CN103864982B - Preparation method of fluorinated acrylate emulsion - Google Patents
Preparation method of fluorinated acrylate emulsion Download PDFInfo
- Publication number
- CN103864982B CN103864982B CN201310695104.4A CN201310695104A CN103864982B CN 103864982 B CN103864982 B CN 103864982B CN 201310695104 A CN201310695104 A CN 201310695104A CN 103864982 B CN103864982 B CN 103864982B
- Authority
- CN
- China
- Prior art keywords
- emulsion
- preparation
- acrylate
- monomer
- methacrylate
- 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.)
- Active
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- -1 acrylic ester Chemical class 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000004945 emulsification Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 239000003002 pH adjusting agent Substances 0.000 claims description 9
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- 239000012875 nonionic emulsifier Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 125000005336 allyloxy group Chemical group 0.000 claims description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 4
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 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
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims 1
- 229910052939 potassium sulfate Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- CRTKHIYQIPONDX-UHFFFAOYSA-N FC(C(C(F)(F)F)(F)F)(C(C(C(C(F)(F)F)(F)F)=C(C(F)(F)F)F)(F)F)F Chemical group FC(C(C(F)(F)F)(F)F)(C(C(C(C(F)(F)F)(F)F)=C(C(F)(F)F)F)(F)F)F CRTKHIYQIPONDX-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000486679 Antitype Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical group [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- KIBLHEASAQAHEB-UHFFFAOYSA-N cyclohexanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OC1CCCCC1 KIBLHEASAQAHEB-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
Abstract
The invention relates to a preparation method of a fluorinated acrylate emulsion. A method of semi-continuous seed emulsion polymerization is used, so that a fluorine monomer is concentrated in a copolymer shell; meanwhile, a reactive emulsifier is used, so that emulsifier molecules are combined on the surface of emulsion particles via stable covalent bonds. Specific method comprises the following steps: firstly, preparing a nuclear emulsion, dropping a shell preemulsion on the basis of the shell preemulsion, and polymerizing through a semi-continuous seed method to obtain an aqueous fluorinated acrylate shell emulsion. Due to the preparation technique, a fluorine-containing monomer is placed in the shell, so that the efficiency is maximized, advantages of a fluorine-containing polymer is shown as much as possible; the emulsion obtained through the method has excellent storage stability, calcium ion stability, freeze-thaw stability and mechanical stability.
Description
Technical field
The present invention relates to coating emulsion and production technical field, and in particular to a kind of preparation of fluorinated acrylate emulsion
Method.
Background technology
Aqueouss (methyl) series of acrylate coating has good good film-forming property, application property, film alkali resistance and colour retention
Good, pollution-free the advantages of, it is widely applied.But (methyl) emulsion acrylic resin heat-resisting quantity is poor, in building coating
Most significantly have the disadvantage that high temperature after-tacks, and causes stain resistance to decline using in, resistance to water and weather resisteant are poor, so which uses model
Enclose and be restricted.In order to obtain the coating of excellent performance, people are grafted a number of fluorochemical monomer in acrylic resin and enter
Row is modified, can keep the original advantage of acrylate copolymer, gives its excellent weatherability, resistance to water, oil resistivity, resistance to again
The features such as hot and stain resistance, so as to be with a wide range of applications, but the price of fluorinated acrylate monomer is very high,
Excessive use such monomer, will certainly improve the price of modified acrylate polymer.
Therefore, on the premise of fluoropolymer plurality of advantages is maximized, how to reduce fluorinated acrylate emulsion cost
Become focus of concern.Simultaneously because the conventional emulsion agent molecule used in emulsion polymerization is easily affected by external environment
Generation is parsed, and makes emulsion particle collide cohesion, and after emulsion film forming, remains emulsifier molecules in the polymer, easily poly-
There is migration in compound and cause the resistance to water of polymeric film to decline.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the fluorinated acrylate emulsion with nucleocapsid structure, is reducing
During the consumption of fluorine monomer, make emulsion that still there is excellent weatherability, resistance to soiling, resistance to water and resistance to acids and bases.Simultaneously using anti-
Type emulsifying agent is answered, and emulsifier molecules is made with more stable covalent with reference on emulsion particle surface, so that the emulsion tool for obtaining
There are excellent bin stability, Calcium ion stability, freeze-thaw stability and mechanical stability.
Hud typed fluorine-containing (methyl) acrylic acid ester emulsion of the present invention is by monomer, the moon/non-emulsifierses, response type emulsifying
Agent, water, initiator and pH adjusting agent, are obtained using the polymerization of semi-continuous seed method Jing after pre-emulsification.Seed emulsion is prepared first,
Then shell pre-emulsion is will be enriched in after the shell monomer mixture pre-emulsification of fluorine monomer obtaining, using the method for Deca by shell pre-emulsion Deca
Target product is obtained after reacting in seed emulsion.
The purpose of the present invention is achieved through the following technical solutions：
One technical scheme of the present invention provides a kind of preparation method of fluorinated acrylate emulsion, comprising following step
Suddenly：
1）Prepare pre-emulsion
I）The preparation of core pre-emulsion
After by anion emulsifier, nonionic emulsifier, reactive emulsifier, initiator and deionized water stirring and dissolving,
The methacrylate-based monomer and acrylic ester monomer mixed liquor with or without fluoroalkyl class monomer is added, is stirred
Mix pre-emulsification and prepare core pre-emulsion, wherein each component mass parts are：
II）The preparation of shell pre-emulsion
After anion emulsifier, nonionic emulsifier, initiator and deionized water stirring and dissolving, add containing fluoroalkyl third
Olefin(e) acid esters monomer and the mixed solution of functional monomer, stir pre-emulsification and prepare shell pre-emulsion, and wherein each component mass parts are：
2）The preparation of seed emulsion
Take step 1）The 20-50% of obtained core pre-emulsion, stirs under inert gas shielding, is warming up to 70-90 DEG C, treats temperature
After degree is stable, residual nucleus emulsion is dripped, afterwards insulation reaction, seed emulsion is obtained；
3）Prepare fluorinated acrylate emulsion
It is kept stirring for, inert gas shielding, temperature are maintained under the conditions of 70-90 DEG C, to step 2）Gained seed emulsion drop
Add step 1）Obtained shell pre-emulsion, drop finish insulation reaction, after reaction completely, are down to 10-30 DEG C, Deca pH adjusting agent to pH
It is worth for 7.0-8.5, mixed liquor filters to obtain fluorinated acrylate emulsion.
According to the preparation method that above-mentioned technical proposal is provided, in some embodiments, the acrylic ester monomer choosing
From acrylic acid methyl ester., ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, lauryl acid esters, Process Conditions of Cetane Acrylate or
Octadecyl acrylate.
According to the preparation method that above-mentioned technical proposal is provided, in some embodiments, the methyl acrylic ester list
Body is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid cyclohexanol, metering system
Sour lauryl or octadecyl methacrylate.
It is according to the preparation method that above-mentioned technical proposal is provided, in some embodiments, described containing fluoroalkyl
Class monomer is compound shown in Formulas I
Wherein R1Selected from H or methyl, R2Selected from C2-C20Containing fluoroalkyl.
In some embodiments, the fluorine-containing alkylacrylate monomer selected from trifluoroethyl methacrylate, third
Olefin(e) acid hexafluoro butyl ester, perluorooctyl acrylate, dodecafluoroheptyl methacrylate, perfluoro butyl ethyl propylene acid esters, perfluor
Butyl ethyl methacrylate, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group acrylate or perfluoro capryl
Ethylmethyl acrylate.
According to the preparation method that above-mentioned technical proposal is provided, in some embodiments, the functional monomer is selected from first
Base acrylic acid, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, methacrylonitrile, acrylic acid, 2-(Acryloyloxy)ethanol, third
Olefin(e) acid hydroxypropyl acrylate, acrylonitrile, acrylamide, N hydroxymethyl acrylamide, Ethylene glycol dimethacrylate, diacetone acrylamide acyl
Amine or adipic acid dihydrazide.
According to the preparation method that above-mentioned technical proposal is provided, in some embodiments, the reactive emulsifier is selected from
2- propenyl ether -3- hydroxy propane -1- sodium sulfonates, alkyl phenol allyl polyether sulfate, 2- acrylamide -2- methylpropane sulphurs
Acid sodium-salt, allyloxy NPE ammonium sulfate, sodium vinyl sulfonate, allyl polyether sulfate or allyloxy
Fatty alcohol oxygen ethylene ether ammonium sulfate.
According to the preparation method that above-mentioned technical proposal is provided, in some embodiments, the anion emulsifier is selected from
Sodium lauryl sulphate, dodecylbenzene sodium sulfonate, 1,2- dodecyl diether disulfonates, decyl polyoxyethylene ether succinum
Acid monoester disodium sulfonate salt, NPE ammonium sulfate, NPE monomester succinate disodium sulfonate salt
Or polyoxyethylenated alcohol sodium sulfate.
This preparation method provided according to above-mentioned technical proposal, in some embodiments, the nonionic emulsifier is
Fatty alcohol-polyoxyethylene ether, OPEO or NPE.
According to the preparation method that above-mentioned technical proposal is provided, in some embodiments, the initiator is persulfate.
In some embodiments, persulfate is selected from sodium peroxydisulfate, potassium peroxydisulfate or Ammonium persulfate..
According to above-mentioned technical proposal provide preparation method, in some embodiments, the pH adjusting agent selected from ammonia,
Alkali-metal carbonate, bicarbonate, phosphate or hydrophosphate.
In other embodiments, pH adjusting agent of the present invention is selected from ammonia, sodium carbonate, sodium bicarbonate, phosphoric acid hydrogen
Disodium, potassium carbonate, potassium hydrogen phosphate or dipotassium hydrogen phosphate or its combination.
Another technical scheme of the present invention provides the fluorine-containing propene prepared using the method that above-mentioned technical proposal is provided
Acid esters emulsion is for the application in building coating is prepared.
Unless explicitly stated otherwise in contrast, otherwise, all scopes that the present invention is quoted include end value.For example, it is coated on
After base material, " being warming up to 70-90 DEG C " represents that temperature range T for heating up is 70 DEG C≤T≤90 DEG C.
The end value that the present invention is quoted potentially includes 0, when a certain end value is 0, represents that its content for representing is optional, example
Such as, in ingredient lists, " fluorine-containing alkylacrylate monomer 0-6.0 parts " is represented in some embodiments it is possible to without containing
Fluoroalkyl class monomer.
Terminology used in the present invention "or" represents alternative, if appropriate, can combine them, that is,
Say, term "or" includes independent alternative and combinations thereof listed by each.For example, " pH adjusting agent selected from ammonia,
Alkali-metal carbonate, bicarbonate, phosphate or hydrophosphate " represents that pH adjusting agent can be ammonia, alkali-metal carbonic acid
Salt, bicarbonate, phosphate, one kind of hydrophosphate, or its more than one combination.
The beneficial effects of the present invention is：The present invention is using (methyl) acrylic ester monomer and contains fluoroalkyl
Method of the class monomer by semi-continuous seed emulsion polymerization, prepares the fluorinated acrylate emulsion with nucleocapsid structure, acquisition
Emulsion is on the basis of (methyl) acrylic acid ester emulsion excellent properties are maintained, and the characteristic with fluorine, and due to fluorine-containing list
Body is enriched on the surface of copolymer, when the consumption of fluorine monomer is reduced, still fully demonstrates the excellent chemically-resistants of C-F
Property, uvioresistant and antioxygenic property.Whole course of reaction adopts Deca mode, and the fluorinated acrylate emulsion solid content of acquisition is big
In 40%, while latex particle size is less in emulsion, particle diameter distribution is narrower, with excellent bin stability, dilution stability,
Freeze-thaw stability and mechanical stability, and preparation process is simple, easy control of reaction conditions can be widely applied to building, industry
The fields such as coating, textile finishing and leather finish.
Specific embodiment
Described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to the following side of being preferable to carry out
Formula.It should be pointed out that for a person skilled in the art on the basis of this innovation and creation design, some deformations for making and
Improve, belong to protection scope of the present invention.
Embodiment 1
By deionized water 125.0g, sodium lauryl sulphate 1.0g, OPEO 2.0g, 2- propenyl ether-
After 3- hydroxy propane -1- sodium sulfonate 1.5g, potassium peroxydisulfate 0.5g stirring and dissolving, be slowly added to methyl methacrylate 58.0g with
The mixed liquor of butyl acrylate 58.0g, high speed machine stirring pre-emulsification 45 minutes, obtains 246.0g pre-emulsion I；
By deionized water 53.0g, sodium lauryl sulphate 0.4g, OPEO 0.8g, potassium peroxydisulfate 0.25g
After stirring and dissolving, the mixed liquor of trifluoroethyl methacrylate 40.0g and hydroxyethyl methylacrylate 7.5g is slowly added to, at a high speed
Mechanical agitation pre-emulsification 30 minutes, obtains 93.7g pre-emulsion II.
In reaction unit nitrogen atmosphere is kept, 80.0g pre-emulsion I are taken, stirred under 200 revs/min, open condensation
Water, is heated to 80 DEG C.After temperature stabilization, remaining pre-emulsion I is slowly added dropwise, rear insulation reaction is dripped 1.5 hours,
Obtain seed emulsion.
The Deca pre-emulsion II on the basis of the seed emulsion of above-mentioned acquisition, reaction mixing speed are 175 revs/min, temperature
Degree control is incubated 2.0 hours after dripping, stopped reaction at 80 DEG C.Emulsion is cooled to into 35 DEG C, Deca 2.0g ammonia adjusts pH value
For 7.8, nitrogen, condensed water are closed, 335.85g emulsions are filtered to obtain.
Embodiment 2
By deionized water 340.0g, dodecylbenzene sodium sulfonate 4.8g, fatty alcohol-polyoxyethylene ether 4.8g, 2- acryloyl
After amine -2- methyl propane sulfonic acid sodium salt 6.4g, potassium peroxydisulfate 2.25g stirring and dissolving, ethyl methacrylate is slowly added to
The mixed liquor of 170.0g, ethyl acrylate 138.0g and hexafluorobutyl acrylate 22.0g, high speed machine stirring pre-emulsification 1 hour,
Obtain 666.25g pre-emulsion I.
By deionized water 70g, dodecylbenzene sodium sulfonate 0.68g, fatty alcohol-polyoxyethylene ether 1.36g, 1.0g persulfuric acid
After potassium stirring and dissolving, the mixed liquor of hexafluorobutyl acrylate 58.0g and methacrylonitrile 19.2g is slowly added to, high speed machine is stirred
Mix pre-emulsification 45 minutes, obtain 149.24g pre-emulsion II.
In reaction unit nitrogen atmosphere is kept, 225.0g pre-emulsion I are taken, stirred under 250 revs/min, opened cold
Solidifying water, is heated to 75 DEG C.After temperature stabilization, remaining pre-emulsion I is slowly added dropwise, insulation reaction is dripped 2.0 hours,
Obtain seed emulsion.
The Deca pre-emulsion II on the basis of the seed emulsion of above-mentioned acquisition, reaction mixing speed are 225 revs/min, temperature
Degree control is incubated 3.0 hours after dripping, stopped reaction at 75 DEG C.Emulsion is cooled to into 40 DEG C, 5% sodium bicarbonate solution of Deca
10.0g, adjusts pH value to be 8.2, closes nitrogen, condensed water, filter to obtain 818.64g emulsions.
Embodiment 3
By deionized water 165.0g, 1,2- dodecyl diether disulfonate 1.6g, NPE 2.0g,
After alkyl phenol allyl polyether sulfate 2.2g, sodium peroxydisulfate 1.35g stirring and dissolving, butyl methacrylate is slowly added to
The mixed liquor of 70.0g, Process Conditions of Cetane Acrylate 90.0g and perluorooctyl acrylate 10.0g, high speed machine 30 points of pre-emulsification of stirring
Clock, obtains 332.15g pre-emulsion I.
By deionized water 40.0g, 1,2- dodecyl diether disulfonate 0.7g, NPE 0.7g,
After 0.40g sodium peroxydisulfate stirring and dissolving, be slowly added to perluorooctyl acrylate 28.0g, N hydroxymethyl acrylamide 8.5g with
The mixed liquor of methacrylic acid 3.0g, high speed machine stirring pre-emulsification 45 minutes, obtains 80.9g pre-emulsion II.
In reaction unit nitrogen atmosphere is kept, 100.0g pre-emulsion I are taken, stirred under 225 revs/min, opened cold
Solidifying water, is heated to 78 DEG C.After temperature stabilization, remaining pre-emulsion I is slowly added dropwise, insulation reaction is dripped 1.0 hours,
Obtain seed emulsion.
The Deca pre-emulsion II on the basis of the seed emulsion of above-mentioned acquisition, reaction mixing speed are 200 revs/min, temperature
Degree control is incubated 2.0 hours after dripping, stopped reaction at 78 DEG C.Emulsion is cooled to into 20 DEG C, 5% potassium hydrogen phosphate of Deca
8.5g, adjusts pH value to be 8.5, closes nitrogen, condensed water, filter to obtain 415.50g emulsions.
Embodiment 4
By deionized water 460.0g, decyl polyoxyethylene ether monomester succinate disodium sulfonate salt 3.75g, fatty alcohol polyoxy second
It is after alkene ether 3.50g, allyloxy NPE ammonium sulfate 6.25g, Ammonium persulfate. 3.75g stirring and dissolving, slow to add
Enter the mixed liquor of lauryl methacrylate 220.0g and lauryl acid esters 200.0g, high speed machine stirring pre-emulsification 1
Hour, obtain 897.25g pre-emulsion I.
By deionized water 110g, decyl polyoxyethylene ether monomester succinate disodium sulfonate salt 1.15g, aliphatic alcohol polyethenoxy
After ether 1.05g, Ammonium persulfate. 1.5g stirring and dissolving, perfluoro butyl ethyl propylene acid esters 96.0g, N- methylol propylene is slowly added to
The mixed liquor of amide 9.5g and hydroxyethyl methylacrylate 18.5g, high speed machine stirring pre-emulsification 1 hour, obtains 236.2g pre-
Emulsion II.
In reaction unit nitrogen atmosphere is kept, 300.0g pre-emulsion I are taken, stirred under 300 revs/min, opened cold
Solidifying water, is heated to 82 DEG C.After temperature stabilization, remaining pre-emulsion I is slowly added dropwise, insulation reaction is dripped 2.5 hours,
Obtain seed emulsion.
The Deca pre-emulsion II on the basis of the seed emulsion of above-mentioned acquisition, reaction mixing speed are 250 revs/min, temperature
Degree control is incubated 3.0 hours after dripping, stopped reaction at 82 DEG C.Emulsion is cooled to into 25 DEG C, 5% potassium carbonate 12.5g of Deca,
Adjust pH value to be 8.0, close nitrogen, condensed water, filter to obtain 1138.84g emulsions.
Embodiment 5
By deionized water 600.0g, NPE ammonium sulfate 5.0g, OPEO 8.0g, allyl
After base polyethers sulfate 8.0g, Ammonium persulfate. 1.8g stirring and dissolving, octadecyl methacrylate 225.0g and propylene are slowly added to
The mixed liquor of the different monooctyl ester 275.0g of acid, high speed machine stirring pre-emulsification 30 minutes, obtains 1122.8g pre-emulsion I；
By deionized water 175.0g, NPE ammonium sulfate 2.6g, OPEO 4.2g, over cure
After sour ammonium 0.9g stirring and dissolving, perfluoro hexyl ethylmethyl acrylate 185.0g and Hydroxypropyl methacrylate are slowly added to
The mixed liquor of 40.5g, high speed machine stirring pre-emulsification 30 minutes, obtains 408.2g pre-emulsion II.
In reaction unit nitrogen atmosphere is kept, 380.0g pre-emulsion I are taken, stirred under 300 revs/min, opened cold
Solidifying water, is heated to 80 DEG C.After temperature stabilization, remaining pre-emulsion I is slowly added dropwise, rear insulation reaction 2.0 is dripped little
When, obtain seed emulsion.
The Deca pre-emulsion II on the basis of the seed emulsion of above-mentioned acquisition, reaction mixing speed are 250 revs/min, temperature
Degree control is incubated 5.0 hours after dripping, stopped reaction at 80 DEG C.Emulsion is cooled to into 30 DEG C, 5% dipotassium hydrogen phosphate of Deca
18.5g, adjusts pH value to be 8.4, closes nitrogen, condensed water, filter to obtain 1518.7g emulsions.
Embodiment 6
Emulsion paint will be configured to by embodiment of the present invention 1-5 emulsion to be detected, detection project is shown in Table 1, testing standard is
HG/T4104-2009。
Table 1 prepares the specific performance of emulsion
Claims (11)
1. a kind of preparation method of fluorinated acrylate emulsion, is characterized in that comprising the steps of：
1) prepare pre-emulsion
I) the preparation of core pre-emulsion
After anion emulsifier, nonionic emulsifier, reactive emulsifier, initiator and deionized water stirring and dissolving, add
With or without the methacrylate-based monomer and acrylic ester monomer mixed liquor of fluoroalkyl class monomer, stirring is pre-
Emulsifying prepares core pre-emulsion, and wherein each component mass parts are：
II) the preparation of shell pre-emulsion
After anion emulsifier, nonionic emulsifier, initiator and deionized water stirring and dissolving, add containing perfluoroalkyl acrylic
Esters monomer and the mixed solution of functional monomer, stir pre-emulsification and prepare shell pre-emulsion, and wherein each component mass parts are：
2) preparation of seed emulsion
Take step 1) obtained by the 20-50% of core pre-emulsion stir under inert gas shielding, be warming up to 70-90 DEG C, treat temperature
After stable, residual nucleus emulsion is dripped, afterwards insulation reaction, seed emulsion is obtained；
3) prepare fluorinated acrylate emulsion
Be kept stirring for, inert gas shielding, temperature are maintained under the conditions of 70-90 DEG C, to step 2) obtained by seed emulsion drip
Step 1) obtained by shell pre-emulsion, drop finishes insulation reaction, after reaction completely, is down to 10-30 DEG C, and Deca pH adjusting agent to pH value is
7.0-8.5, mixed liquor filters to obtain fluorinated acrylate emulsion；
The anion emulsifier is selected from sodium lauryl sulphate, dodecylbenzene sodium sulfonate, two sulphur of 1,2- dodecyls diether
Acid disodium, decyl polyoxyethylene ether monomester succinate disodium sulfonate salt, NPE ammonium sulfate, polyoxyethylene nonyl phenyl second
Alkene ether monomester succinate disodium sulfonate salt or polyoxyethylenated alcohol sodium sulfate；
The nonionic emulsifier is selected from fatty alcohol-polyoxyethylene ether, OPEO or NPE.
2. preparation method according to claim 1, it is characterised in that the acrylic ester monomer is selected from acrylic acid first
Ester, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, Process Conditions of Cetane Acrylate or octadecyl acrylate.
3. preparation method according to claim 1, it is characterised in that the methacrylate-based monomer is selected from methyl-prop
E pioic acid methyl ester, ethyl methacrylate, butyl methacrylate, lauryl methacrylate or octadecyl methacrylate.
4. preparation method according to claim 1, it is characterised in that the fluorine-containing alkylacrylate monomer is Formulas I
Compound
Wherein R1Selected from H or methyl, R2Selected from C2-C20Containing fluoroalkyl.
5. preparation method according to claim 4, it is characterised in that the fluorine-containing alkylacrylate monomer is selected from first
Base acrylic acid trifluoro ethyl ester, hexafluorobutyl acrylate, perluorooctyl acrylate, dodecafluoroheptyl methacrylate, perfluor fourth
Base ethyl propylene acid esters, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group
Acrylate or perfluorooctylethyl group methacrylate.
6. preparation method according to claim 1, it is characterised in that the functional monomer is selected from methacrylic acid, first
Base 2-(Acryloyloxy)ethanol, Hydroxypropyl methacrylate, methacrylonitrile, acrylic acid, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate,
Acrylonitrile, acrylamide, N hydroxymethyl acrylamide, Ethylene glycol dimethacrylate or N-[2-(2-methyl-4-oxopentyl) or its group
Close.
7. preparation method according to claim 1, it is characterised in that the reactive emulsifier selected from 2- propenyl ethers-
3- hydroxy propane -1- sodium sulfonates, alkyl phenol allyl polyether sulfate, 2- acrylamide -2- methyl propane sulfonic acid sodium salts, allyl
Epoxide NPE ammonium sulfate, sodium vinyl sulfonate, allyl polyether sulfate or allyloxy fatty alcohol oxygen second
Alkene ether ammonium sulfate.
8. preparation method according to claim 1, it is characterised in that the initiator is persulfate.
9. preparation method according to claim 8, it is characterised in that the persulfate is selected from sodium peroxydisulfate, persulfuric acid
Potassium or Ammonium persulfate..
10. preparation method according to claim 1, it is characterised in that the pH adjusting agent is selected from ammonia, alkali-metal carbon
Hydrochlorate, bicarbonate, phosphate or hydrophosphate.
11. preparation methoies according to claim 1, it is characterised in that the pH adjusting agent is selected from ammonia, sodium carbonate, carbon
Sour hydrogen sodium, disodium hydrogen phosphate, potassium carbonate, potassium hydrogen phosphate or dipotassium hydrogen phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310695104.4A CN103864982B (en) | 2012-12-15 | 2013-12-14 | Preparation method of fluorinated acrylate emulsion |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105425738 | 2012-12-15 | ||
| CN201210542573.8 | 2012-12-15 | ||
| CN201210542573 | 2012-12-15 | ||
| CN201310695104.4A CN103864982B (en) | 2012-12-15 | 2013-12-14 | Preparation method of fluorinated acrylate emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103864982A CN103864982A (en) | 2014-06-18 |
| CN103864982B true CN103864982B (en) | 2017-05-03 |
Family
ID=50904035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310695104.4A Active CN103864982B (en) | 2012-12-15 | 2013-12-14 | Preparation method of fluorinated acrylate emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103864982B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626912A (en) * | 2013-05-17 | 2014-03-12 | 佛山市三水灏诚合成树脂有限公司 | Aqueous acrylate emulsion adhesive for colorful metallic tiles and preparation method thereof |
| CN104403471A (en) * | 2014-03-04 | 2015-03-11 | 上海大学 | Polyacrylic acid emulsion hydrophobic coating material with low fluorine content and preparation method thereof |
| CN105440201A (en) * | 2014-08-13 | 2016-03-30 | 南京理工大学 | Core-shell type short-chain fluorine-containing acrylate emulsion and preparation method thereof |
| CN104387516B (en) * | 2014-10-22 | 2016-10-26 | 陕西延长石油（集团）有限责任公司 | A kind of preparation method of the fluorine-contaninig polyacrylate core shell emulsion of Oil repellent Gradient distribution |
| CN104710557A (en) * | 2014-12-31 | 2015-06-17 | 佛山市顺德区巴德富实业有限公司 | Fluorine-containing acrylate emulsion and preparation method thereof |
| CN105175616B (en) * | 2015-09-22 | 2017-12-05 | 齐齐哈尔大学 | A kind of Organic fluoride acrylate copolymer emulsion finishing agent, its preparation method and application |
| CN106674416B (en) * | 2015-11-05 | 2019-08-06 | 中昊晨光化工研究院有限公司 | A kind of Fluorine-Containing Copolymer Emulsion and its synthetic method, application |
| CN105401429B (en) * | 2015-11-24 | 2017-09-29 | 苏州市职业大学 | A kind of low temperature three-proof finishing agent, preparation method and its application on fabric |
| CN105622852A (en) * | 2015-12-31 | 2016-06-01 | 西北工业大学 | Preparing method for synthesizing shape-controlled anisotropic particles through emulsion polymerization based on asymmetry monomer-swelling non-crosslinking seed particles |
| CN105504177A (en) * | 2015-12-31 | 2016-04-20 | 西北工业大学 | Method for preparing shape-controlled particles by high-pressure swelling seed emulsion polymerization synthesis |
| CN105669914B (en) * | 2016-03-23 | 2018-12-28 | 广州天赐高新材料股份有限公司 | A kind of freeze-thaw stable type acrylate polymer emulsion and preparation method thereof |
| CN105801746B (en) * | 2016-03-28 | 2017-12-01 | 齐齐哈尔大学 | A kind of Organic fluoride modification acrylate flax finishing agent and its preparation method and application |
| CN105837739A (en) * | 2016-05-05 | 2016-08-10 | 常熟林润氟硅材料有限公司 | Method for preparing water-based fluorine-containing hydroxyl acrylic emulsion |
| CN105859949B (en) * | 2016-06-27 | 2018-03-06 | 南京信息工程大学 | A kind of copolymerization of perfluoro alkyl ethylene prepare without soap fluorine carbon emulsion and preparation method thereof |
| CN106189632A (en) * | 2016-08-05 | 2016-12-07 | 宁波江东仑斯福环保科技有限公司 | A kind of preparation method of fire-retardant water-retaining type thermal insulation coatings |
| CN106589216A (en) * | 2016-12-03 | 2017-04-26 | 范进 | Fluorine-containing polyacrylic acid latex and preparation method thereof |
| CN110540614B (en) * | 2018-05-28 | 2021-09-03 | 中国科学院上海有机化学研究所 | Water-based fluorine-containing acrylate copolymer, hybrid membrane, preparation method and application thereof |
| CN109183412B (en) * | 2018-09-13 | 2021-04-20 | 江苏大同宝富纺织科技有限公司 | Polyester fabric water repellent finishing method based on graft copolymerization |
| CN110713771A (en) * | 2019-10-17 | 2020-01-21 | 刘杰 | Waterproof emulsion and preparation method thereof |
| CN110760228A (en) * | 2019-11-16 | 2020-02-07 | 漳州鑫展旺化工有限公司 | Water-based environment-friendly corrugated paint and preparation method thereof |
| CN110951001A (en) * | 2019-12-26 | 2020-04-03 | 江苏智泰科技发展有限公司 | Preparation method of water-based fluorine-containing acrylic emulsion |
| CN111363443A (en) * | 2020-04-03 | 2020-07-03 | 杨海青 | Anticorrosive paint for building materials and preparation method thereof |
| CN115000627A (en) * | 2022-06-17 | 2022-09-02 | 岳阳耀宁新能源科技有限公司 | Lithium ion battery diaphragm coating and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029110A (en) * | 2006-11-08 | 2007-09-05 | 吉林大学 | Fluoride core-shell acrylic-resin emulsion, its production and use |
| CN101104659A (en) * | 2007-05-24 | 2008-01-16 | 吉林大学 | Method for preparing non-soap fluorine-containing polyacrylate core-shell emulsion with crosslinking network structure |
| CN101348595A (en) * | 2008-07-28 | 2009-01-21 | 北京大学 | Fluorine-silicon modified self-crosslinking acrylic ester emulsion and preparation thereof |
| CN101633715A (en) * | 2009-05-07 | 2010-01-27 | 大连理工大学 | Fluorine-containing resin emulsion and preparation method thereof |
| CN102174143A (en) * | 2011-01-29 | 2011-09-07 | 锦州惠发天合化学有限公司 | Method for preparing fluorine-containing acrylate emulsion |
-
2013
- 2013-12-14 CN CN201310695104.4A patent/CN103864982B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029110A (en) * | 2006-11-08 | 2007-09-05 | 吉林大学 | Fluoride core-shell acrylic-resin emulsion, its production and use |
| CN101104659A (en) * | 2007-05-24 | 2008-01-16 | 吉林大学 | Method for preparing non-soap fluorine-containing polyacrylate core-shell emulsion with crosslinking network structure |
| CN101348595A (en) * | 2008-07-28 | 2009-01-21 | 北京大学 | Fluorine-silicon modified self-crosslinking acrylic ester emulsion and preparation thereof |
| CN101633715A (en) * | 2009-05-07 | 2010-01-27 | 大连理工大学 | Fluorine-containing resin emulsion and preparation method thereof |
| CN102174143A (en) * | 2011-01-29 | 2011-09-07 | 锦州惠发天合化学有限公司 | Method for preparing fluorine-containing acrylate emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103864982A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103864982B (en) | Preparation method of fluorinated acrylate emulsion | |
| CN106188407A (en) | The synthetic method of organic-silicon-modified hud typed room temperature dual self-crosslinking acrylic emulsion | |
| CN104277172B (en) | Water-based waterproof acrylate emulsion and preparation method thereof | |
| CN106749878B (en) | A kind of preparation of quaternary ammonium salt cationic type aqueous fluorine-containing polyacrylate and lotion and the lotion | |
| CN102060956B (en) | Method for preparing water-oil repellent fluorine-containing textile finishing agent | |
| CN102433750B (en) | Environmental-friendly stiffening agent and preparation method thereof | |
| CN106565893B (en) | A kind of bottom surface unification metallic paint waterborne styrene-acrylic emulsion and preparation method thereof | |
| CN103435745B (en) | Fluorine-containing hud typed water-refusing oil-refusing finishing agent emulsion of a kind of crosslinked at low temperature and preparation method thereof | |
| CN104311718B (en) | High Oil repellent aqueous fluorine polymer emulsion and preparation method thereof | |
| CN102850479B (en) | Preparation method of cationic styrene-acrylic microemulsion | |
| CN105859949A (en) | Soap-free fluorocarbon emulsion prepared from perfluoroalkyl ethylenes through copolymerization and preparation method of soap-free fluorocarbon emulsion | |
| CN103087255B (en) | Crosslinking fluorine modified acrylic ester nanometer polymer emulsion and preparation method thereof | |
| CN102199239A (en) | Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure | |
| CN108795208A (en) | The preparation method of extinguishing waterborn hud typed acrylic resin coating and paint | |
| CN102304316A (en) | Polyacrylate/nanometer ZnO composite finishing agent and preparation method thereof | |
| CN104031514B (en) | The preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance | |
| CN109705256A (en) | A kind of highlight water-based finishing varnish acrylic acid ester emulsion and preparation method with lotus leaf effect | |
| CN103130950B (en) | Preparation method of fluorine-containing acrylate terpolymer emulsion | |
| CN101475507B (en) | Fluorinated acrylate, preparation method and preparation of copolymer thereof | |
| CN105440201A (en) | Core-shell type short-chain fluorine-containing acrylate emulsion and preparation method thereof | |
| CN104403049A (en) | Method for preparing phase-change microcapsule through suspension polymerization | |
| CN105418826A (en) | Preparation of self-emulsifying perfluoropolyether monomer and application of self-emulsifying perfluoropolyether monomer in synthesis of fluorine-containing miniemulsion | |
| CN105088787A (en) | Water-repellent and oil-repellent fluorine-containing acrylate fabric finishing agent and preparation method thereof | |
| CN104403471A (en) | Polyacrylic acid emulsion hydrophobic coating material with low fluorine content and preparation method thereof | |
| CN106065044A (en) | A kind of preparation method of woodcare paint styrene-acrylic emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Applicant after: DONGGUAN HEC TECH R&D Co.,Ltd. Address before: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Applicant before: DONGGUAN CHANG'AN DONGYANGGUANG ALUMINUM R&D Co.,Ltd. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171227 Address after: 512000 Ruyuan County Development Zone, Shaoguan, Guangdong Patentee after: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Address before: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Patentee before: DONGGUAN HEC TECH R&D Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180528 Address after: 101300 room 711, 2 building, 1 Jin Hang Zhong Road, Shunyi District, Beijing (Tianzhu comprehensive bonded zone -031) Patentee after: Beijing culture science and technology finance leasing Limited by Share Ltd. Address before: 512000 Ruyuan County Development Zone, Shaoguan, Guangdong Patentee before: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210707 Address after: 512600 Development Zone, Ruyuan County, Shaoguan City, Guangdong Province Patentee after: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Address before: 101300 room 711, 2 building, 1 Jin Hang Zhong Road, Shunyi District, Beijing (Tianzhu comprehensive bonded zone -031) Patentee before: Beijing culture science and technology finance leasing Limited by Share Ltd. |
|
| TR01 | Transfer of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of fluoroacrylate lotion Effective date of registration: 20230523 Granted publication date: 20170503 Pledgee: Jiangxi Bank Co.,Ltd. Guangzhou Branch Pledgor: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Registration number: Y2023980041541 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20170503 Pledgee: Jiangxi Bank Co.,Ltd. Guangzhou Branch Pledgor: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Registration number: Y2023980041541 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of fluoroacrylate lotion Granted publication date: 20170503 Pledgee: Jiangxi Bank Co.,Ltd. Guangzhou Branch Pledgor: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Registration number: Y2024980006169 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |