CN118005836A - Biomass cement-based waterproof emulsion and preparation method and application thereof - Google Patents
Biomass cement-based waterproof emulsion and preparation method and application thereof Download PDFInfo
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- CN118005836A CN118005836A CN202410221829.8A CN202410221829A CN118005836A CN 118005836 A CN118005836 A CN 118005836A CN 202410221829 A CN202410221829 A CN 202410221829A CN 118005836 A CN118005836 A CN 118005836A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 117
- 239000004568 cement Substances 0.000 title claims abstract description 30
- 239000002028 Biomass Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004945 emulsification Methods 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000003999 initiator Substances 0.000 claims abstract description 42
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 34
- -1 isobornyl (methyl) acrylate Chemical compound 0.000 claims abstract description 20
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000004908 Emulsion polymer Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 30
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 27
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 229920000858 Cyclodextrin Polymers 0.000 claims description 10
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 235000015424 sodium Nutrition 0.000 claims description 9
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 8
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 8
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000012874 anionic emulsifier Substances 0.000 claims description 8
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 8
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 8
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 239000012875 nonionic emulsifier Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 239000008367 deionised water Substances 0.000 description 40
- 229910021641 deionized water Inorganic materials 0.000 description 40
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 27
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 18
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 12
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 230000008030 elimination Effects 0.000 description 6
- 238000003379 elimination reaction Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- CQVPPLWYIDMWDA-UHFFFAOYSA-N OS(=O)(=O)c1ccccc1.CCCCCCCCCCCC[Na] Chemical compound OS(=O)(=O)c1ccccc1.CCCCCCCCCCCC[Na] CQVPPLWYIDMWDA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- BRPNNYXZQLLLSN-UHFFFAOYSA-N sodium;dodecane Chemical compound [Na+].CCCCCCCCCCC[CH2-] BRPNNYXZQLLLSN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a biomass cement-based waterproof emulsion, a preparation method and application thereof, wherein the emulsion is an emulsion polymer formed by polymerizing monomers through a mixture containing an emulsifying agent, water and an initiator, and the monomers comprise monomers containing vinyl unsaturated groups, long-chain alkyl esters with biological sources and isobornyl (methyl) acrylate with biological sources; the sum of the long-chain alkyl ester and the isobornyl (methyl) acrylate accounts for 15-60% of the solid weight of the emulsion polymer, and compared with the prior art, the emulsion has the advantages of high biobased content, easily obtained biological source monomers, low cost, high stability of the obtained emulsion and excellent mechanical property when being used for cement-based waterproof coatings.
Description
Technical Field
The invention relates to the field of waterproof materials, in particular to a biomass cement-based waterproof emulsion and a preparation method and application thereof.
Background
The cement-based waterproof coating is a double-component water-based building waterproof coating prepared by taking polymer emulsion such as acrylic ester and cement as main raw materials and adding other additives, wherein the polymer emulsion is dehydrated to become an elastic film layer with adhesiveness and continuity, the cement absorbs moisture in a formula to harden, and the flexible polymer film layer and a cement hardened body penetrate each other to firmly adhere to form a firm and elastic waterproof layer. The paint has the advantages of convenient construction, low comprehensive cost, short construction period, no toxicity and environmental protection, and becomes an indispensable important material in the field of building waterproof materials.
Polymer emulsions are critical for cement-based waterproof coatings. The polymer emulsion is prepared by emulsion polymerization of monomers through a mixture containing an emulsifier, water and an initiator, and the green renewable bio-based monomer becomes an ideal raw material, and the higher bio-based content ratio is more environment-friendly.
In the prior art, some bio-based emulsions are reported, for example, in U.S. Dow chemical publication US20210324114A1, which discloses a synthesis method of bio-based emulsions, which uses bio-ethanol to prepare ethyl acrylate, and combines part of bio-based lauryl acrylate and the like to obtain the final emulsion. The Guangdong Baderfu New Material Co-Ltd uses C13-C17 long chain acrylic ester as a single bio-based source in a patent document CN112300343A, adopts a reactive emulsifier and combines a reactive stable monomer to prepare a bio-based emulsion for an inner wall. The Netherlands DSM company discloses in the patent literature, CN106939060B, et al, a series of emulsion synthesis methods based on itaconate bio-based monomers. The germany Evonik company reports in patent document WO2021191348A1, et al, that a polymerization process of longer-chain acrylic/methacrylic esters of C16 and above, using a combination of sodium di (2-ethylhexyl) sulfosuccinate and sodium thiobutenedioic acid-1, 4-ditridecyl ester as emulsifier, requires the addition of a relatively large amount of additional organic solvent during the polymerization process.
Although some bio-based emulsions are obtained by the method, the problems of difficult polymerization (easy slag formation or oil slick when the content of long-chain monomers is high), high raw material cost (such as itaconate), limited sources (such as bio-based ethyl acrylate) and the like still exist, and the bio-based emulsions are not particularly used for cement-based waterproof coatings, and further research on improving the performance of the cement-based emulsions is still needed.
Disclosure of Invention
The invention aims to solve the problems and provides a biomass cement-based waterproof emulsion and a preparation method and application thereof.
The aim of the invention is achieved by the following technical scheme:
A biomass cement-based waterproof emulsion is an emulsion polymer formed by polymerizing monomers through a mixture containing an emulsifier, water and an initiator, wherein the monomers comprise monomers containing vinyl unsaturated groups, long-chain alkyl esters with biological sources and isobornyl (meth) acrylate with biological sources; the sum of the long-chain alkyl ester and the isobornyl (meth) acrylate accounts for 15-60%, preferably 20-40%, and more preferably 22-35% of the solid content of the emulsion polymer.
As a preferable technical scheme of the invention, the weight ratio of the long-chain alkyl ester to the isobornyl (meth) acrylate is 4-6:8-12, preferably 5-6:9-11.
As a preferable technical scheme of the invention, the monomer containing vinyl unsaturated group consists of hard monomer and soft monomer, and the weight ratio of the hard monomer to the soft monomer is 2-10:25-35, preferably 3-8:28-33;
Preferably, the hard monomer is a monomer with a glass transition temperature of more than or equal to 20 ℃ and comprises one or more of styrene, methacrylic acid, methyl methacrylate and vinyl acetate;
Preferably, the soft monomer is a monomer with a glass transition temperature of <20 ℃, including one or more of butyl acrylate, butyl methacrylate, isooctyl acrylate, ethyl acrylate.
According to the preferable technical scheme, the long-chain alkyl ester is a C12-C18 alkyl ester monomer, and comprises C12-C18 alkyl ester of (methyl) acrylic acid, cardanol (methyl) acrylate, allyl glycidyl ether cardanol ether, glycidyl methacrylate cardanol ether and hydroxyethyl (methyl) acrylate cardanol ether;
preferably, the long chain alkyl ester is Lauryl Methacrylate (LMA), such as Terra C13-MA、BASF LMA 1214F。
As a preferred technical scheme of the invention, the emulsifier accounts for 0.05% -10%, preferably 1% -8%, and more preferably 2% -5% of the total weight of the monomers;
The emulsifier is an anionic emulsifier and/or a nonionic emulsifier;
The anionic emulsifier comprises one or two of fatty alcohol polyoxyethylene ether sulfate (such as fatty alcohol polyoxyethylene ether sodium sulfate, CAS No. 9004-82-4), alkyl diphenyl ether sulfonate (such as dodecyl diphenyl ether sodium disulfonate, CAS No. 28519-02-0), dodecyl sodium sulfate (CAS No. 151-21-3), dodecyl sodium sulfonate (CAS No. 2386-53-0), dodecyl sodium benzenesulfonate (CAS No. 25155-30-0) and dodecyl sodium polyoxyethylene ether sulfate (CAS No. 9004-82-4);
The nonionic emulsifier comprises alkyl polyoxyethylene ether and isomeric alcohol polyoxyethylene ether.
As a preferable technical scheme of the invention, the initiator is persulfate or azo initiator, and the initiator accounts for 0.05% -5%, preferably 0.1% -3%, and more preferably 0.3% -1% of the total weight of the monomers;
As examples of persulfates, potassium persulfate, sodium persulfate, ammonium persulfate, preferably sodium persulfate; examples of azo initiators include azobisisobutyrimidine hydrochloride, azobisisopropylimidazoline hydrochloride, azobisisobutyronitrile, and azobisisoheptonitrile. In a particularly preferred embodiment, the initiator is a persulfate, for example, sodium persulfate may be preferably employed.
The water content in the emulsion is added according to the solid content, and the solid content of the biomass cement-based waterproof emulsion is 50-60%;
the monomer also comprises a functional monomer and/or a crosslinking monomer, wherein the functional monomer and/or the crosslinking monomer account for 0.1-5% of the total weight of the monomer, and preferably 0.5-3%;
The functional monomer comprises one or more of acrylic acid, methacrylic acid, itaconic acid, beta-acryloxypropionic acid, maleic anhydride, fumaric acid, (meth) acrylamide, methylolacrylamide, acrylonitrile, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
The crosslinking monomer comprises one or more of vinyl trimethoxy silane (A-171), gamma-methacryloxypropyl trimethoxy silane (A-174), a Michael silane coupling agent Coatosil MP200, trimethylolpropane triacrylate (TMPTA) and 1, 6-hexanediol diacrylate (HDDA).
The preparation method of the biomass cement-based waterproof emulsion comprises the following steps:
(1) Preparation of a pre-emulsion: mixing and stirring the emulsifier a, all monomers and water uniformly to obtain a pre-emulsion;
(2) Preparing a kettle substrate material: adding water, an emulsifying agent b and a buffer stabilizer into a reaction kettle, and uniformly stirring to obtain a kettle substrate material;
(3) Polymerization reaction: adding seed emulsion and an initiator a into the kettle substrate material under the stirring state, and then simultaneously dripping a pre-emulsion and an initiator b within 2-6 hours, wherein the temperature is controlled at 83-85 ℃;
(4) Post-treatment: after the dripping is finished, preserving the temperature at 83-85 ℃ for 30-120 minutes, and finally eliminating residual monomers and adjusting the pH value to obtain the product.
As a preferable technical scheme of the invention, the mass ratio of the emulsifier a in the step (1) to the emulsifier b in the step (2) is 30-70:1, the emulsifier a is preferably a mixture of an anionic emulsifier and a nonionic emulsifier, and the emulsifier b is an anionic emulsifier;
And/or the mass ratio of the water used in the step (1) to the monomer is 1:4-6; the mass ratio of the water consumption to the monomer in the step (2) is 1:2-3;
The mass ratio of the water to the monomer is 1:4-6; the mass ratio of the water consumption to the monomer in the step (2) is 1:2-3;
And/or, the buffer stabilizer in the step (2) comprises one or more of cyclodextrin, sodium bicarbonate, ammonium bicarbonate and sodium dihydrogen phosphate, preferably cyclodextrin, and the adding amount of the buffer stabilizer accounts for 0.1-1% of the total mass of the monomers; preferably 0.4-0.8%;
And/or, the mass ratio of the initiator a to the initiator b in the step (3) is 1:2-4;
And/or, the seed emulsion in the step (3) is seed emulsion with particle size of 70-100nm and solid content of 35-45%, and the addition amount of the seed emulsion is 1-5% of the total mass of the monomers; preferably 2-3%;
and/or, in the step (4), the residual monomer is eliminated by adding an oxidant and a reducing agent, and the pH is adjusted by adding a neutralizing agent;
The oxidant comprises tert-butyl hydroperoxide and hydrogen peroxide, and the addition amount of the oxidant is 0.05-2wt%, preferably 0.1-1wt%, relative to the total weight of the monomers, and is preferably added in the form of an aqueous solution;
The reducing agent comprises sodium metabisulfite, FF6M, L-anti-septic acid and sodium anti-septic acid, and the addition amount of the reducing agent is 0.01wt% -2wt%, preferably 0.1wt% -1wt%, relative to the total weight of the monomers, and is preferably added in the form of an aqueous solution;
The neutralizing agent comprises ammonia water, triethylamine, dimethylethanolamine and 2-amino-2-methylpropanol.
As a preferable technical scheme of the invention, the seed emulsion in the step (3) is prepared by the following method:
(1-1) uniformly mixing water, an emulsifying agent, a mixed monomer and an initiator to prepare a pre-emulsion of the seed emulsion;
(1-2) adding water and an emulsifying agent into a reaction kettle, uniformly mixing, heating to 75-85 ℃, and adding an initiator;
(1-3) adding 1-5 wt% of the pre-emulsion of the seed emulsion in the step (1-1) into a reaction kettle, after the temperature is raised to 75-85 ℃, starting to uniformly dropwise add the rest pre-emulsion of the seed emulsion, wherein the total dropwise adding time is 2-4 hours, and cooling to room temperature after the dropwise adding is completed, thus obtaining the seed emulsion;
The mixed monomer consists of the following components in parts by weight: 17-19 parts of butyl acrylate, 17-19 parts of methyl methacrylate and 0.7-0.9 part of methacrylic acid.
And/or the emulsifier in step (1-1) is used in an amount of 1-15wt%, preferably 5-10wt%, based on the total weight of the mixed monomers; the water is used in an amount of 70 to 85wt%, preferably 75 to 85wt%, based on the total weight of the mixed monomers; the initiator is used in an amount of 0.1 to 2wt%, preferably 0.5 to 1wt%, based on the total weight of the mixed monomers;
And/or the emulsifier in step (1-2) is used in an amount of 2-10wt%, preferably 6-8wt%, based on the total weight of the mixed monomers; the water is used in an amount of 50 to 70wt%, preferably 50 to 60wt%, based on the total weight of the mixed monomers; the initiator is used in an amount of 0.1 to 1.5wt%, preferably 0.6 to 1.2wt%, based on the total weight of the mixed monomers.
The cement-based waterproof coating comprises the waterproof emulsion.
Compared with the prior art, the invention has the following beneficial effects:
The acrylic ester emulsion is prepared from high-content C12-C17 alkyl (methyl) acrylate and isobornyl (methyl) acrylate, and the two raw materials have wide biological sources, are relatively easy to obtain and low in cost, and ensure that the bio-base content of the emulsion is kept at a higher level. Meanwhile, by matching long-chain alkyl ester with isobornyl (methyl) acrylate in a proper proportion, the problem that slag or oil slick is easy to occur in polymerization when the content of long-chain monomers is high can be avoided, and the two bio-based monomers have strong hydrophobic performance, so that the water absorption rate of the prepared waterproof coating is far lower than that of other waterproof coatings. In addition, a small amount of seed emulsion with specific particle size is added into the kettle substrate material during emulsion polymerization, so that the batch stability of the final particle size of the emulsion is greatly improved, and the stability of the emulsion is improved. The acrylate emulsion has excellent performance when being applied to cement-based waterproof emulsion, and experimental results show that the tensile strength and the elongation of a paint film are excellent.
Detailed Description
The invention is described in detail below in connection with specific examples, but in no way limits the invention.
The seed emulsion used below was prepared by the following method:
Preparing a pre-emulsion: uniformly mixing 25 parts of deionized water, 2 parts of sodium dodecyl sulfate and 34.8 parts of mixed monomers (17 parts of butyl acrylate, 17 parts of methyl methacrylate and 0.8 part of methacrylic acid) and an initiator (0.2 part of ammonium persulfate is dissolved in 2 parts of deionized water) to prepare a pre-emulsion;
preparing kettle base solution: adding 20 parts of deionized water and 2.4 parts of sodium dodecyl sulfate into a reaction kettle, uniformly mixing, heating to 78 ℃, and adding an initiator (0.24 part of ammonium persulfate is dissolved in 2 parts of deionized water);
polymerization reaction: adding about 4wt% of pre-emulsion into a reaction kettle, after the temperature is raised to 78 ℃, starting to drop the rest pre-emulsion at a constant speed, wherein the total drop time is 3 hours, cooling to room temperature after the drop is completed, and obtaining seed emulsion, testing the particle size of the emulsion by adopting a Markov particle size tester, wherein the particle size of the tested seed emulsion is 89nm, and the solid content is 42%.
Example 1
(1) Preparation of a pre-emulsion: to 10.7 parts of deionized water, an emulsifier (0.168 parts of sodium fatty alcohol polyoxyethylene ether sulfate, 0.42 parts of sodium dodecyl diphenyl ether disulfonate, 0.1 parts of alkyl polyoxyethylene ether, 0.1 parts of isomeric alcohol polyoxyethylene ether), 1 part of acrylamide, and stirring for 10 minutes, 3.9 parts of styrene, 10.6 parts of isobornyl acrylate (CAS No. 5888-33-5), 32.3 parts of butyl acrylate, 0.06 parts of methacrylic acid, 5.4 parts of lauryl methacrylate (CAS No. 142-90-5) were sequentially added, and stirring was carried out at 200-300rpm for 30 minutes;
(2) Preparing a kettle substrate material: adding 19 parts of deionized water into a reaction kettle, heating to 83-85 ℃, adding 0.02 part of sodium dodecyl diphenyl ether disulfonate and 0.27 part of cyclodextrin, and stirring for 30 minutes;
(3) Polymerization process: 1.4 parts of seed emulsion with the particle size of 89nm and the solid content of 42% is added into the kettle substrate material under stirring, 0.047 part of pre-dissolved sodium persulfate initiator (0.047 part of sodium persulfate is dissolved in 1.5 parts of deionized water) is added, then the pre-emulsion and 0.14 part of pre-dissolved sodium persulfate initiator solution (0.14 part of sodium persulfate is dissolved in 3 parts of deionized water) are simultaneously added dropwise, the dropwise addition process is completed for 4 hours, and the temperature is controlled between 83 and 85 ℃;
(4) And (3) heat preservation: after the dripping is finished, preserving the temperature for 90 minutes at 83-85 ℃;
(5) Residual list elimination: cooling to 78 ℃, dropwise adding 0.35 part of 70% tertiary butyl hydroperoxide (dissolved in 3.85 parts of deionized water) and 0.3 part of sodium metabisulfite (dissolved in 4 parts of deionized water) step by step, and eliminating residual monomers in the emulsion;
(6) And (3) adding: cooling to below 40 ℃, adding caustic soda to neutralize the emulsion until the pH is 7.5, and obtaining the product.
Example 2
(1) Preparation of a pre-emulsion: to 10.7 parts of deionized water, an emulsifier (0.168 parts of sodium fatty alcohol polyoxyethylene ether sulfate, 0.42 parts of sodium dodecyl diphenyl ether disulfonate, 0.1 parts of alkyl polyoxyethylene ether, 0.1 parts of isomeric alcohol polyoxyethylene ether), 1 part of acrylamide, and stirring for 10 minutes, 7.5 parts of styrene, 10.6 parts of isobornyl acrylate (CAS No. 5888-33-5), 28.7 parts of butyl acrylate, 0.06 parts of methacrylic acid, 5.4 parts of lauryl methacrylate (CAS No. 142-90-5) were sequentially added, and stirring was carried out at 200-300rpm for 30 minutes;
(2) Preparing a kettle substrate material: adding 19 parts of deionized water into a reaction kettle, heating to 83-85 ℃, adding 0.02 part of sodium dodecyl diphenyl ether disulfonate and 0.27 part of cyclodextrin, and stirring for 30 minutes;
(3) Polymerization process: 1.4 parts of seed emulsion with the particle size of 89nm and the solid content of 42% is added into the kettle substrate material under stirring, 0.047 part of pre-dissolved sodium persulfate initiator (0.047 part of sodium persulfate is dissolved in 1.5 parts of deionized water) is added, then the pre-emulsion and 0.14 part of pre-dissolved sodium persulfate initiator solution (0.14 part of sodium persulfate is dissolved in 3 parts of deionized water) are simultaneously added dropwise, the dropwise addition process is completed for 4 hours, and the temperature is controlled between 83 and 85 ℃;
(4) And (3) heat preservation: after the dripping is finished, preserving the temperature for 90 minutes at 83-85 ℃;
(5) Residual list elimination: cooling to 78 ℃, dropwise adding 0.35 part of 70% tertiary butyl hydroperoxide (dissolved in 3.85 parts of deionized water) and 0.3 part of sodium metabisulfite (dissolved in 4 parts of deionized water) step by step, and eliminating residual monomers in the emulsion;
(6) And (3) adding: cooling to below 40 ℃, adding caustic soda to neutralize the emulsion until the pH is 7.5, and obtaining the product.
Example 3
(1) Preparation of a pre-emulsion: to 10.7 parts of deionized water, an emulsifier (0.168 parts of sodium fatty alcohol polyoxyethylene ether sulfate, 0.42 parts of sodium dodecyl diphenyl ether disulfonate, 0.1 parts of alkyl polyoxyethylene ether, 0.1 parts of isomeric alcohol polyoxyethylene ether), 1 part of acrylamide, and stirring for 10 minutes, 3.9 parts of styrene, 10.6 parts of isobornyl acrylate (CAS No. 5888-33-5), 32.3 parts of butyl acrylate, 5.4 parts of lauryl methacrylate (CAS No. 142-90-5) were sequentially added, and stirring was performed at 200-300rpm for 30 minutes;
(2) Preparing a kettle substrate material: adding 19 parts of deionized water into a reaction kettle, heating to 83-85 ℃, adding 0.02 part of sodium dodecyl diphenyl ether disulfonate and 0.27 part of cyclodextrin, and stirring for 30 minutes;
(3) Polymerization process: 1.4 parts of seed emulsion with the particle size of 89nm and the solid content of 42% is added into the kettle substrate material under stirring, 0.047 part of pre-dissolved sodium persulfate initiator (0.047 part of sodium persulfate is dissolved in 1.5 parts of deionized water) is added, then the pre-emulsion and 0.14 part of pre-dissolved sodium persulfate initiator solution (0.14 part of sodium persulfate is dissolved in 3 parts of deionized water) are simultaneously added dropwise, the dropwise addition process is completed for 4 hours, and the temperature is controlled between 83 and 85 ℃;
(4) And (3) heat preservation: after the dripping is finished, preserving the temperature for 90 minutes at 83-85 ℃;
(5) Residual list elimination: cooling to 78 ℃, dropwise adding 0.35 part of 70% tertiary butyl hydroperoxide (dissolved in 3.85 parts of deionized water) and 0.3 part of sodium metabisulfite (dissolved in 4 parts of deionized water) step by step, and eliminating residual monomers in the emulsion;
(6) And (3) adding: cooling to below 40 ℃, adding caustic soda to neutralize the emulsion until the pH is 7.5, and obtaining the product.
Example 4
(1) Preparation of a pre-emulsion: to 10.7 parts of deionized water, an emulsifier (0.168 parts of sodium fatty alcohol polyoxyethylene ether sulfate, 0.42 parts of sodium dodecyl diphenyl ether disulfonate, 0.1 parts of alkyl polyoxyethylene ether, 0.1 parts of isomeric alcohol polyoxyethylene ether), 1 part of acrylamide, and stirring for 10 minutes, 7.5 parts of styrene, 10.6 parts of isobornyl acrylate (CAS No. 5888-33-5), 28.7 parts of butyl acrylate, 5.4 parts of lauryl methacrylate (CAS No. 142-90-5) were sequentially added, and stirring was carried out at 200-300rpm for 30 minutes;
(2) Preparing a kettle substrate material: adding 19 parts of deionized water into a reaction kettle, heating to 83-85 ℃, adding 0.02 part of sodium dodecyl diphenyl ether disulfonate and 0.27 part of cyclodextrin, and stirring for 30 minutes;
(3) Polymerization process: 1.4 parts of seed emulsion with the particle size of 89nm and the solid content of 42% is added into the kettle substrate material under stirring, 0.047 part of pre-dissolved sodium persulfate initiator (0.047 part of sodium persulfate is dissolved in 1.5 parts of deionized water) is added, then the pre-emulsion and 0.14 part of pre-dissolved sodium persulfate initiator solution (0.14 part of sodium persulfate is dissolved in 3 parts of deionized water) are simultaneously added dropwise, the dropwise addition process is completed for 4 hours, and the temperature is controlled between 83 and 85 ℃;
(4) And (3) heat preservation: after the dripping is finished, preserving the temperature for 90 minutes at 83-85 ℃;
(5) Residual list elimination: cooling to 78 ℃, dropwise adding 0.35 part of 70% tertiary butyl hydroperoxide (dissolved in 3.85 parts of deionized water) and 0.3 part of sodium metabisulfite (dissolved in 4 parts of deionized water) step by step, and eliminating residual monomers in the emulsion;
(6) And (3) adding: cooling to below 40 ℃, adding caustic soda to neutralize the emulsion until the pH is 7.5, and obtaining the product.
Comparative example 1
(1) Preparation of a pre-emulsion: adding an emulsifier (0.168 part of fatty alcohol polyoxyethylene ether sodium sulfate, 0.42 part of sodium dodecyl diphenyl ether disulfonate, 0.1 part of alkyl polyoxyethylene ether, 0.1 part of isomeric alcohol polyoxyethylene ether) and 1 part of acrylamide into 10.7 parts of deionized water, stirring for 10 minutes, sequentially adding 7.5 parts of styrene, 28.7 parts of butyl acrylate, 0.06 part of methacrylic acid and 16 parts of lauryl methacrylate (CAS number 142-90-5), and stirring for 30 minutes at 200-300 rpm;
(2) Preparing a kettle substrate material: adding 19 parts of deionized water into a reaction kettle, heating to 83-85 ℃, adding 0.02 part of sodium dodecyl diphenyl ether disulfonate and 0.27 part of cyclodextrin, and stirring for 30 minutes;
(3) Polymerization process: 1.4 parts of seed emulsion with the particle size of 89nm and the solid content of 42% is added into the kettle substrate material under stirring, 0.047 part of pre-dissolved sodium persulfate initiator (0.047 part of sodium persulfate is dissolved in 1.5 parts of deionized water) is added, then the pre-emulsion and 0.14 part of pre-dissolved sodium persulfate initiator solution (0.14 part of sodium persulfate is dissolved in 3 parts of deionized water) are simultaneously added dropwise, the dropwise addition process is completed for 4 hours, and the temperature is controlled between 83 and 85 ℃;
(4) And (3) heat preservation: after the dripping is finished, preserving the temperature for 90 minutes at 83-85 ℃;
(5) Residual list elimination: cooling to 78 ℃, dropwise adding 0.35 part of 70% tertiary butyl hydroperoxide (dissolved in 3.85 parts of deionized water) and 0.3 part of sodium metabisulfite (dissolved in 4 parts of deionized water) step by step, and eliminating residual monomers in the emulsion;
(6) And (3) adding: cooling to below 40 ℃, adding caustic soda to neutralize the emulsion until the pH is 7.5, and obtaining the product.
Comparative example 2
(1) Preparation of a pre-emulsion: to 10.7 parts of deionized water, an emulsifier (0.168 parts of sodium fatty alcohol polyoxyethylene ether sulfate, 0.42 parts of sodium dodecyl diphenyl ether disulfonate, 0.1 parts of alkyl polyoxyethylene ether, 0.1 parts of isomeric alcohol polyoxyethylene ether), 1 part of acrylamide, and stirring for 10 minutes, 0.25 parts of styrene, 14 parts of isobornyl acrylate (CAS No. 5888-33-5), 36.9 parts of butyl acrylate, 0.06 parts of methacrylic acid, 2 parts of lauryl methacrylate (CAS No. 142-90-5) were sequentially added, and stirring was carried out at 200-300rpm for 30 minutes;
(2) Preparing a kettle substrate material: adding 19 parts of deionized water into a reaction kettle, heating to 83-85 ℃, adding 0.02 part of sodium dodecyl diphenyl ether disulfonate and 0.1 part of cyclodextrin, and stirring for 30 minutes;
(3) Polymerization process: 1.4 parts of seed emulsion with the particle size of 89nm and the solid content of 42% is added into the kettle substrate material under stirring, 0.047 part of pre-dissolved sodium persulfate initiator (0.047 part of sodium persulfate is dissolved in 1.5 parts of deionized water) is added, then the pre-emulsion and 0.14 part of pre-dissolved sodium persulfate initiator solution (0.14 part of sodium persulfate is dissolved in 3 parts of deionized water) are simultaneously added dropwise, the dropwise addition process is completed for 4 hours, and the temperature is controlled between 83 and 85 ℃;
(4) And (3) heat preservation: after the dripping is finished, preserving the temperature for 90 minutes at 83-85 ℃;
(5) Residual list elimination: cooling to 78 ℃, dropwise adding 0.35 part of 70% tertiary butyl hydroperoxide (dissolved in 3.85 parts of deionized water) and 0.3 part of sodium metabisulfite (dissolved in 4 parts of deionized water) step by step, and eliminating residual monomers in the emulsion;
(6) And (3) adding: cooling to below 40 ℃, adding caustic soda to neutralize the emulsion until the pH is 7.5, and obtaining the product.
Comparative example 3
With reference to example 2, no seed emulsion was added in step (3), and the remainder was the same as in example 2.
[ Emulsion Performance test ]
The above acrylate emulsion was tested as follows, and the experimental results are shown in Table 1.
Emulsion solids content was measured according to GB/T20623-2006, 4.3.
Viscosity testing was performed using Brookfield LV 25 ℃,2#,60rpm.
The particle size test adopts a Markov particle size tester.
The slag rate was calculated after filtration through a 100 mesh screen.
The residues were determined according to standard GB/T20623-2006 appendix A.
The biobased content is calculated by the content of the biobased monomer in the solid content of the emulsion polymer.
TABLE 1 emulsion Performance test results
| Solid content | Viscosity/mPa.s | Particle size/nm | Slag rate | Residual monomer/ppm | Biobased content | |
| Example 1 | 55.9％ | 129.5 | 456.8 | 0.013％ | 113 | 28.8％ |
| Example 2 | 55.1％ | 156.5 | 434.5 | 0.025％ | 422 | 28.7％ |
| Example 3 | 55.2％ | 130.6 | 440 | 0.023％ | 324 | 29％ |
| Example 4 | 55.3％ | 160 | 430 | 0.015％ | 370 | 28.6％ |
| Comparative example 1 | 55.6％ | 143.7 | 450 | 0.03％ | 300 | 28.2％ |
| Comparative example 2 | 55.8％ | 153.8 | 438 | 0.040％ | 372 | 28.1％ |
| Comparative example 3 | 55.4％ | 120 | 420 | 0.15％ | 280 | 28.4％ |
As is clear from the results in Table 1, the present invention uses long-chain alkyl ester and isobornyl (meth) acrylate to compound according to a certain proportion, the amount of gel produced by polymerization is minimum, and the particle sizes of batches obtained by using seed emulsion are consistent.
The emulsion obtained above is adopted to prepare cement waterproof paint according to the formula shown in Table 2 (the weight ratio of liquid to powder is 1:1.5), the tensile strength/elongation of a paint film is tested according to GB/T23445-2009 standard (the standard required tensile strength is more than or equal to 1.8MPa, and the elongation is more than or equal to 80%), and the experimental result is shown in Table 3 in detail.
Table 2 cement waterproof paint formulation
TABLE 3 mechanical Property experiment results
| Tensile Strength | Elongation percentage | |
| Example 1 | 2.1 | 122.8 |
| Example 2 | 2.9 | 128.2 |
| Example 3 | 2.3 | 156.3 |
| Example 4 | 2.6 | 139.5 |
| Comparative example 1 | 3.6 | 80 |
| Comparative example 2 | 2.35 | 70.3 |
| Comparative example 3 | 2.6 | 110 |
As is clear from the results in Table 3, the mechanical properties of the coating obtained by polymerizing lauryl methacrylate and isobornyl acrylate in a certain ratio are more excellent than those of the coating obtained by using only isobornyl acrylate, and it is possible that the Tg is higher than that of lauryl methacrylate and the flexibility is poorer than that of isobornyl acrylate because isobornyl acrylate has a methyl and cyclic structure. Even increasing the amount of n-butyl acrylate does not pull down the strength improvement of isobornyl acrylate, and is not as flexible as lauryl methacrylate itself.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A biomass cement-based waterproof emulsion is an emulsion polymer formed by polymerizing monomers through a mixture containing an emulsifier, water and an initiator, and is characterized in that,
The monomer comprises a monomer containing vinyl unsaturated groups, and further comprises long-chain alkyl esters with biological sources and isobornyl (methyl) acrylate with biological sources;
the sum of the long-chain alkyl ester and the isobornyl (meth) acrylate accounts for 15-60%, preferably 20-40%, and more preferably 22-35% of the solid content of the emulsion polymer.
2. The biomass cement-based waterproof emulsion according to claim 1, wherein the weight ratio of the long-chain alkyl ester to the isobornyl (meth) acrylate is 4-6:8-12, preferably 5-6:9-11.
3. The biomass cement-based waterproof emulsion according to claim 1, wherein the monomer containing vinyl unsaturated group consists of a hard monomer and a soft monomer, and the weight ratio of the hard monomer to the soft monomer is 2-10:25-35, preferably 3-8:28-33;
the hard monomer is a monomer with a glass transition temperature of more than or equal to 20 ℃, and comprises one or more of styrene, methacrylic acid, methyl methacrylate and vinyl acetate;
the soft monomer is a monomer with a glass transition temperature of less than 20 ℃ and comprises one or more of butyl acrylate, butyl methacrylate, isooctyl acrylate and ethyl acrylate.
4. The biomass cement-based waterproof emulsion according to claim 1, wherein the long-chain alkyl ester is a C12-C18 alkyl ester monomer, and comprises a C12-C18 alkyl ester of (meth) acrylic acid, cardanol (meth) acrylate, allyl glycidyl ether cardanol ether, glycidyl methacrylate cardanol ether, hydroxyethyl (meth) acrylate cardanol ether.
5. A biomass cement-based waterproof emulsion according to claim 1, wherein the emulsifier comprises 0.05% -10%, preferably 1% -8%, further preferably 2% -5% of the total weight of the monomers;
The emulsifier is an anionic emulsifier and/or a nonionic emulsifier;
The anionic emulsifier comprises one or two of fatty alcohol polyoxyethylene ether sulfate, alkyl diphenyl ether sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and sodium dodecyl polyoxyethylene ether sulfate;
The nonionic emulsifier comprises alkyl polyoxyethylene ether and isomeric alcohol polyoxyethylene ether.
6. The biomass cement-based waterproof emulsion according to claim 1, wherein the initiator is persulfate or azo initiator, and the initiator accounts for 0.05% -5%, preferably 0.1% -3%, and further preferably 0.3% -1% of the total weight of the monomers;
the monomer also comprises a functional monomer and/or a crosslinking monomer, wherein the functional monomer and/or the crosslinking monomer account for 0.1-5% of the total weight of the monomer, and preferably 0.5-3%;
The functional monomer comprises one or more of acrylic acid, methacrylic acid, itaconic acid, beta-acryloxypropionic acid, maleic anhydride, fumaric acid, (meth) acrylamide, methylolacrylamide, acrylonitrile, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
The crosslinking monomer comprises one or more of vinyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane, michaelsen silane coupling agent CoatosilMP200,200, trimethylolpropane triacrylate and 1, 6-hexanediol diacrylate.
7. The method for preparing the biomass cement-based waterproof emulsion according to claim 1, comprising the following steps:
(1) Preparation of a pre-emulsion: mixing and stirring the emulsifier a, all monomers and water uniformly to obtain a pre-emulsion;
(2) Preparing a kettle substrate material: adding water, an emulsifying agent b and a buffer stabilizer into a reaction kettle, and uniformly stirring to obtain a kettle substrate material;
(3) Polymerization reaction: adding seed emulsion and an initiator a into the kettle substrate material under the stirring state, and then simultaneously dripping a pre-emulsion and an initiator b within 2-6 hours, wherein the temperature is controlled at 83-85 ℃;
(4) Post-treatment: after the dripping is finished, preserving the temperature at 83-85 ℃ for 30-120 minutes, and finally eliminating residual monomers and adjusting the pH value to obtain the product.
8. The method for preparing the biomass cement-based waterproof emulsion according to claim 7, wherein the emulsifier a is preferably a mixture of an anionic emulsifier and a nonionic emulsifier, and the emulsifier b is an anionic emulsifier;
And/or the mass ratio of the water used in the step (1) to the monomer is 1:4-6; the mass ratio of the water consumption to the monomer in the step (2) is 1:2-3;
The mass ratio of the water to the monomer is 1:4-6; the mass ratio of the water consumption to the monomer in the step (2) is 1:2-3;
And/or, the buffer stabilizer in the step (2) comprises one or more of cyclodextrin, sodium bicarbonate, ammonium bicarbonate and sodium dihydrogen phosphate, preferably cyclodextrin, and the adding amount of the buffer stabilizer accounts for 0.1-1% of the total mass of the monomers; preferably 0.4-0.8%;
And/or, the mass ratio of the initiator a to the initiator b in the step (3) is 1:2-4;
And/or, the seed emulsion in the step (3) is seed emulsion with particle size of 70-100nm and solid content of 35-45%, and the addition amount of the seed emulsion is 1-5% of the total mass of the monomers; preferably 2-3%;
and/or, in the step (4), the residual monomer is eliminated by adding an oxidant and a reducing agent, and the pH is adjusted by adding a neutralizing agent;
The oxidant comprises tert-butyl hydroperoxide and hydrogen peroxide, and the addition amount of the oxidant is 0.05-2wt%, preferably 0.1-1wt%, relative to the total weight of the monomers, and is preferably added in the form of an aqueous solution;
The reducing agent comprises sodium metabisulfite, FF6M, L-anti-septic acid and sodium anti-septic acid, and the addition amount of the reducing agent is 0.01wt% -2wt%, preferably 0.1wt% -1wt%, relative to the total weight of the monomers, and is preferably added in the form of an aqueous solution;
The neutralizing agent comprises ammonia water, triethylamine, dimethylethanolamine and 2-amino-2-methylpropanol.
9. The method for preparing a biomass cement-based waterproof emulsion according to claim 8, wherein the seed emulsion in the step (3) is prepared by the following method:
(1-1) uniformly mixing water, an emulsifying agent, a mixed monomer and an initiator to prepare a pre-emulsion of the seed emulsion;
(1-2) adding water and an emulsifying agent into a reaction kettle, uniformly mixing, heating to 75-85 ℃, and adding an initiator;
(1-3) adding 1-5 wt% of the pre-emulsion of the seed emulsion in the step (1-1) into a reaction kettle, after the temperature is raised to 75-85 ℃, starting to uniformly dropwise add the rest pre-emulsion of the seed emulsion, wherein the total dropwise adding time is 2-4 hours, and cooling to room temperature after the dropwise adding is completed, thus obtaining the seed emulsion;
The mixed monomer consists of the following components in parts by weight: 17-19 parts of butyl acrylate, 17-19 parts of methyl methacrylate and 0.7-0.9 part of methacrylic acid;
and/or the emulsifier in step (1-1) is used in an amount of 1-15wt%, preferably 5-10wt%, based on the total weight of the mixed monomers; the water is used in an amount of 70 to 85wt%, preferably 75 to 85wt%, based on the total weight of the mixed monomers; the initiator is used in an amount of 0.1 to 2wt%, preferably 0.5 to 1wt%, based on the total weight of the mixed monomers;
And/or the emulsifier in step (1-2) is used in an amount of 2-10wt%, preferably 6-8wt%, based on the total weight of the mixed monomers; the water is used in an amount of 50 to 70wt%, preferably 50 to 60wt%, based on the total weight of the mixed monomers; the initiator is used in an amount of 0.1 to 1.5wt%, preferably 0.6 to 1.2wt%, based on the total weight of the mixed monomers.
10. A cement-based waterproof coating, characterized in that the preparation raw material comprises the waterproof emulsion according to any one of claims 1 to 9.
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