame retardant is obtained;
(2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g of water, and gradually The temperature was raised to 85 ° C, and 22 g of coconut fatty acid, 16 g of diethanolamide, 3.9 g of trimethylolpropane, 4.4 g of aminotrimethylene phosphonate and 0.7 g of tetramethylethylenediamine were added in that order, and the mixture was uniformly heated to 70 ° C. Stir until completely dissolved, and react for 2h to obtain the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel:
water 55-75 parts, emulsifier 0.2-2.2 parts, acrylic acid 0.6-3.0 parts, heating to 50 ° C, stirring for 30 min, adding A monomer, the emulsification time is 30~60min;
warming up to 70 °C to start reflux water, warming up to 75 °C, heat preservation, adding initiator A0.2-0.6 parts by weight, the dropping time lasts for 1-2h, after the addition, the reaction is 2-5h, core layer emulsion, the monomer A is prepared by mixing 3-8 parts by weight of butyl acrylate, 2-6 parts by weight of methyl methacrylate, and 3~3.5 parts by weight of ethyl acrylate; (4) simultaneously adding B monomer, 0.3-0.6 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time lasts for 1 to 4 hours. After the completion of the dropwise addition, the reaction was stirred at 75-85 ° C for 2 h, then 0.5-1.0 parts by weight of the cross-linking agent was added, the reaction time was maintained at 75-85 ° C for 1-2 h, the temperature was lowered to 50 ° C, 0.3 parts by weight of the emulsifier was added, and the step (2) The obtained water repellent agent is 0.7 parts, the reaction time is 30 min, and the pH value is adjusted to 7-8 by adding ammonia water to obtain the flame retardant, water-repellent water-based core-shell type acrylate resin coating and paint; The B monomer is prepared by mixing 4 to 8 parts by weight of butyl acrylate, 3 to 6 parts by weight of methyl methacrylate, and 3 to 5 parts by weight of ethyl acrylate.
(1) Preparation of flame retardant: 1 mol of tetramethylolsulfate, 0.4 mol of y-aminopropyltriethoxysilane and 3 mol of phosphoric acid were added to a three-necked flask, and then 5% of triethylamine was added. 5% of the total weight of phosphorus sulphate and .gamma.-aminopropyltriethoxysilane and Catalyst A is 4.2g, reacting at 90-120 ° C for 3~5h, cooling to 70-80 °C, reaction for 2~5h, then heating up To 90~100 ° C, adding 1~2mol diethanolamine, chlorobutanol 0.3mol, 0.3mol vinyl phosphine and 1.6-aminoisobutyric acid 1.6g, the reaction time is 2~6h, the flame retardant is obtained;
(2) Preparation of water repellent: 10 g of acrylic acid, 1.6 g of trimethylhydroxyethyl propylenediamine and 0.7 g of hydroxyethyl acrylate were added to a three-necked bottle, and then an initiator A 0.6 g was added, followed by 70 g of water, and gradually The temperature was raised to 85 ° C, and 22 g of coconut fatty acid, 16 g of diethanolamide, 3.9 g of trimethylolpropane, 4.4 g of aminotrimethylene phosphonate and 0.7 g of tetramethylethylenediamine were added in that order, and the mixture was uniformly heated to 70 ° C. Stir until completely dissolved, and react for 2h to obtain the water repellent;
(3) Adding the following weight ratio raw materials to the reaction vessel:
water 55-75 parts, emulsifier 0.2-2.2 parts, acrylic acid 0.6-3.0 parts, heating to 50 ° C, stirring for 30 min, adding A monomer, the emulsification time is 30~60min;
warming up to 70 °C to start reflux water, warming up to 75 °C, heat preservation, adding initiator A0.2-0.6 parts by weight, the dropping time lasts for 1-2h, after the addition, the reaction is 2-5h, core layer emulsion, the monomer A is prepared by mixing 3-8 parts by weight of butyl acrylate, 2-6 parts by weight of methyl methacrylate, and 3~3.5 parts by weight of ethyl acrylate; (4) simultaneously adding B monomer, 0.3-0.6 parts by weight of initiator A and 4.4 parts by weight of the flame retardant obtained in the step (1) to the core layer emulsion obtained in the step (3), and the dropping time lasts for 1 to 4 hours. After the completion of the dropwise addition, the reaction was stirred at 75-85 ° C for 2 h, then 0.5-1.0 parts by weight of the cross-linking agent was added, the reaction time was maintained at 75-85 ° C for 1-2 h, the temperature was lowered to 50 ° C, 0.3 parts by weight of the emulsifier was added, and the step (2) The obtained water repellent agent is 0.7 parts, the reaction time is 30 min, and the pH value is adjusted to 7-8 by adding ammonia water to obtain the flame retardant, water-repellent water-based core-shell type acrylate resin coating and paint; The B monomer is prepared by mixing 4 to 8 parts by weight of butyl acrylate, 3 to 6 parts by weight of methyl methacrylate, and 3 to 5 parts by weight of ethyl acrylate.
2. The method for preparing a flame-retardant, waterproof, light-resistant aqueous polyurethane coating and an adhesive according to claim 1, wherein the catalyst A is 2,4-dichloronitrobenzene, p-nitroaniline, hydroxylamine sulfate, hydroxylamine chloride any of them.
3. The method for preparing a flame-retardant core-shell type aqueous acrylate-based resin coating according to claim 1, wherein the emulsifier is sodium dodecylbenzenesulfonate and a fatty alcohol polyoxyethylene ether. A mixture of 4:1 by weight.
4. The flame-retardant, water-repellent aqueous core-shell type acrylate resin coating and the method for producing a paint according to claim 1, wherein the vinyl phosphine is any one of diethyl vinylphosphonate and vinylphosphonic acid.
5. The flame-retardant, water-repellent aqueous core-shell type acrylate resin coating according to claim 1, wherein the initiator A is any one of ammonium persulfate and potassium persulfate.
6. The flame-retardant, water-repellent aqueous core-shell type acrylate resin coating and the preparation method of the paint according to claim 1, wherein the crosslinking agent is prepared by: hydroxyethylidene diphosphonic acid 4.6 g and 2- 3.5 g of hydroxypropanetricarboxylic acid was added to a three-necked flask, and 6.2 g of pentaerythritol and 4.1 g of trimethylolpropane were added at 90 ° C, and the reaction was incubated for 2 to 4 hours, and then 7-hydroxycoumarin-3-carboxylic acid 1.1 g was added. The reaction was carried out at 110 ° C for 3-4 h to obtain the crosslinking agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810664863.7A CN108912928B (en) | 2018-06-25 | 2018-06-25 | Preparation method of flame retardant, waterproof water-based core-shell acrylic resin coating and paint |
| CN2018106648637 | 2018-06-25 |
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| CA3028431A1 true CA3028431A1 (en) | 2019-12-25 |
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| Country | Link |
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| CN (2) | CN112266679B (en) |
| CA (1) | CA3028431A1 (en) |
| WO (1) | WO2020000918A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023011799A1 (en) | 2021-08-02 | 2023-02-09 | Röhm Gmbh | Improved resin system for foaming fire protection coatings |
| CN116462808A (en) * | 2023-04-06 | 2023-07-21 | 惠州市舜丰印材科技有限公司 | A kind of fluorosilicone emulsion for aqueous varnish and preparation method thereof |
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| CN1308110A (en) * | 2000-12-28 | 2001-08-15 | 衡水恒基建工材料有限公司 | Composite waterproofing agent and its making process |
| CN1886411B (en) * | 2003-11-28 | 2010-09-08 | 北兴化学工业株式会社 | Manufacturing method of borate phosphate ester compound, novel borate phosphate ester compound and method of use thereof |
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| CN103361084A (en) * | 2013-05-09 | 2013-10-23 | 苏州萃智新技术开发有限公司 | Environment-friendly household flame retardant |
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| CN104371059B (en) * | 2014-12-09 | 2016-08-24 | 烟台史密得机电设备制造有限公司 | Anti-flammability and water proofing property acrylic resin coating and the preparation method of adhesive |
| CN104497768B (en) * | 2014-12-12 | 2016-07-06 | 南阳理工学院 | The preparation method of anti-flammability and water proofing property acrylic resin coating |
| JP6355132B2 (en) * | 2014-12-16 | 2018-07-11 | 関西ペイント株式会社 | Water-based paint composition for can coating |
| CN104861108B (en) * | 2015-06-15 | 2016-08-31 | 东莞市项华电子科技有限公司 | Anti-flammability hud typed acrylic resin coating and the preparation method of adhesive |
| CN104861852A (en) * | 2015-06-22 | 2015-08-26 | 朱明德 | Method for preparing flame-retardant water-based polyurethane coating and adhesive for building |
| CN112266679B (en) * | 2018-06-25 | 2023-08-04 | 广东蓝柯路新材料有限公司 | Preparation method of flame-retardant waterproof water-based core-shell resin coating and paint |
-
2018
- 2018-06-25 CN CN202011300559.8A patent/CN112266679B/en active Active
- 2018-06-25 CN CN201810664863.7A patent/CN108912928B/en active Active
- 2018-12-13 WO PCT/CN2018/120888 patent/WO2020000918A1/en not_active Ceased
- 2018-12-27 CA CA3028431A patent/CA3028431A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023011799A1 (en) | 2021-08-02 | 2023-02-09 | Röhm Gmbh | Improved resin system for foaming fire protection coatings |
| CN116462808A (en) * | 2023-04-06 | 2023-07-21 | 惠州市舜丰印材科技有限公司 | A kind of fluorosilicone emulsion for aqueous varnish and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020000918A1 (en) | 2020-01-02 |
| CN112266679B (en) | 2023-08-04 |
| CN108912928B (en) | 2020-12-01 |
| CN112266679A (en) | 2021-01-26 |
| CN108912928A (en) | 2018-11-30 |
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