CN108250347A - A kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance - Google Patents
A kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance Download PDFInfo
- Publication number
- CN108250347A CN108250347A CN201711377667.3A CN201711377667A CN108250347A CN 108250347 A CN108250347 A CN 108250347A CN 201711377667 A CN201711377667 A CN 201711377667A CN 108250347 A CN108250347 A CN 108250347A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- phosphate
- emulsion
- salt spray
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 83
- 239000010452 phosphate Substances 0.000 title claims abstract description 83
- -1 phosphate modified Acrylate Chemical group 0.000 title claims abstract description 79
- 239000000839 emulsion Substances 0.000 title claims abstract description 69
- 150000003839 salts Chemical class 0.000 title claims abstract description 41
- 239000011258 core-shell material Substances 0.000 title claims abstract description 31
- 239000007921 spray Substances 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 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 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 4
- 239000004615 ingredient Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000004816 latex Substances 0.000 claims description 9
- 229920000126 latex Polymers 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 5
- CJGJYOBXQLCLRG-UHFFFAOYSA-M sodium;2-hydroxy-3-prop-2-enoxypropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)COCC=C CJGJYOBXQLCLRG-UHFFFAOYSA-M 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 210000000481 breast Anatomy 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 13
- 239000003973 paint Substances 0.000 abstract description 13
- 150000005690 diesters Chemical group 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000003999 initiator Substances 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002585 base Substances 0.000 description 12
- 239000006210 lotion Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical group OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000646 scanning calorimetry Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance, contain chain alkyl acrylate phosphate diester functional group on shell；Its ingredient has the soft or hard monomer of acrylate, acrylic acid, chain alkyl acrylate phosphate diester, neutralizer, initiator, emulsifier and water；The chain alkyl acrylate phosphate is by hydroxy-acrylate monomer, R6‑10OH and phosphorus pentoxide are made by reacting；The present invention also provides a kind of preparation methods of the phosphate modified Acrylate Core-shell Emulsion of salt spray resistance.The phosphate modified Acrylate Core-shell Emulsion, glass transition temperature is 30~45 DEG C, grain size is 60~150nm；The phosphate modified Acrylate Core-shell Emulsion of salt spray resistance produced by the present invention, with excellent adhesive force, water resistance, resistance to acid and alkali, salt fog resistance, anti-flash rusting and corrosion resistance, it is widely used in aqueous rust-proof coatings, aqueous steel structure coating, aqueous engineering coating, aqueous concrete anti-corrosive paint etc..
Description
Technical field
The present invention relates to a kind of modified acrylic acid emulsion more particularly to a kind of phosphate modified acrylic acid cores of salt spray resistance
Shell lotion belongs to water-base resin synthesis technical field.
Background technology
In recent years, as the pay attention to day by day of mankind's environmental pollution and the withered of Global Oil resource lack, solvent type
The use scope of coating is restricted significantly, and coating such as water paint, high solid coating, the powder wood of low VOC and hypotoxicity apply
Material, the research and development of radiation curable coating and production are grown rapidly.Wherein water paint, due to being situated between using water as dispersion
Matter, pollution-free, no fire hazard, production cost is low, meets green production, has very vast potential for future development.
Corrosion of metal brings hundreds billion of dollars of economic losses to countries in the world every year, and all the time, people are using a variety of
Metal is protected in technology, prevents the generation of corrosion.Wherein, anticorrosion with coat is that anticorrosive metal is most effective, most common side
One of method.At present, as the development of modern industrial technology and people are to the raising of environmental requirement and sternly going out for environmental regulation
Platform, the Water-borne modification of anticorrosive coating have become inevitable.
Water-based acrylic resin is usually prepared by free radical polymerisation process, and it is many to manufacture the available monomer of this resinoid,
Arrcostab, hydroxy alkyl ester and vinyl monomer including acrylic acid, such as styrene.The final performance of acrylic resin can lead to
It crosses and appropriate monomeric species is selected to be controlled, resin hardness, impact resistance can be controlled by adjusting the ratio of soft or hard monomer
With flexible mutual balance.Waterborne acrylic paint has good flexibility, fabulous resistance to ag(e)ing and solvent resistance,
Since its shrinking percentage is low, therefore there is preferable adhesive force to various base materials, be widely used as building coating, aqueous industrial painting
In material.
Since general acrylic acid ester emulsion is polymerized in the presence of emulsifier, emulsifier since its molecular weight is small,
Film coated surface easily is migrated to, so as to influence the Corrosion Protections such as the adhesive force after emulsion film forming, water resistance, salt fog resistance.
Phosphate is a kind of common adhesion promoter, special suitable for the various grounds such as copper, iron, aluminium, timber, plastics
It is not that effect is obviously promoted to being attached with for the metal bases such as copper, iron, aluminium, this is because in the highly polar and base material of phosphate group
Iron ion produce strong passivation, one layer of fine and close passivating film can be formed, so as to reach antirust, anti-corrosive function.
Chinese patent CN102408513A discloses a kind of preparation method of phosphate modified acrylic acid ester emulsion, institute
It is trichloroethyl phosphate, trichlorine propyl phosphate or the positive ethyl ester of phosphoric acid with phosphate ester monomer, the phosphate modified acrylic acid of gained
The molecular weight of polymer is 2000~3000 in ester lotion, and grain size is 0.2~0.6 μm, and initiator used is ammonium persulfate, is closed
Into emulsion particle diameter it is larger, influence filming performance, and phosphate ester monomer alkyl carbon number used is less, water resistance, salt fog resistance
It is poor.
Chinese patent CN101412781A discloses a kind of preparation method of phosphate modified acrylic acid ester emulsion, used
Phosphate ester monomer is the PMA-100 (hydroxyethyl methacrylate phosphate monoester) of Rhodia or PMA-200 (hydroxyethyl methacrylate second
Ester phosphate diester), the acrylic resin of preparation is configured to aqueous double-component coating, has excellent water resistance and salt fog resistance,
But prepared acrylic resin is not nucleocapsid, is aqueous dispersion, it is necessary to two-component system, increase application cost.
Zhang Dongyang (synthesis of phosphate modified acrylic acid ester emulsion and performance study, Chinese coating, 2014,29 (10)；
38-43) report has synthesized phosphorus using methyl methacrylate, styrene, butyl acrylate, acrylic acid, phosphate function monomer
Acid esters modified acrylate emulsion, phosphate ester monomer used are the PMA-100 or PMA-200 of Rhodia, and initiator is persulfuric acid
Ammonium, emulsifier are single anionic emulsifier, and a kind of technology actually phosphate modified styrene-acrylate core/shell emulsion is ageing-resistant
Property, salt fog resistance are also less desirable.
Water-based anticorrosive paint is short there are anticorrosion time limit at present, and erosion, emulsion intercalation method, water resistance and antirust are easily dodged after application
The problems such as property.A kind of phosphate modified acrylic resin of salt fog resistance is developed, the antiseptic property for improving water paint is particularly important.
Invention content
In order to solve the technical issues of described, the present invention is introduced on acrylic resin molecular structure with alkyl acrylic
Ester phosphate diester function monomer, the chain alkyl in bound phosphate groups have the function of the heat-resistant stable that self-emulsifying improves lotion
Property, the hydrophobic performance of chain alkyl improves the water resistance of film；And bound phosphate groups can be produced with the iron in base material it is strong
Passivation can form one layer of fine and close passivating film；It is attached between fortified resin and base material due to the double action of the phosphate
Put forth effort and compactness, enter between resin and base material so as to be effectively isolated hydrone, chlorion, sodium ion etc., in hygrometric state ring
Adhesive force and anti-flash rusting performance are improved under border, so as to improve its water resistance, salt fog resistance and antirust, anti-corrosive performance.
It is an object of the invention to provide a kind of phosphate modified Acrylate Core-shell Emulsions of salt spray resistance.
The present invention is that alkyl acrylate phosphate diester function monomer is introduced into acrylic copolymer shell molecular structure
On side chain end group, ensure in resin film forming procedure, bound phosphate groups are easier to be enriched in substrate surface, and it is unique blunt to play its
Change anti-flash rusting function.
The phosphate modified Acrylate Core-shell Emulsion of the salt spray resistance of the present invention, is made of stratum nucleare and shell, contains on shell
Chain alkyl-acrylate phosphate diester functional group, molecular structural formula are as follows：
Wherein, the R in molecular structural formula is C6-10Chain alkyl；N is 1~3；R2、R3For H ,-CH3And other alkyls take
For group；R4For butyl ester base, different monooctyl ester base, laruyl alcohol ester group, bay ester group, octadecyl ester base；M is 18~26；The salt spray resistance
Phosphate modified Acrylate Core-shell Emulsion, glass transition temperature Tg is 30~45 DEG C, grain size is 60~150nm.
The phosphate modified acrylate core-shell latex of salt spray resistance of the present invention, by weight, ingredient is：Propylene
30.0~50.0 parts of the soft or hard monomer of acid esters, 1.5~4.0 parts of acrylic acid, chain alkyl-acrylate phosphate diester 2.0~5.0
Part, 1.0~3.0 parts of neutralizer, 0.5~2.0 part of initiator, 1.5~3.0 parts of emulsifier, 40.0~60.0 parts of deionized water.
Wherein, the acrylate hard monomer for methyl acrylate, methyl methacrylate, ethyl methacrylate,
The combination of the middle one or more of ethyl acrylate；The acrylate soft monomer is butyl acrylate, methacrylic acid fourth
Ester, tert-butyl acrylate, n-BMA, Isobutyl methacrylate, isooctyl methacrylate, methacrylic acid
Bay alcohol ester, lauryl acrylate, octadecyl methacrylate, octadecyl acrylate middle one or more combination；It is described
The molar ratio of acrylate soft monomer and acrylate hard monomer be 1:0.1~1.
The chain alkyl-acrylate phosphate diester, is made by following reaction equation：
Wherein, the R in molecular structural formula1For H ,-CH3And other alkyls substituent groups, R C6-10Chain alkyl；N is 1
~3.
The chain alkyl-acrylate phosphate diester, by weight, ingredient is：Hydroxy acryl acid ester list
35.0~45.0 parts of body, R6-1030~40.0 parts of OH, 0.1~0.5 part of hydroquinone, 20~30.0 parts of phosphorus pentoxide.
The hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methyl
Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, methacrylate middle one or more combination.
The R6-10OH is containing C6-10Chain alkyl single methanol.
The chain alkyl-acrylate phosphate diester, preparation process are as follows：
In a kettle, quantitative hydroxy acryl acid ester monomer and quantitative hydroquinone are added in, is stirred evenly, is heated up
To 50 DEG C, by quantitative phosphorus pentoxide and R6-10OH is added portionwise, and is added in 1.5h, and temperature then is raised to 82 DEG C, protects
Temperature reaction 3h, measures acid value, cools down after qualified, discharge, obtain the chain alkyl-acrylate phosphate diester.
The initiator uses azodiisobutyronitrile, because azodiisobutyronitrile initiator than peroxide can obtain molecule
Amount is uniform, and distribution is narrower, and lotion is made to reach nanoscale.
Combination of the emulsifier for one or more of COPS-I, CO-436, OP-10.
The neutralizer is at least one of triethylamine, ammonium hydroxide, dimethylethanolamine.
The present invention also provides a kind of preparation method of the phosphate modified Acrylate Core-shell Emulsion of salt spray resistance, preparation processes
It is as follows：
A) the soft or hard monomer of acrylic acid, 50~60% emulsifiers and deionized water, are weighed by formulation weight part ratio, at 50 DEG C
High speed dispersion 30min, prepares pre-emulsion；
B) pre-emulsion, quantitative chain alkyl-acrylate phosphate diester and part azo two for, taking 20% or so are different
Butyronitrile mixes, and stirs evenly, obtains phosphate diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 10~20% pre-emulsions, part
Azodiisobutyronitrile and remaining emulsifier are warming up to 80~84 DEG C of reactions and seed emulsion are made；
D), when blueing light occurs in reaction, the acrylic acid, remaining pre-emulsion and remaining azo of mixing is slowly added dropwise
Bis-isobutyronitrile is added dropwise in 1.5h~2.0h；Then phosphate diester mixing pre-emulsion is added dropwise, is dripped in 1.0h~1.5h
Finish, heat up 85~90 DEG C, insulation reaction 1h, be cooled to 45 DEG C hereinafter, with neutralizer adjusting pH value between 7~8, filter out
Material obtains the phosphate modified Acrylate Core-shell Emulsion of the salt spray resistance.
The phosphate modified Acrylate Core-shell Emulsion of salt spray resistance of the present invention, is prepared using solventless method, meets green
Production requirement.The phosphate modified Acrylate Core-shell Emulsion of salt spray resistance produced by the present invention has excellent adhesive force, water-fast
Property, resistance to acid and alkali, resistance to ag(e)ing, salt fog resistance, anti-flash rusting and corrosion resistance, are widely used in aqueous rust-proof coatings, aqueous steel
Structural paint, aqueous engineering coating, aqueous concrete anti-corrosive paint etc..
Specific embodiment
The present invention with the following Examples does further the preparation of the phosphate modified Acrylate Core-shell Emulsion of salt spray resistance
Description.
Embodiment 1
A kind of octyl group-hydroxy-ethyl acrylate phosphate diester A, preparation process are as follows：
In a kettle, 0.2 part of 35.0 parts of hydroxy-ethyl acrylate and hydroquinone are added in, stirs evenly, is warming up to 50 DEG C,
28.0 parts of phosphorus pentoxide with octanol is added portionwise for 36.8 parts, is added in 1.5h, temperature is then raised to 82 DEG C, heat preservation is anti-
3h is answered, acid value is measured, cools down after qualified, discharge, obtain the octyl group-hydroxy-ethyl acrylate phosphate diester A.
Embodiment 2
It is a kind of that base-hydroxyethyl methacrylate phosphate diester B, preparation process are as follows：
In a kettle, 0.2 part of 40.0 parts of hydroxyethyl methacrylate and hydroquinone are added in, stirs evenly, is warming up to
50 DEG C, phosphorus pentoxide with 33.8 parts of alcohol is added portionwise for 26.0 parts, is added in 1.5h, temperature is then raised to 82 DEG C,
Insulation reaction 3h measures acid value, cools down after qualified, discharge, obtains the base-hydroxyethyl methacrylate phosphate diester B.
Embodiment 3
A kind of octyl group-hydroxypropyl acrylate phosphate diester C, preparation process are as follows：
In a kettle, 0.2 part of 38.0 parts of hydroxypropyl acrylate and hydroquinone are added in, stirs evenly, is warming up to 50 DEG C,
30.0 parts of phosphorus pentoxide with octanol is added portionwise for 31.8 parts, is added in 1.5h, temperature is then raised to 82 DEG C, heat preservation is anti-
3h is answered, acid value is measured, cools down after qualified, discharge, obtain the octyl group-hydroxypropyl acrylate phosphate diester C.
Embodiment 4
A kind of phosphate modified Acrylate Core-shell Emulsion A of salt spray resistance1, preparation process is as follows：
A) 12.0 parts of methyl acrylate, 15.0 parts of methyl methacrylate, methyl-prop, are weighed by formulation weight part ratio
20.0 parts of 6.0 parts of olefin(e) acid butyl ester, 8.0 parts of isooctyl methacrylate, 0.3 part of OP-10 and deionized water, at 50 DEG C at a high speed
Disperse 30min, prepare pre-emulsion；
B) 0.2 part of 12 parts of pre-emulsions, A4.0 parts of phosphate diester and azodiisobutyronitrile mixing, are taken, stirs evenly, obtains phosphorus
Acid diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 7.3 parts of pre-emulsions, deionizations
0.5 part of 30.0 parts of water, 0.2 part of azodiisobutyronitrile and emulsifier COPS-I are warming up to 80~84 DEG C of reactions and seed breast are made
Liquid；
D), when blueing light occurs in reaction, two isobutyl of 2.0 parts of acrylic acid, 42.0 parts of pre-emulsion and azo is slowly added dropwise
The mixed liquor that 0.4 part of nitrile, is added dropwise in 1.5h~2.0h；Then 16.2 parts of phosphate diester mixing pre-emulsion is added dropwise,
1.0h~1.5h is added dropwise, and heats up 85~90 DEG C, insulation reaction 1h, is cooled to 45 DEG C hereinafter, with 1.4 parts of adjusting pH of triethylamine
Value is between 7~8, filtering and discharging, obtains the phosphate modified Acrylate Core-shell Emulsion A of the salt spray resistance1。
Embodiment 5
A kind of phosphate modified Acrylate Core-shell Emulsion B of salt spray resistance1, preparation process is as follows：
A) 18.0 parts of methyl acrylate, 15.0 parts of methyl methacrylate, methacrylic acid, are weighed by formulation weight part ratio
20.0 parts of 10.0 parts of butyl ester, 0.3 part of OP-10 and deionized water, high speed dispersion 30min, prepares pre-emulsion at 50 DEG C；
B) 0.2 part of 12.5 parts of pre-emulsions, 3.0 parts of phosphate diester B and azodiisobutyronitrile mixing, are taken, is stirred evenly,
Obtain phosphate diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 7.5 parts of pre-emulsions, deionizations
0.5 part of 28.0 parts of water, 0.2 part of azodiisobutyronitrile and emulsifier COPS-I are warming up to 80~84 DEG C of reactions and seed breast are made
Liquid；
D), when blueing light occurs in reaction, two isobutyl of 2.5 parts of acrylic acid, 43.3 parts of pre-emulsion and azo is slowly added dropwise
The mixed liquor that 0.4 part of nitrile, is added dropwise in 1.5h~2.0h；Then 15.7 parts of phosphate diester mixing pre-emulsion is added dropwise,
1.0h~1.5h is added dropwise, and heats up 85~90 DEG C, insulation reaction 1h, is cooled to 45 DEG C hereinafter, with 1.9 parts of adjusting pH of triethylamine
Value is between 7~8, filtering and discharging, obtains the phosphate modified Acrylate Core-shell Emulsion B of the salt spray resistance1。
Embodiment 6
A kind of phosphate modified Acrylate Core-shell Emulsion C of salt spray resistance1, preparation process is as follows：
A) 28.0 parts of methyl methacrylate, 10.0 parts of lauryl acrylate, metering system, are weighed by formulation weight part ratio
20.0 parts of 5.0 parts of acid butyl ester, 0.3 part of OP-10 and deionized water, high speed dispersion 30min, prepares pre-emulsion at 50 DEG C；
B) 0.2 part of 12.5 parts of pre-emulsions, 2.5 parts of phosphate diester C and azodiisobutyronitrile mixing, are taken, is stirred evenly,
Obtain phosphate diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 7.0 parts of pre-emulsions, deionizations
0.5 part of 29.0 parts of water, 0.2 part of azodiisobutyronitrile and emulsifier COPS-I are warming up to 80~84 DEG C of reactions and seed breast are made
Liquid；
D), when blueing light occurs in reaction, two isobutyl of 2.0 parts of acrylic acid, 43.8 parts of pre-emulsion and azo is slowly added dropwise
The mixed liquor that 0.4 part of nitrile, is added dropwise in 1.5h~2.0h；Then 15.2 parts of phosphate diester mixing pre-emulsion is added dropwise,
1.0h~1.5h is added dropwise, and heats up 85~90 DEG C, insulation reaction 1h, is cooled to 45 DEG C hereinafter, with 1.9 parts of dimethylethanolamine
Adjusting pH value is between 7~8, filtering and discharging, obtains the phosphate modified Acrylate Core-shell Emulsion C of the salt spray resistance1。
According to relevant criterion, to the embodiment of the present invention lotion and the phosphate modified acrylic emulsion D of comparative example PMA-200
It is compared, the performance of lotion is as shown in table 1.
Glass transition temperature：It is tested with differentia scanning calorimetry DSC.
Grain size and particle diameter distribution：The samples of latex of 100g or so is taken, is tested with particle diameter distribution instrument.
Water-resistance property of coating：The water resistance of film is characterized with the water absorption rate of film, water absorption rate is higher, and water resistance is poorer；It will
Coalescents are added to stirred evenly in lotion after be coated on polyfluortetraethylene plate, drying at room temperature 7 days peels film and weighs weight
For W1, then film is totally immersed in deionized water, it takes out afterwards for 24 hours, the water on surface is blotted with filter paper, weigh weight as W2, then
The water absorption rate of film=(W2- W1)/W1× 100%.
Anti- flash rusting：By lotion applicator on the tinplate handled well, drying at room temperature, range estimation dried coating film whether there is in the process
Flash rusting.
Table 1：The embodiment of the present invention and comparative example emulsion film performance comparison
As seen from Table 1, the embodiment of the present invention is better than comparative example in water resistance, heat-resisting quantity, this is because phosphate
Chain alkyl on group has the heat-resistant stable that self-emulsifying function improves lotion, and the hydrophobic performance of chain alkyl improves film
Water resistance.
By the embodiment of the present invention latex A1、B1、C1It is pressed with comparative example (the phosphate modified acrylic emulsion D of PMA-200)
It states formula and water-based anticorrosive paint A is respectively prepared2、B2、C2With comparative example D1。
Water-based anticorrosive paint formula：Lotion 30~50%, filler (talcum powder, mica powder) 10~18%, iron oxide red 10~
20%th, composite zinc phosphate 20~30%, dispersant 0.5~1.5%, coalescents 1.0~5.0%, other auxiliary agents 1.0~
4.0%th, remaining is deionized water.
According to relevant criterion, performance contrasting detection, performance technologies index such as table 2 are carried out to above-mentioned water-based anticorrosive paint
It is shown.
Table 2：Water-based anticorrosive paint technical performance index
As seen from Table 2, water-based anticorrosive paint made of lotion of the invention is in water resistance, salt fog resistance, hygrometric state attachment
Power is better than comparative example, this is that (passivation is water-fast with height for the double action based on the ester modified acrylic resin of phosphide of the invention
Property), strengthen the adhesive force and compactness between film and base material, be effectively isolated hydrone, chlorion, sodium ion etc. and enter tree
Between fat and base material, adhesive force and anti-flash rusting performance are improved under wet condition, so as to improve its water resistance, salt fog resistance and prevent
Become rusty antiseptic property.
Although the present invention has described it in detail and cited embodiments, it but for those of ordinary skill in the art, shows
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (6)
1. a kind of phosphate modified Acrylate Core-shell Emulsion of salt spray resistance, which is characterized in that the salt spray resistance it is phosphate modified
Acrylate Core-shell Emulsion is made of stratum nucleare and shell, and chain alkyl-acrylate phosphate diester functional group is contained on shell,
Its molecular structural formula is as follows：
Wherein, the R in molecular structural formula1、R2、R3For H ,-CH3Or other alkyls substituent groups；R4For butyl ester base, different monooctyl ester
Base, laruyl alcohol ester group, bay ester group, octadecyl ester base；R is C6-10Chain alkyl；N=1~3；M=18~26；
The phosphate modified acrylate core-shell latex of the salt spray resistance, by weight, ingredient is：The soft or hard list of acrylate
30.0~50.0 parts of body, 1.5~4.0 parts of acrylic acid, chain alkyl -2.0~5.0 parts of acrylate phosphate diester, neutralizer 1.0
~3.0 parts, 0.5~2.0 part of azodiisobutyronitrile, 1.5~3.0 parts of emulsifier, 40.0~60.0 parts of deionized water；
The chain alkyl-acrylate phosphate diester, is made by following reaction equation：
The phosphate modified Acrylate Core-shell Emulsion of the salt spray resistance, glass transition temperature Tg is 30~45 DEG C, grain size be 60~
150nm。
2. the phosphate modified acrylate core-shell latex of salt spray resistance according to claim 1, which is characterized in that the propylene
Acid esters hard monomer is methyl acrylate, methyl methacrylate, ethyl methacrylate, the middle one or more of ethyl acrylate
Combination；The acrylate soft monomer is butyl acrylate, butyl methacrylate, tert-butyl acrylate, methacrylic acid
N-butyl, Isobutyl methacrylate, isooctyl methacrylate, lauryl alcohol ester, lauryl acrylate, methyl
Octadecyl acrylate, octadecyl acrylate middle one or more combination；The acrylate soft monomer and acrylate are hard
The molar ratio of monomer is 1:0.1~1.
3. the phosphate modified acrylate core-shell latex of salt spray resistance according to claim 1, which is characterized in that the long-chain
Alkyl-acrylate phosphate diester, by weight, consisting of：35.0~45.0 parts of hydroxy acryl acid ester monomer, R6- 1030~40.0 parts of OH, 0.1~0.5 part of hydroquinone, 20~30.0 parts of phosphorus pentoxide；
Wherein, the hydroxy acryl acid ester monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methyl
Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, methacrylate middle one or more combination；The R6- 10OH is containing C6-10Chain alkyl single methanol；
The chain alkyl-acrylate phosphate diester, preparation process are as follows：In a kettle, quantitative hydroxyl is added in
Acrylate monomer and quantitative hydroquinone, stir evenly, and are warming up to 50 DEG C, by quantitative phosphorus pentoxide and R6-10OH points
It batch adds in, is added in 1.5h, be then warming up to 82 DEG C, insulation reaction 3h, measured acid value, cool down after qualified, discharge, obtained described
Chain alkyl-acrylate phosphate diester.
4. the phosphate modified acrylate core-shell latex of salt spray resistance according to claim 1, which is characterized in that the breast
Combination of the agent for one or more of COPS-I, CO-436, OP-10.
5. the phosphate modified acrylate core-shell latex of salt spray resistance according to claim 1, which is characterized in that in described
With the combination that agent is one or more of triethylamine, ammonium hydroxide, dimethylethanolamine.
6. a kind of preparation method of the phosphate modified acrylate core-shell latex of salt spray resistance as described in claim 1, feature
It is, preparation process is as follows：
A) the soft or hard monomer of acrylic acid, 50~60% emulsifiers and deionized water, are weighed by formulation weight part ratio, at 50 DEG C at a high speed
Disperse 30min, prepare pre-emulsion；
B) 20% or so pre-emulsion, quantitative chain alkyl-acrylate phosphate diester and part azodiisobutyronitrile, is taken
Mixing, stirs evenly, obtains phosphate diester mixing pre-emulsion；
C), with thermometer, reflux condensing tube, blender reaction kettle in, add in 10~20% pre-emulsions, part azo
Bis-isobutyronitrile and remaining emulsifier are warming up to 80~84 DEG C of reactions and seed emulsion are made；
D), when blueing light occurs in reaction, the acrylic acid, remaining pre-emulsion and remaining azo two that mixing is slowly added dropwise are different
Butyronitrile is added dropwise in 1.5h~2.0h；Then phosphate diester mixing pre-emulsion is added dropwise, is added dropwise in 1.0h~1.5h,
Be warming up to 85~90 DEG C, insulation reaction 1h, be cooled to 45 DEG C hereinafter, with neutralizer adjust pH value between 7~8, filtering and discharging,
Obtain the phosphate modified Acrylate Core-shell Emulsion of the salt spray resistance.
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| CN110452567A (en) * | 2019-08-28 | 2019-11-15 | 林芬 | A kind of selfreparing anticorrosive paint and preparation method for seawater hypersaline environment |
| CN110511318A (en) * | 2019-09-24 | 2019-11-29 | 泰兴盛嘉树脂有限公司 | A kind of method that methacrylic acid phosphoric acid ester is acrylic resin modified |
| CN110511318B (en) * | 2019-09-24 | 2021-03-30 | 泰兴盛嘉树脂有限公司 | Method for modifying acrylic resin by methacrylic acid phosphate |
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| CN114133846A (en) * | 2021-12-15 | 2022-03-04 | 合众（佛山）化工有限公司 | Allyl polyoxyethylene ether phosphate modified alkyd resin water-based paint |
| WO2023219305A1 (en) * | 2022-05-10 | 2023-11-16 | 삼성에스디아이 주식회사 | Separator for lithium secondary battery and lithium secondary battery including same |
| WO2023219306A1 (en) * | 2022-05-10 | 2023-11-16 | 삼성에스디아이 주식회사 | Separator for rechargeable lithium battery and rechargeable lithium battery comprising same |
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