CN118994465A - Hydrophobic modified emulsion thickener for waterproof paint and preparation method thereof - Google Patents
Hydrophobic modified emulsion thickener for waterproof paint and preparation method thereof Download PDFInfo
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- CN118994465A CN118994465A CN202411490947.5A CN202411490947A CN118994465A CN 118994465 A CN118994465 A CN 118994465A CN 202411490947 A CN202411490947 A CN 202411490947A CN 118994465 A CN118994465 A CN 118994465A
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- China
- Prior art keywords
- monomer
- parts
- water
- thickener
- vinyl
- Prior art date
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- Granted
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- 239000002562 thickening agent Substances 0.000 title claims abstract description 88
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 52
- 239000000839 emulsion Substances 0.000 title claims abstract description 44
- 239000003973 paint Substances 0.000 title claims description 25
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 134
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 58
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003999 initiator Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 29
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 37
- -1 alkenyl imidazole Chemical compound 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 16
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 14
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- 239000005871 repellent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- VPNZAQYBGUPBSV-UHFFFAOYSA-M sodium;2-pentadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O VPNZAQYBGUPBSV-UHFFFAOYSA-M 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229940091181 aconitic acid Drugs 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- PYODKQIVQIVELM-UHFFFAOYSA-M sodium;2,3-bis(2-methylpropyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CC(C)C)C(CC(C)C)=CC2=C1 PYODKQIVQIVELM-UHFFFAOYSA-M 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- WWVMHGUBIOZASN-UHFFFAOYSA-N 1-methyl-3-prop-2-enylimidazol-1-ium Chemical compound CN1C=C[N+](CC=C)=C1 WWVMHGUBIOZASN-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 7
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 abstract 1
- 229920000098 polyolefin Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 13
- JQGGYGKXKWTXTF-UHFFFAOYSA-N 1-ethenoxy-3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COC=C JQGGYGKXKWTXTF-UHFFFAOYSA-N 0.000 description 12
- 230000015784 hyperosmotic salinity response Effects 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- IIGSHYXWVIGLSI-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(=O)O.C(CCCCCCCCCCCCCC)[Na] Chemical compound C1(=CC=CC=C1)S(=O)(=O)O.C(CCCCCCCCCCCCCC)[Na] IIGSHYXWVIGLSI-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YRIIZJQGTIBOBU-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;phosphoric acid Chemical group OP(O)(O)=O.CC(O)COC(=O)C=C YRIIZJQGTIBOBU-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011414 polymer cement Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])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])[H] 0.000 description 3
- QQBZFCFCMKHPPC-UHFFFAOYSA-N 2-pentadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O QQBZFCFCMKHPPC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 229920000058 polyacrylate Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 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 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000037048 polymerization activity Effects 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
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
本发明属于增稠剂技术领域，具体涉及一种用于防水涂料的憎水改性型乳液增稠剂及其制备方法。由质量比为1：（2‑5）的有效原料组分和水制备而成；按重量份计，所述有效原料组分包括：亲水性乙烯基单体 100份、烯基咪唑离子液体单体 15‑40份、乙烯基疏水单体 40‑100份、多烯基丙烯酸单体 2‑8份、乳化剂 3‑10份、引发剂 0.1‑1.5份。本发明中的增稠剂具有优异的憎水性，将其用于防水涂料中，能显著提升防水涂料的性能，同时具有优异的抗盐性和耐高温性。The present invention belongs to the technical field of thickeners, and specifically relates to a hydrophobic modified emulsion thickener for waterproof coatings and a preparation method thereof. It is prepared from effective raw material components and water in a mass ratio of 1: (2-5); by weight, the effective raw material components include: 100 parts of hydrophilic vinyl monomers, 15-40 parts of vinyl imidazole ionic liquid monomers, 40-100 parts of vinyl hydrophobic monomers, 2-8 parts of polyolefin acrylic acid monomers, 3-10 parts of emulsifiers, and 0.1-1.5 parts of initiators. The thickener in the present invention has excellent hydrophobicity. When used in waterproof coatings, it can significantly improve the performance of waterproof coatings, and at the same time has excellent salt resistance and high temperature resistance.
Description
Technical Field
The invention belongs to the technical field of thickeners, and particularly relates to a hydrophobic modified emulsion thickener for waterproof paint and a preparation method thereof.
Background
The thickener for coating is an additive for increasing the viscosity of coating, which can improve the rheological property of coating and enhance the coatability and stability of coating. In the paint formulation, the thickener can prevent pigment sedimentation and improve the uniformity and hiding power of the coating film. Common thickeners for coatings include celluloses, polyacrylates, bentonites, and the like. The choice of suitable thickeners is critical to the final properties of the coating.
The thickener for the coating mainly comprises the following types: 1. cellulose thickener: such as hydroxypropyl methylcellulose (HPMC) and carboxymethyl cellulose (CMC). The advantages of the water-soluble or water-swellable polymers are that the thickening effect is good, the stability is high, the water-soluble or water-swellable polymers are environment-friendly, the viscosity can be effectively regulated, but the water resistance of the coating can be influenced due to the fact that the water resistance is improved; 2. polymeric thickeners: including polyacrylates and polyurethanes. The thickener has the advantages of good weather resistance and wide application range, but may not be satisfactory in improving the waterproof performance; 3. inorganic thickener: such as bentonite and magnesium silicate. Their advantages are low cost, good stability, but the thickening effect may not be as organic thickener and may affect the gloss and leveling of the coating; 4. natural gum thickener: such as xanthan gum and guar gum. The thickener has the advantages of good biodegradability, environmental friendliness, possibility of being influenced by microbial degradation and poor stability; 5. organosilicon thickener: their advantages are high-temp and low-temp resistance, and high shearing stability. Disadvantages are the high cost and the possible influence of the thixotropic properties of the coating. The most widely used at present are polymeric thickeners. A weak ionic polyurethane thickener with side long chain alkyl groups and a preparation method thereof are provided in the patent with the publication number CN112898530B, and the method comprises the steps of raw material preparation, prepolymerization, chain extension, end capping and the like, wherein the polymerized monomer comprises diisocyanate, polyethylene glycol, chain extender, end capping agent and the like. The weak-ion polyurethane thickener with the side long chain alkyl groups prepared by the method has higher thickening capacity and salt tolerance, has longer side chain alkyl groups, improves the emulsifying and dispersing properties of the thickener, and has limited enhanced salt tolerance due to the separate side long chain alkyl groups although the longer side chain alkyl groups can increase thickening hydrophobicity to a certain extent, and the monomer containing the longer side chain alkyl groups has poor polymerization activity in a polymerization system, so that the thickener has poor stability.
Therefore, there is a need for a hydrophobically modified emulsion thickener for water-resistant coatings having excellent hydrophobicity and salt tolerance.
Disclosure of Invention
The object of the present invention is to provide a hydrophobically modified emulsion thickener for water-repellent coatings which has excellent salt resistance and hydrophobicity.
In order to achieve the above object, the present invention provides the following technical solutions:
In a first aspect, the invention provides a hydrophobic modified emulsion thickener for waterproof paint, which comprises the following components in percentage by mass: the active raw material components of (2-5) and water; the effective raw material components comprise, by weight: 100 parts of hydrophilic vinyl monomer, 15-40 parts of alkenyl imidazole ionic liquid monomer, 40-100 parts of vinyl hydrophobic monomer, 2-8 parts of polyalkenyl acrylic acid monomer, 3-10 parts of emulsifier and 0.1-1.5 parts of initiator.
Further, the mass ratio of the effective raw material components to water is 1: (2.8-3.2).
Further, the effective raw material components comprise, by weight: 100 parts of hydrophilic vinyl monomer, 18-23 parts of alkenyl imidazole ionic liquid monomer, 65-70 parts of vinyl hydrophobic monomer, 4.2-5 parts of polyalkenyl acrylic acid monomer, 6-8 parts of emulsifier and 0.6-1 part of initiator.
Hydrophilic vinyl monomers are a class of vinyl compounds containing hydrophilic groups that are capable of introducing hydrophilic groups during polymerization, thereby imparting good water solubility or water dispersibility to the polymer. Further, the hydrophilic vinyl monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, methacrylamide, -methyl-2-acrylic acid-2-hydroxyethyl phosphate, vinylpyrrolidone, crotonic acid and aconitic acid.
Further, the hydrophilic vinyl monomer is a combination of acrylic acid and 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate.
In the invention, the addition of 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate is found to not only increase the dispersibility of the thickener in water, but also further increase the salt resistance of the thickener, probably because the phosphate group has a certain complexing ability with ions (such as Ca 2+), thereby increasing the salt resistance of the thickener. And it was found that when 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate alone is used as a hydrophilic vinyl monomer, the overall performance of the thickener is reduced, probably because 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate alone cannot form a main chain of the thickener well and cannot be copolymerized with other monomers well.
Further, in order to make 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate better able to increase the salt resistance of the thickener in the polymerization system, the weight ratio of acrylic acid to 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate is 1: (0.2-0.8), for example 1:0.2, 1:0.3, 1:0.35, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, preferably 1: (0.35-0.4).
Vinyl hydrophobic monomers are a class of compounds containing vinyl groups (-ch=ch 2) that exhibit chemical hydrophobicity, i.e., repellency to water. Such monomers may be copolymerized with other monomers in the polymerization reaction to form polymers having hydrophobic character, further, in order to better increase the hydrophobicity of the thickener, the vinyl hydrophobic monomer is selected from the group consisting of long chain alkyl acrylates in a weight ratio of 1: (0.1-0.5), for example 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, preferably 1: (0.35-0.4).
Further, the long chain alkyl acrylate is selected from C8-C20 alkyl (meth) acrylates, preferably from C12-C18 alkyl (meth) acrylates.
Examples of the C12-C18 alkyl (meth) acrylate used in the present invention include dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, and octadecyl (meth) acrylate.
Further, the phenyl-containing vinyl hydrophobic monomer is selected from styrene and/or alpha-methylstyrene, preferably styrene.
The use of a combination of a long-chain alkyl acrylate with a phenyl-containing vinyl hydrophobic monomer as the introduction of a benzene ring in the vinyl hydrophobic monomer in the present invention can increase the temperature resistance of the thickener to some extent.
The alkenyl imidazole ionic liquid monomer is an ionic liquid containing alkenyl and imidazole ring structures. Such compounds generally consist of an imidazole cation having one or more alkenyl substituents in its structure and the corresponding anion. Further, the alkenyl imidazole ionic liquid monomer is at least one selected from 1-allyl-3-methylimidazole tetrafluoroborate, 1-propenyl-2, 3-dimethylimidazole p-toluenesulfonate and 1-vinyl-3-butylimidazole hexafluorophosphate, preferably 1-vinyl-3-butylimidazole hexafluorophosphate.
According to the invention, the structural unit provided by the alkenyl imidazole ionic liquid monomer is introduced into the molecular chain of the polymer, so that not only can the salt resistance of the thickener be increased, but also the high-temperature stability of the thickener can be increased, on one hand, the thickener can better undergo polymerization reaction, on the other hand, the special imidazole structure can prevent molecules from curling under the high-salt condition, the salt resistance of the thickener is improved, meanwhile, imidazole has a certain steric hindrance effect, the thermal movement of the molecular chain at high temperature can be prevented, and the stability of the thickener is improved.
The multi-alkenyl acrylic monomer is a type of acrylic compound containing multiple double bonds, which contain two or more acrylic groups in the chemical structure. Such compounds, because of their multiple reactive double bonds, can give thickeners a network structure or a multiscale dendritic structure. Further, the polyalkenyl acrylic monomer is at least one selected from the group consisting of tetraallyl pentaerythritol ether, diallyl phthalate, N-methylenebisacrylamide, trimethylolpropane diallyl ether and polyethylene glycol dimethacrylate.
Further, the polyalkenyl acrylic monomer is a combination of tetraallyl pentaerythritol ether and trimethylolpropane diallyl ether.
Further, the weight ratio of the tetraallyl pentaerythritol ether to the trimethylolpropane diallyl ether is 1: (0.6-2), for example 1:0.6, 1:0.8, 1:1. 1:1.2, 1:1.5, 1:1.8, 1:2, preferably 1: (0.8-1.2).
In the invention, experiments show that the tetraallyl pentaerythritol ether and the trimethylolpropane diallyl ether are used together as the polyalkenyl acrylic acid monomer, so that the thickener has better hydrophobicity, and when the water-proof paint is used for the water-proof paint, the water-proof paint has better water resistance, probably because the polymerization reaction has different reactivity at polymerization sites in the polymerization process, one of the tetraallyl pentaerythritol ether and the trimethylolpropane diallyl ether contains four alkenyl groups, and the other contains two double-bond alkenyl groups and has different reactivity, and the interaction of the tetraallyl pentaerythritol ether and the trimethylolpropane diallyl ether can promote the polymerization of polymer molecules, especially promote the hydrophobic association of long-chain alkyl acrylate in vinyl hydrophobic monomers in a polymerization system, so as to enhance the tendency of the thickener to form a hydrophobic three-dimensional network structure.
Further, the emulsifier is at least one selected from the group consisting of span-80, tween, mono-diglyceride, sodium pentadecyl benzene sulfonate, sodium diisobutyl naphthalene sulfonate and sodium dodecyl benzene sulfonate, preferably a combination of mono-diglyceride and sodium pentadecyl benzene sulfonate.
Further, the weight ratio of the mono-diglyceride to the pentadecyl sodium benzenesulfonate is 1: (0.5-1), for example 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, preferably 1: (0.6-0.7).
Through researches, the integral performance of the thickener can be further ensured by using the mono-diglyceride and sodium pentadecyl benzene sulfonate together as the emulsifier, and the emulsion system formed by the mono-diglyceride and the sodium pentadecyl benzene sulfonate is beneficial to smooth and steady polymerization of specific monomers in the invention, so that the problem of low reaction conversion rate caused by unstable emulsion in the reaction process and influence on the integral performance of the thickener is avoided.
Initiators are compounds that are used to initiate or accelerate the polymerization process. In the polymerization reaction, the monomer molecules form polymer chains by the action of an initiator. Further, the initiator is persulfate initiator, preferably ammonium persulfate or potassium persulfate.
In a second aspect, the present invention provides a method for preparing the hydrophobically modified emulsion thickener for water-repellent paint according to the first aspect of the present invention, comprising the steps of:
(1) Firstly mixing the emulsifier with water accounting for 65-70% of the total water to obtain an emulsifier solution;
(2) Mixing the initiator with water accounting for 5-10% of the total amount of water for the second time to obtain an initiator solution;
(3) Thirdly mixing a hydrophilic vinyl monomer, an alkenyl imidazole ionic liquid monomer, a vinyl hydrophobic monomer and a polyalkenyl acrylic acid monomer to obtain a mixed monomer;
(4) Weighing 5-8% of the total weight of the mixed monomers, and performing fourth mixing on the mixed monomers and the emulsifier solution to obtain seed emulsion;
(5) And (3) dropwise adding an initiator solution into the seed emulsion at 82-95 ℃, starting to dropwise add the rest mixed monomer after 1/4-2/5 of the initiator solution is left, keeping the temperature for 2-3 hours after the rest mixed monomer and the initiator solution are dropwise added, cooling the reaction product to 50-65 ℃ and adding the rest water for fifth mixing, and filtering to obtain the hydrophobic modified emulsion thickener for the waterproof coating.
Further, in the step (1), the first mixing condition is stirring for 30-60min at the rotating speed of 300-500 r/min.
Further, in the step (2), the second mixing condition is stirring for 5-20min at the rotating speed of 300-500 r/min.
Further, in the step (3), the third mixing condition is stirring for 30-60min at the rotating speed of 300-500 r/min.
Further, in the step (4), the fourth mixing condition is stirring for 30-60min at the rotating speed of 300-500 r/min.
Further, in the step (5), the drop rate of the initiator solution is 30 to 35 drops/min, and the drop rate of the remaining mixed monomer is 50 to 60 drops/min.
The method of filtration in step (5) of the present invention may be a method conventional in the art, for example filtration of the effluent using a 340-600 mesh filter cloth.
Compared with the prior art, the invention has the advantages that:
1. The thickeners of the prior art, while effective in adjusting viscosity when used in coatings, may be unsatisfactory in improving water resistance, particularly in a continuous humid environment. In addition, these thickeners may reduce the overall hydrophobicity of the coating, and the hydrophobically modified emulsion thickeners prepared by incorporating specific effective raw material components of vinyl hydrophobic monomers in the present invention provide the thickener with better hydrophobicity, which can be used in water-resistant coatings to significantly enhance the performance of the water-resistant coatings.
2. According to the invention, the structural unit brought by the alkenyl imidazole ionic liquid monomer is introduced into the modified emulsion thickener, so that the hydrophobic modified emulsion thickener has excellent high-temperature stability.
3. The reaction system of the invention uses water as a medium, and has remarkable advantages in the process and the product with high environmental protection performance requirements.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a hydrophobic modified emulsion thickener for waterproof paint, which comprises the following components in percentage by mass: 3, the active raw material component and water; the effective raw material components comprise the following components in parts by weight: 100 parts of hydrophilic vinyl monomer, 20 parts of alkenyl imidazole ionic liquid monomer, 68 parts of vinyl hydrophobic monomer, 4.5 parts of polyalkenyl acrylic acid monomer, 7.2 parts of emulsifier and 0.7 part of initiator;
The hydrophilic vinyl monomer is a composition of acrylic acid and 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate; the weight ratio of acrylic acid to 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate is 1:0.38;
The vinyl hydrophobic monomer is the combination of long-chain alkyl acrylate and vinyl hydrophobic monomer containing phenyl; the weight ratio of the long-chain alkyl acrylate to the vinyl hydrophobic monomer containing phenyl is 1:0.4; the long-chain alkyl acrylate is octadecyl (meth) acrylate; the vinyl hydrophobic monomer containing phenyl is styrene;
the alkenyl imidazole ionic liquid monomer is 1-vinyl-3-butyl imidazole hexafluorophosphate;
the polyalkenyl acrylic acid monomer is a combination of tetraallyl pentaerythritol ether and trimethylolpropane diallyl ether; the weight ratio of the tetraallyl pentaerythritol ether to the trimethylolpropane diallyl ether is 1:1, a step of;
the emulsifier is the combination of mono-diglyceride and pentadecyl sodium benzenesulfonate; the weight ratio of the mono-diglyceride to the pentadecyl sodium benzenesulfonate is 1:0.65;
The initiator is ammonium persulfate.
The preparation method of the hydrophobic modified emulsion thickener for the waterproof paint comprises the following steps:
(1) Firstly mixing an emulsifier with water accounting for 70% of the total amount of water to obtain an emulsifier solution;
(2) Mixing an initiator with water accounting for 8% of the total amount of water for the second time to obtain an initiator solution;
(3) Thirdly mixing a hydrophilic vinyl monomer, an alkenyl imidazole ionic liquid monomer, a vinyl hydrophobic monomer and a polyalkenyl acrylic acid monomer to obtain a mixed monomer;
(4) Weighing mixed monomers accounting for 6 percent of the total weight of the mixed monomers, and performing fourth mixing on the mixed monomers and the emulsifier solution to obtain seed emulsion;
(5) Dropwise adding an initiator solution into the seed emulsion at 88 ℃, starting to dropwise add the rest mixed monomer after 1/4 of the weight of the initiator solution is left, preserving heat for 2.5 hours after the rest mixed monomer and the initiator solution are dropwise added, cooling a reaction product to 55 ℃ and adding the rest water for fifth mixing, and filtering to obtain the hydrophobic modified emulsion thickener for the waterproof coating;
In the step (1), stirring for 40min at the rotation speed of 400r/min under the first mixing condition; in the step (2), stirring for 10min at the rotation speed of 400r/min under the condition of the second mixing; in the step (3), stirring for 30min at the rotation speed of 400r/min under the third mixing condition; in the step (4), stirring for 50min at the rotation speed of 400r/min under the fourth mixing condition; in the step (5), the drop velocity of the initiator solution is 30 drops/min, and the drop velocity of the rest mixed monomers is 55 drops/min; in the step (5), the filtering method is to filter and discharge materials by using 400-mesh filter cloth.
Example 2
The embodiment provides a hydrophobic modified emulsion thickener for waterproof paint, which comprises the following components in percentage by mass: 4, the active raw material component and water; the effective raw material components comprise the following components in parts by weight: 100 parts of hydrophilic vinyl monomer, 23 parts of alkenyl imidazole ionic liquid monomer, 70 parts of vinyl hydrophobic monomer, 5 parts of polyalkenyl acrylic acid monomer, 8 parts of emulsifier and 0.8 part of initiator;
The hydrophilic vinyl monomer is a composition of acrylic acid and 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate; the weight ratio of acrylic acid to 2-methyl-2-acrylic acid-2-hydroxyethyl ester phosphate is 1:0.4;
The vinyl hydrophobic monomer is the combination of long-chain alkyl acrylate and vinyl hydrophobic monomer containing phenyl; the weight ratio of the long-chain alkyl acrylate to the vinyl hydrophobic monomer containing phenyl is 1:0.4; the long-chain alkyl acrylate is octadecyl (meth) acrylate; the vinyl hydrophobic monomer containing phenyl is styrene;
the alkenyl imidazole ionic liquid monomer is 1-vinyl-3-butyl imidazole hexafluorophosphate;
The polyalkenyl acrylic acid monomer is a combination of tetraallyl pentaerythritol ether and trimethylolpropane diallyl ether; the weight ratio of the tetraallyl pentaerythritol ether to the trimethylolpropane diallyl ether is 1:1.2;
the emulsifier is the combination of mono-diglyceride and pentadecyl sodium benzenesulfonate; the weight ratio of the mono-diglyceride to the pentadecyl sodium benzenesulfonate is 1:0.7;
The initiator is ammonium persulfate.
The preparation method of the hydrophobic modified emulsion thickener for the waterproof paint comprises the following steps:
(1) Firstly mixing an emulsifier with water accounting for 70% of the total amount of water to obtain an emulsifier solution;
(2) Mixing an initiator with water accounting for 10% of the total amount of water for the second time to obtain an initiator solution;
(3) Thirdly mixing a hydrophilic vinyl monomer, an alkenyl imidazole ionic liquid monomer, a vinyl hydrophobic monomer and a polyalkenyl acrylic acid monomer to obtain a mixed monomer;
(4) Weighing mixed monomers accounting for 8 percent of the total weight of the mixed monomers, and performing fourth mixing on the mixed monomers and the emulsifier solution to obtain seed emulsion;
(5) Dropwise adding an initiator solution into the seed emulsion at 90 ℃, starting to dropwise add the rest mixed monomer after the initiator solution is 2/5 of the weight, keeping the temperature for 3 hours after the rest mixed monomer and the initiator solution are dropwise added, cooling the reaction product to 65 ℃ and adding the rest water for fifth mixing, and filtering to obtain the hydrophobic modified emulsion thickener for the waterproof coating;
In the step (1), stirring for 40min at the rotation speed of 400r/min under the first mixing condition; in the step (2), stirring for 10min at the rotation speed of 400r/min under the condition of the second mixing; in the step (3), stirring for 30min at the rotation speed of 400r/min under the third mixing condition; in the step (4), stirring for 50min at the rotation speed of 400r/min under the fourth mixing condition; in the step (5), the drop velocity of the initiator solution is 30 drops/min, and the drop velocity of the rest mixed monomers is 55 drops/min; in the step (5), the filtering method is to filter and discharge materials by using 400-mesh filter cloth.
Comparative example 1
The difference between this comparative example and example 1 is:
The hydrophilic vinyl monomer is a composition of acrylic acid and methacrylic acid; the weight ratio of the acrylic acid to the methacrylic acid is 1:0.38.
Comparative example 2
The difference between this comparative example and example 1 is:
the hydrophilic vinyl monomer is acrylic acid.
Comparative example 3
The difference between this comparative example and example 1 is:
the hydrophilic vinyl monomer is 2-methyl-2-hydroxyethyl acrylate phosphate.
Comparative example 4
The difference between this comparative example and example 1 is:
the alkenyl imidazole ionic liquid monomer is 0 part.
Comparative example 5
The difference between this comparative example and example 1 is:
the polyalkenyl acrylic monomer is tetraallyl pentaerythritol ether.
Comparative example 6
The difference between this comparative example and example 1 is:
the polyalkenyl acrylic monomer is trimethylolpropane diallyl ether.
Comparative example 7
The difference between this comparative example and example 1 is:
the emulsifier is mono-diglyceride.
Comparative example 8
The difference between this comparative example and example 1 is:
the emulsifier is pentadecyl sodium benzenesulfonate.
Performance testing
1. Stability test: the thickeners of examples and comparative examples were left to stand at 55℃for 24 hours, respectively, and were not layered to be acceptable, otherwise, were not acceptable.
2. Salt tolerance test: firstly, using a No. 6 rotor, respectively testing the viscosity of the thickener at a rotating speed of 5rpm and a room temperature by using an NB-3 digital viscometer, before marking eta, respectively adding 0.05wt% of calcium chloride into the thickener, uniformly stirring, then testing the viscosity by using the same method, after marking eta, calculating the viscosity reduction rate; the viscosity decrease rate= (ηfront- ηback)/ηfront×100%.
3. The polymer cement waterproof paint was prepared as follows using the thickeners in examples and comparative examples, respectively:
(1) Preparing liquid materials in parts by weight: 65 parts of Jitian aqueous fluorocarbon resin emulsion with the model of F13-0801, 0.3 part of defoamer, 6 parts of water, 0.1 part of thickener and twelve 3 parts of alcohol ester;
(2) Preparing liquid: twelve of Jitian aqueous fluorocarbon resin emulsion, defoamer, water, thickener and alcohol ester are added into a stirring kettle, the stirring kettle is started, stirring is carried out for 15 minutes, and liquid materials are obtained after uniform dispersion;
(3) Preparing powder according to parts by weight: 32.5 parts of white cement 66 parts, quartz sand 36 parts, heavy calcium carbonate 48 parts and melamine high-efficiency water reducer 1 part;
(4) Preparing powder: placing 32.5 white cement, quartz sand, heavy calcium carbonate and melamine high-efficiency water reducer into a mortar stirrer to fully disperse powder, and stirring for 15 minutes to obtain powder;
(5) Preparation of polymer cement waterproof paint: mixing liquid material and powder material according to a mass ratio of 1:1.2 in a vessel at 600 rpm for 10 minutes to obtain a polymer cement waterproof coating.
The polymer cement waterproof paint was then tested for its impermeability according to GB/T23445-2009, respectively.
The test results are shown in table 1:
TABLE 1 Performance test results
From the above performance test results, the effects of water resistance, salt tolerance and high temperature stability of examples 1-2 are excellent, and especially the comprehensive performance of example 1 is most remarkable, and it is presumed that the structural unit brought by the alkenyl imidazole ionic liquid monomer is introduced into the modified emulsion thickener, so that the hydrophobic modified emulsion thickener has excellent high temperature stability, and meanwhile, the hydrophobic modified emulsion thickener prepared from the specific effective raw material components of the vinyl hydrophobic monomer has better hydrophobicity, and can be used in waterproof paint, thereby remarkably improving the performance of the waterproof paint. In contrast, the comparative example, in which 2-methyl-2-hydroxyethyl acrylate phosphate was replaced with methacrylic acid in comparative example 1, shows a decrease in salt tolerance, in which only acrylic acid was used as the hydrophilic vinyl monomer in comparative example 2, a decrease in salt tolerance, in which only 2-methyl-2-hydroxyethyl acrylate phosphate was used as the hydrophilic vinyl monomer in comparative example 3, and a decrease in salt tolerance and high temperature stability, namely, a synergistic effect of the specific hydrophilic vinyl monomer acrylic acid and 2-methyl-2-hydroxyethyl acrylate phosphate in comparative examples 1 to 3, can increase the salt tolerance of the thickener, were significantly inferior to those of the examples. In comparative example 4, no alkenyl imidazole ionic liquid monomer is added, and the salt tolerance and the high temperature stability of the thickener are reduced, which proves that the addition of the alkenyl imidazole ionic liquid monomer has an effect on the high temperature stability and the salt tolerance of the thickener. The comparative example 5 shows that the polyallylacryl acrylic acid monomer is only tetra allyl pentaerythritol ether, the water resistance of the paint is reduced when the thickener is used in the paint, the polyallylacryl acrylic acid monomer is only trimethylolpropane diallyl ether, the water resistance of the paint is reduced when the thickener is used in the paint, and the comparative example 5-6 shows that the use of tetra allyl pentaerythritol ether and trimethylolpropane diallyl ether together as the polyallylacryl acrylic acid monomer ensures that the thickener has better hydrophobicity and can ensure that the waterproof paint has better water resistance when the thickener is used in the waterproof paint. The emulsifier in comparative example 7 has only mono-diglyceride, the overall effect is reduced, the emulsifier in comparative example 8 has only pentadecyl benzene sulfonic acid, the overall effect is reduced, and the use of mono-diglyceride and pentadecyl benzene sulfonic acid together as the emulsifier is demonstrated by comparative examples 7-8, so that the overall performance of the thickener can be further ensured. The above experimental results further demonstrate the importance of the technical solutions defined in the present invention to the technical effects thereof.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A hydrophobic modified emulsion thickener for waterproof paint is characterized by comprising the following components in percentage by mass: the active raw material components of (2-5) and water; the effective raw material components comprise, by weight: 100 parts of hydrophilic vinyl monomer, 15-40 parts of alkenyl imidazole ionic liquid monomer, 40-100 parts of vinyl hydrophobic monomer, 2-8 parts of polyalkenyl acrylic acid monomer, 3-10 parts of emulsifier and 0.1-1.5 parts of initiator.
2. The hydrophobically modified emulsion thickener for water-repellent coatings of claim 1, wherein said effective raw material components comprise, in parts by weight: 100 parts of hydrophilic vinyl monomer, 18-23 parts of alkenyl imidazole ionic liquid monomer, 65-70 parts of vinyl hydrophobic monomer, 4.2-5 parts of polyalkenyl acrylic acid monomer, 6-8 parts of emulsifier and 0.6-1 part of initiator.
3. The hydrophobically modified emulsion thickener for water-repellent coatings according to claim 1 or 2, wherein said hydrophilic vinyl monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, methacrylamide, -methyl-2-acrylic acid-2-hydroxyethyl phosphate, vinylpyrrolidone, crotonic acid and aconitic acid.
4. A hydrophobically modified emulsion thickener for water-repellent coatings according to claim 1 or 2 wherein said vinyl hydrophobic monomer is selected from the group consisting of long chain alkyl acrylates in combination with phenyl-containing vinyl hydrophobic monomers, said long chain alkyl acrylates and phenyl-containing vinyl hydrophobic monomers having a weight ratio of 1: (0.1-0.5).
5. The hydrophobically modified emulsion thickener for water-repellent coatings of claim 4 wherein the weight ratio of long chain alkyl acrylate to phenyl-containing vinyl hydrophobic monomer is 1: (0.1-0.5); the long chain alkyl acrylate is selected from C8-C20 alkyl (meth) acrylate; the phenyl-containing vinyl hydrophobic monomer is selected from styrene and/or alpha-methyl styrene.
6. A hydrophobically modified emulsion thickener for water-repellent coatings according to claim 1 or 2, wherein said alkenyl imidazole ionic liquid monomer is selected from at least one of 1-allyl-3-methylimidazolium tetrafluoroborate, 1-propenyl-2, 3-dimethylimidazole p-toluenesulfonate and 1-vinyl-3-butylimidazole hexafluorophosphate.
7. A hydrophobically modified emulsion thickener for water-repellent coatings according to claim 1 or 2, wherein said polyalkenyl acrylic monomer is selected from at least one of tetraallyl pentaerythritol ether, diallyl phthalate, N-methylenebisacrylamide, trimethylolpropane diallyl ether and polyethylene glycol dimethacrylate.
8. A hydrophobically modified emulsion thickener for water-repellent coatings according to claim 1 or 2 wherein said emulsifier is selected from at least one of spandex-80, tween, mono-di-glyceride, sodium pentadecyl benzene sulfonate, sodium diisobutyl naphthalene sulfonate and sodium dodecyl benzene sulfonate.
9. A process for preparing a hydrophobically modified emulsion thickener for water-repellent coatings according to any of claims 1 to 8, comprising the steps of:
(1) Firstly mixing the emulsifier with water accounting for 65-70% of the total water to obtain an emulsifier solution;
(2) Mixing the initiator with water accounting for 5-10% of the total amount of water for the second time to obtain an initiator solution;
(3) Thirdly mixing a hydrophilic vinyl monomer, an alkenyl imidazole ionic liquid monomer, a vinyl hydrophobic monomer and a polyalkenyl acrylic acid monomer to obtain a mixed monomer;
(4) Weighing 5-8% of the total weight of the mixed monomers, and performing fourth mixing on the mixed monomers and the emulsifier solution to obtain seed emulsion;
(5) And (3) dropwise adding an initiator solution into the seed emulsion at 82-95 ℃, starting to dropwise add the rest mixed monomer after 1/4-2/5 of the initiator solution is left, keeping the temperature for 2-3 hours after the rest mixed monomer and the initiator solution are dropwise added, cooling the reaction product to 50-65 ℃ and adding the rest water for fifth mixing, and filtering to obtain the hydrophobic modified emulsion thickener for the waterproof coating.
10. The method for preparing a hydrophobically modified emulsion thickener for water-repellent coatings according to claim 9, wherein in step (1), said first mixing is carried out at a rotational speed of 300-500r/min for 30-60min; in the step (2), stirring for 5-20min at the rotation speed of 300-500r/min under the second mixing condition; in the step (3), stirring for 30-60min at the rotating speed of 300-500r/min under the third mixing condition; in the step (4), stirring for 30-60min at the rotating speed of 300-500r/min under the fourth mixing condition; in the step (5), the drop rate of the initiator solution is 30-35 drops/min, and the drop rate of the rest mixed monomers is 50-60 drops/min.
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