CN110606918B - Preparation method of benzene ring core-shell emulsion polymer for cement - Google Patents
Preparation method of benzene ring core-shell emulsion polymer for cement Download PDFInfo
- Publication number
- CN110606918B CN110606918B CN201910873932.XA CN201910873932A CN110606918B CN 110606918 B CN110606918 B CN 110606918B CN 201910873932 A CN201910873932 A CN 201910873932A CN 110606918 B CN110606918 B CN 110606918B
- Authority
- CN
- China
- Prior art keywords
- parts
- monomer
- aqueous solution
- benzene ring
- shell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011258 core-shell material Substances 0.000 title claims abstract description 45
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 42
- 239000004568 cement Substances 0.000 title claims abstract description 36
- 239000004908 Emulsion polymer Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 104
- 238000000034 method Methods 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004945 emulsification Methods 0.000 claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims description 81
- 239000000839 emulsion Substances 0.000 claims description 69
- 238000003756 stirring Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000007800 oxidant agent Substances 0.000 claims description 50
- 230000001590 oxidative effect Effects 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 47
- 229910021641 deionized water Inorganic materials 0.000 claims description 47
- 239000003995 emulsifying agent Substances 0.000 claims description 37
- -1 propylene alcohol Chemical compound 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 239000004530 micro-emulsion Substances 0.000 claims description 16
- WUEXSUKILNOBLI-UHFFFAOYSA-N 1-phenylethenoxyboronic acid Chemical compound OB(O)OC(=C)C1=CC=CC=C1 WUEXSUKILNOBLI-UHFFFAOYSA-N 0.000 claims description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 15
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 15
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 15
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 15
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical group FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 claims description 14
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 14
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 claims description 14
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 14
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 14
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 13
- ONCGZEUOJDTERQ-UHFFFAOYSA-N 2-ethenyl-4-methoxyaniline Chemical compound COC1=CC=C(N)C(C=C)=C1 ONCGZEUOJDTERQ-UHFFFAOYSA-N 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 8
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012792 core layer Substances 0.000 claims description 3
- NYFIDHXRJSCAOZ-UHFFFAOYSA-N 1-fluoro-4-prop-2-enylbenzene Chemical compound FC1=CC=C(CC=C)C=C1 NYFIDHXRJSCAOZ-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005913 Maltodextrin Substances 0.000 claims description 2
- 229920002774 Maltodextrin Polymers 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229940035034 maltodextrin Drugs 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- 229940001607 sodium bisulfite Drugs 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 41
- 239000011248 coating agent Substances 0.000 abstract description 40
- 229920000642 polymer Polymers 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 241000238367 Mya arenaria Species 0.000 abstract description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 3
- 238000010979 pH adjustment Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 230000003487 anti-permeability effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 58
- YJCPVMYUISTDKG-UHFFFAOYSA-N 1-phenylethenylboronic acid Chemical compound OB(O)C(=C)C1=CC=CC=C1 YJCPVMYUISTDKG-UHFFFAOYSA-N 0.000 description 13
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 9
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000005395 methacrylic acid group Chemical group 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011414 polymer cement Substances 0.000 description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 230000002087 whitening effect Effects 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a preparation method of a benzene ring core-shell emulsion polymer for cement, which takes a hydroxyl hydrophilic monomer and a benzene ring hydrophobic monomer as raw materials, and prepares a high-molecular polymer waterproof coating with narrow distribution and strong binding force through a series of processes such as emulsification reaction, constant-temperature polymerization, pH adjustment and the like in an emulsification reaction system, wherein hydrogen bonds in hydroxyl molecules can strengthen the internal binding force of the polymer, the strong hydrophilic action can strengthen the adhesive force with a matrix, and the hydroxyl can stably complex calcium ions and is tightly and firmly bound with cement particles, so that a good waterproof and anti-permeability effect is achieved; the invention combines the special synergistic effect of the core-shell structure on performance or function, has the characteristics of hard core and soft shell, has good permeability and wettability on the surface of the combination body, is anti-aging and not easy to crack, and can prolong the service life.
Description
Technical Field
The invention belongs to the technical field of building materials, relates to the field of building surface waterproof and adhesive coatings, and particularly relates to a preparation method of a benzene ring core-shell emulsion polymer for cement.
Background
Due to the fact that the quality levels of real estate houses are not uniform, the roofs, kitchens, toilets, basements and other places are prone to cracks, and the phenomena of water seepage, mildew and falling off are caused. Although the existing waterproof coating on the market has certain elongation and mechanical strength, the surface of a coating film is easy to generate micro cracks, pinholes and other defects, and a good waterproof effect cannot be achieved, so that the waterproof engineering fails. The emulsion polymer prepared by the traditional process is slow in film forming after being dried at normal temperature, poor in leveling property, small in solid content and small in viscosity drop, and the common emulsifier is not environment-friendly and has great influence on the water resistance of the formed film of the emulsion. The product adopts a core-shell emulsion polymerization technology to synthesize a functional polymer through a simple process, and utilizes the special forced mutual dissolution to enable functional monomers to be tightly combined to form a stable macromolecular polymer. Due to the structural characteristics of a special core-shell structure, interface interpenetration, two-phase continuity and the like, the polymer generates a special synergistic effect on the performance or function, so that the waterproof coating has good waterproof and weather-resistant properties.
Patent CN200910041338.0 discloses a polymer cement waterproof coating acrylic emulsion, wherein the weight percentage of each component in the total amount of the emulsion is as follows: 10-20% of styrene, 1-10% of methyl methacrylate, 30-45% of butyl acrylate, 0.1-0.5% of methacrylic acid, 1-3% of ethylene glycol dimethacrylate, 1-3% of emulsifier, 0.3-0.8% of persulfate and the balance of water. Compared with the prior art, the invention has better chemical stability and cracking resistance. The cement has good delayed coagulation property when mixed with cement, and is convenient for field construction.
Patent CN201310471864.7 discloses a composite strong waterproof silica gel coating, which is prepared by the following steps: taking 32-48 parts of raw material emulsion base material, 8-12 parts of vinyl acetate, 4-6 parts of polyvinyl alcohol, 8-12 parts of sodium methyl silicate, 1.2-1.8 parts of white carbon black, 1.2-1.8 parts of titanium dioxide, 15.2-22.8 parts of filler, 5.6-8.4 parts of auxiliary agent and 4.8-7.2 parts of water; secondly, adding vinyl acetate into the emulsion base material, stirring, dispersing and carrying out polymerization reaction; thirdly, adding white carbon black, and stirring uniformly; fourthly, adding titanium dioxide, filler and auxiliary agent, and stirring uniformly; fifthly, adding sodium methyl silicate, polyvinyl alcohol and water; stirring uniformly, and reacting for 9-11 min; the composite strong waterproof silica gel coating is prepared. It is environment-friendly and nontoxic; a double-layer waterproof structure can be formed; the low-temperature tensile property is good; the anti-cracking performance is good; the service life is long; the paint is not stained with water; the mechanical strength is good.
Patent CN200910092846.1 discloses an acrylic core-shell polymer emulsion for low temperature resistant polymer cement waterproof material, which is prepared from components including (1) and (2) by emulsion polymerization, wherein (1) is a core layer component of the polymer emulsion, and includes at least the following two monomers: 60-95 parts of butyl acrylate and 6-10 parts of acrylonitrile; (2) is a shell component of the polymer emulsion and comprises at least the following two monomers: 5-15 parts of butyl acrylate and 5-15 parts of methyl methacrylate. The invention also provides a preparation method of the acrylic core-shell polymer emulsion. The acrylic core-shell polymer emulsion has a lower tg value, and a polymer cement composition formed by the acrylic core-shell polymer emulsion and cement has higher tensile strength, freeze-thaw resistance, and better waterproofness and flexibility.
However, products in the prior art are only improved on one aspect, and the comprehensive performance is difficult to achieve the effects of excellent stain resistance, heat resistance, tensile strength and water resistance, so that a waterproof coating with more excellent performance needs to be further developed on the basis of the prior art.
Disclosure of Invention
The invention aims to solve the technical problem of building waterproofing, provides a preparation method of a benzene ring core-shell emulsion polymer for cement, and solves the problem that the stain resistance, heat resistance and water resistance of a coating in the prior art cannot be simultaneously achieved.
The invention adopts a core-shell emulsion polymerization method to prepare a branched long-chain polymer emulsion coating containing hydroxyl benzene rings, the distribution of molecular weight is narrow, the core-shell emulsion polymerization method is adopted, a series of processes such as emulsification, constant-temperature polymerization, pH adjustment and the like are carried out in an emulsification reaction system, and the reaction process is strictly controlled, so that the polymer waterproof coating which is provided with a soft shell and a hard core, is compact and stable, has higher hardness and strong affinity and takes hydrophilic hydroxyl as a shell and hydrophobic benzene rings as a core is prepared. In the preparation process, the oxidizing agent and the self-made emulsifier are reasonably selected for distribution polymerization in consideration of the characteristics of the hydrophobic monomer and the hydrophilic monomer, and the stirring speed and the corresponding temperature are adjusted according to the polymerization process, so that the high molecular weight and narrow distribution of the final polymer are ensured, and the stability in the polymerization process and the storage stability of the emulsion coating are ensured by multiple times of pH adjustment.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the benzene ring core-shell emulsion polymer for cement is characterized by sequentially comprising the following operation steps of:
preparing an emulsifier in step (1): directly adding 8-12 parts of deionized water, 3.0-5.5 parts of hydroxyl hydrophilic small monomer for emulsification, 8.0-17.0 parts of benzene ring hydrophobic small monomer for emulsification, 0.2-0.45 part of emulsion initiator and 0.35-0.75 part of chain transfer agent into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react at 70-90 ℃ for 2-3 hours, preserving heat and curing for 1-2 hours, and cooling to obtain an emulsifier; the hydroxyl hydrophilic small monomer for emulsification is monomer propylene alcohol and/or methyl propylene alcohol; the benzene ring hydrophobic small monomer for emulsification is 1-phenyl vinyl boric acid and/or 4-methoxy-2-vinylaniline;
preparing a nuclear monomer aqueous solution in step (2): mixing 8.2-12.0 parts of hydroxyl hydrophilic small monomer, 180-230 parts of acrylic soft monomer and 0.8-1.2 parts of reducing agent to prepare a nuclear monomer aqueous solution; mixing 1.0-2.1 parts of oxidant and 60-80 parts of deionized water to prepare an oxidant aqueous solution a, and uniformly stirring for later use;
preparing shell monomer emulsion in step (3): mixing 265 parts of benzene ring hydrophobic small monomer 200-265 parts, 23-40 parts of fluorine functional monomer, 0.5-1.0 part of reducing agent and 1/3 part of emulsifier prepared in the step (1), stirring, dispersing and emulsifying at the rotation speed of 1000-1200rpm for 30-60min to prepare shell monomer emulsion; mixing 1.0-2.1 parts of oxidant and 60-80 parts of deionized water to prepare an oxidant aqueous solution b, and uniformly stirring for later use; the fluorine functional monomer is trifluoroethyl acrylate and/or perfluorooctyl ethyl acrylate;
step (4) adding 300 and 450 parts of deionized water and the rest of 2/3 of the emulsifier prepared in the step (1) into a reaction vessel, uniformly stirring, heating to 45-50 ℃, adding 20% of nuclear monomer aqueous solution and 20% of oxidant aqueous solution a at one time, continuously stirring and preserving heat for 40-60min to obtain seed microemulsion; dropwise adding the rest 80% of the nuclear monomer aqueous solution and 80% of the oxidant aqueous solution a into the seed microemulsion at a constant speed for 80-120min, and stirring and preserving heat for 30-40min at the rotation speed of 600-800rpm after the dropwise adding is finished to obtain nuclear layer emulsion; cooling to 40-45 ℃, adding 1.2-2.5 parts of neutralizer, adjusting the pH to 8-8.5, and slowly dripping the shell monomer aqueous solution and the oxidant aqueous solution b into the core layer emulsion for 260 min; after the shell monomer aqueous solution is dripped for 60min, 2.8-6.5 parts of cross-linking agent is added at one time;
and (5) after the dropwise addition, adding 2.1-4.0 parts of neutralizer, adjusting the pH of the solution to 9.5-10, adding deionized water to 1000 parts of the total mass of the solution, heating to 50-60 ℃, adjusting to the rotation speed of 400-ion-doped 600rpm, preserving heat, curing for 2-5 hours, and naturally cooling to room temperature to obtain the benzene ring core-shell emulsion polymer for cement.
Preferably, in the step (1), the emulsion initiator is any one or more of lauroyl peroxide, tert-butyl peroxypivalate and dicyclohexyl peroxydicarbonate.
Preferably, in the step (1), the chain transfer agent is sodium hypophosphite and/or sodium methallyl sulfonate.
Preferably, in the step (2), the hydroxyl hydrophilic small monomer is any one or more of allyl alcohol, methyl allyl alcohol, isoamylene alcohol and 4- (ethyleneoxy) -1-butanol.
Preferably, in the step (3), the benzene ring type hydrophobic small monomer is any one or more of styrene, 1-allyl-2-fluorobenzene, 1-allyl-4-fluorobenzene, 1-phenylvinyl boronic acid and 4-methoxy-2-vinylaniline.
Preferably, in the step (2), the oxidizing agent is any one or more of Benzoyl Peroxide (BPO) and/or di-tert-butyl peroxide (DTBP).
Preferably, in the step (4), the crosslinking agent is pyromellitic dianhydride hydroxyethyl dimethacrylate.
Preferably, in the step (2), the reducing agent is any one or more of sodium hydrosulfite, ascorbic acid, sodium formaldehyde sulfoxylate, maltodextrin, sodium bisulfite, sodium metabisulfite and sodium hypophosphite.
Preferably, in the step (5), the neutralizing agent is any one or more of sodium hydroxide solution with 30% solubility, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium ethoxide, ethanolamine, diethanolamine, triethanolamine and triisopropanolamine.
Preferably, in the step (2), the acrylate soft monomer is any one or more of butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, ethyl acrylate and acrylic acid.
The benzene ring core-shell emulsion polymer for cement is prepared by any one of the methods, and comprises the following raw materials in parts by mass of 1000:
3.0-5.5 parts of hydroxyl hydrophilic small monomer for emulsification
8.0-17.0 parts of benzene ring hydrophobic small monomer for emulsification
0.2 to 0.45 portion of emulsion initiator
0.35 to 0.75 portion of chain transfer agent
8.2-12.0 parts of hydroxyl hydrophilic small monomer
Oxidant 1.5-5.6 parts
15-22 parts of emulsifier
200 portions of 265 portions of benzene ring hydrophobic small monomer
1.3 to 3.2 portions of reducing agent
Acrylic ester soft monomer 180 parts
23-40 parts of fluorine functional monomer
2.8-6.5 parts of cross-linking agent
Neutralizing agent 2.2-5.7 parts
The remaining component was deionized water.
The invention has the beneficial effects that:
the waterproof coating of the invention adopts a method of core-shell emulsion polymerization to synthesize a high-molecular emulsion polymer with narrow hydrophilic and hydrophobic group tight combination distribution. The invention utilizes the structural characteristics of core-shell emulsion polymerization to synthesize the functional polymer waterproof coating with strong internal binding force and uniform and stable distribution. The self-made emulsifier is selected, the reaction is carried out, the temperature and the stirring speed are reasonably regulated and controlled, the particle size and the distribution of the emulsion are effectively controlled, the relative molecular weight of the polymer is well controlled, the stability of the emulsion coating is ensured, the special synergistic effect of the core-shell structure on the performance or the function is combined, the emulsion coating has the characteristics of hard core and soft shell, the permeability and the wettability on the surface of a combined body are good, the aging resistance and the cracking resistance are not easy to cause, the service life can be prolonged, and in addition, the emulsion coating also has the following advantages:
1. the soft-shell hard-core structure emulsion waterproof coating prepared by the invention not only has higher glass transition temperature, but also has lower film forming temperature, and ensures good film forming property.
2. The core/shell structure emulsion waterproof coating prepared by the invention ensures strong binding force between the coating and a substrate through the design that the molar ratio of the hydrophobic monomer to the hydrophilic monomer is 14.3-18.2: 1, and the coating cannot be pulverized and peeled off in the service life.
3. The invention reasonably regulates and controls the temperature through the difference of the half-life period of the oxidant in the emulsion polymerization process, properly adjusts the stirring speed and the dropping speed of the pre-emulsion and the oxidant, strives to reduce the molecular weight distribution range of the high molecular polymer, reasonably adjusts the pH value, greatly improves the stability of the emulsion, and can realize batch production, stable storage and remote scheduling.
4. The core-shell emulsion polymer waterproof coating adopts the self-made emulsifier, the emulsifier participates in the reaction process, the problem of emulsion breaking is well solved, the problem of foaming and whitening of the final coating is not worried about, and the core-shell emulsion polymer waterproof coating has good water resistance.
5. The waterproof coating is suitable for being mixed with cement, a large number of hydroxyl groups can stably complex calcium ions, hydrolysis of the calcium ions is effectively inhibited, the strength of the cement is improved, the waterproof effect is enhanced, the internal bonding force of a polymer can be enhanced through the hydroxyl group intramolecular hydrogen bonds, the adhesive force between the polymer and a matrix is enhanced through the strong hydrophilic effect, and the waterproof coating is very suitable for being used as the waterproof coating for the cement.
6. According to the core-shell emulsion polymer waterproof coating, a proper amount of fluorine functional monomer is added into the raw materials, so that the waterproof effect of a coating film is improved, a good defoaming effect is exerted, the polymer reaction is more sufficient, the coating film is smoother, and the waterproof effect of the coating film is more excellent.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not intended to be limiting.
Example 1
A preparation method of a benzene ring core-shell emulsion polymer for cement is prepared by polymerizing the following components, wherein the total mass of the raw materials is 1000 parts, and the components and process parameters are as follows:
methacrylic alcohol: 3.5 parts of
1-phenyl vinyl boronic acid: 14.5
Dicyclohexyl peroxydicarbonate: 0.3 part
Sodium methallyl sulfonate: 0.5 portion
Isopentenol: 9 portions of
2-ethylhexyl acrylate: 200 portions of
1-phenyl vinyl boronic acid: 230 portions of
Benzoyl peroxide: 1.5 parts of
Di-tert-butyl peroxide: 1.5 parts of
Sodium hypophosphite: 2.0 part by weight
A composition of bis (methacryloyloxyethyl) pyromellitic anhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1: 4 portions of
Diethanolamine: 1.2 parts of
Sodium bicarbonate: 2.8 parts of
The composition with the mass ratio of trifluoroethyl acrylate to perfluorooctyl ethyl acrylate being 1: 30 portions of
The remaining component was deionized water.
1) Preparing an emulsifier: directly adding 10 parts of deionized water, 3.5 parts of methyl allyl alcohol, 14.5 parts of 1-phenyl vinyl boric acid, 0.3 part of dicyclohexyl peroxydicarbonate and 0.5 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 2 hours at 80 ℃, preserving heat, curing for 1 hour, and cooling to obtain the emulsifier.
2) Preparation of an aqueous nuclear monomer solution: mixing 9 parts of isopentenol, 200 parts of acrylic acid-2-ethylhexyl ester and 1.0 part of sodium hypophosphite to prepare a nuclear monomer aqueous solution with the mass fraction of 50%; 1.5 parts of benzoyl peroxide and 60 parts of deionized water are mixed to prepare an oxidant aqueous solution a, and the oxidant aqueous solution a is uniformly stirred for later use.
3) Preparing a shell monomer emulsion: mixing 230 parts of 1-phenyl vinyl boric acid, 1.0 part of sodium hypophosphite, 1/3 parts of the emulsifier prepared in the step (1) and 30 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 1:1, and stirring, dispersing and emulsifying at the rotating speed of 1000-1200rpm for 30min to prepare a shell monomer emulsion with the mass fraction of 50%; 1.5 parts of di-tert-butyl peroxide and 60 parts of deionized water are mixed to prepare an initiator aqueous solution b, and the initiator aqueous solution b is uniformly stirred for later use.
4) Adding 350 parts of deionized water and the rest of the emulsifying agent prepared in the step (1) 2/3 into a reaction container, uniformly stirring, heating to about 45 ℃, adding 20% of nuclear monomer aqueous solution and 20% of oxidant aqueous solution a at one time, continuously stirring and preserving heat for 60min to obtain seed microemulsion; dropwise adding the rest 80% of the nuclear monomer aqueous solution and 80% of the oxidant aqueous solution a into the seed microemulsion at a constant speed for 80-120min, and stirring and preserving heat for 40min at the rotation speed of 600-800rpm after the dropwise adding is finished to obtain nuclear layer emulsion; cooling to about 40 ℃, adding 1.2 parts of diethanolamine, adjusting the pH value to 8-8.5, and slowly dripping the shell monomer emulsion and the oxidant aqueous solution b into the nuclear layer emulsion for 260 min; after the shell monomer emulsion is dripped for 30min, 4 parts of the composition of bis (methacryloyloxyethyl) pyromellitic dianhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1:1 are added at a time.
5) After the dropwise addition, adding 2.8 parts of sodium bicarbonate, adjusting the pH value of the solution to 9.5-10, adding deionized water to 1000 parts of the total mass of the solution, heating to about 50 ℃, adjusting to the rotation speed of 400-600rpm, preserving heat, curing for 3 hours, and naturally cooling to room temperature to obtain the 50 mass percent benzene ring core-shell emulsion polymer (waterproof coating) for cement.
Example 2
A preparation method of a benzene ring core-shell emulsion polymer for cement is prepared by polymerizing the following components, wherein the total mass of the raw materials is 1000 parts, and the components and process parameters are as follows:
methacrylic alcohol: 3.5 parts of
1-phenyl vinyl boronic acid: 14.5
The composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate with the mass ratio of 3:1 is as follows: 0.3 part
Sodium methallyl sulfonate: 0.5 portion
Isopentenol: 9 portions of
2-ethylhexyl acrylate: 200 portions of
1-phenyl vinyl boronic acid: 230 portions of
Benzoyl peroxide: 1.5 parts of
Di-tert-butyl peroxide: 1.5 parts of
A composition of sodium dithionite and ascorbic acid in a mass ratio of 1: 3: 2.0 part by weight
A composition of bis (methacryloyloxyethyl) pyromellitic anhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1: 4 portions of
Diethanolamine: 1.4 parts of
Sodium bicarbonate: 2.6 parts of
The composition with the mass ratio of trifluoroethyl acrylate to perfluorooctyl ethyl acrylate being 1: 30 portions of
The remaining component was deionized water.
1) Preparing an emulsifier: directly adding 10 parts of deionized water, 3.5 parts of methyl allyl alcohol, 14.5 parts of 1-phenyl vinyl boric acid, 0.3 part of a composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate with the mass ratio of 3:1 and 0.5 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 2 hours at 80 ℃, preserving heat and curing for 1 hour, and cooling to obtain the emulsifier.
2) Preparation of an aqueous nuclear monomer solution: mixing 9 parts of prenol, 200 parts of 2-ethylhexyl acrylate, 1.0 part of a composition of sodium hydrosulfite and ascorbic acid in a mass ratio of 1:3 to prepare a nuclear monomer aqueous solution with the mass fraction of 50%; 1.5 parts of benzoyl peroxide and 60 parts of deionized water are mixed to prepare an oxidant aqueous solution a, and the oxidant aqueous solution a is uniformly stirred for later use.
3) Preparing a shell monomer emulsion: mixing 230 parts of 1-phenyl vinyl boric acid, 1.0 part of a composition of sodium hydrosulfite and ascorbic acid in a mass ratio of 1:3, 1/3 part of an emulsifier prepared in the step (1) and 30 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 1:1, stirring, dispersing and emulsifying at the rotation speed of 1000-1200rpm for 30min to prepare a shell monomer emulsion with the mass fraction of 50%; 1.5 parts of di-tert-butyl peroxide and 60 parts of deionized water are mixed to prepare an initiator aqueous solution b, and the initiator aqueous solution b is uniformly stirred for later use.
4) Adding 350 parts of deionized water and the rest of the emulsifying agent prepared in the step (1) 2/3 into a reaction container, uniformly stirring, heating to 45 ℃, adding 20% of nuclear monomer aqueous solution and 20% of oxidant aqueous solution a at one time, continuously stirring and preserving heat for 60min to obtain seed microemulsion; dropwise adding the rest 80% of the nuclear monomer aqueous solution and 80% of the oxidant aqueous solution a into the seed microemulsion at a constant speed for 80-120min, and stirring and preserving heat for 40min at the rotation speed of 600-800rpm after the dropwise adding is finished to obtain nuclear layer emulsion; cooling to about 40 ℃, adding 1.4 parts of diethanolamine, adjusting the pH value to 8-8.5, and slowly dripping the shell monomer emulsion and the oxidant aqueous solution b into the nuclear layer emulsion for 260 min; after the shell monomer emulsion is dripped for 30min, 4 parts of the composition of bis (methacryloyloxyethyl) pyromellitic dianhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1:1 are added at a time.
5) After the dropwise addition, adding 2.6 parts of sodium bicarbonate, adjusting the pH value of the solution to 9.5-10, adding deionized water to 1000 parts of the total mass of the solution, heating to about 50 ℃, adjusting to the rotation speed of 400-600rpm, preserving heat, curing for 3 hours, and naturally cooling to room temperature to obtain the 50 mass percent benzene ring core-shell emulsion polymer (waterproof coating) for cement.
Example 3
A preparation method of a benzene ring core-shell emulsion polymer for cement is prepared by polymerizing the following components, wherein the total mass of the raw materials is 1000 parts, and the components and process parameters are as follows:
methacrylic alcohol: 3.5 parts of
1-phenyl vinyl boronic acid: 14.5
Dicyclohexyl peroxydicarbonate: 0.3 part
Sodium methallyl sulfonate: 0.5 portion
The composition of 4- (ethyleneoxy) -1-butanol and isopentenol with the mass ratio of 1:1 comprises the following components: 9 portions of
2-ethylhexyl acrylate: 200 portions of
1:2 composition of 1-phenyl vinyl boronic acid and 4-methoxy-2-vinyl aniline: 230 portions of
Benzoyl peroxide: 1.5 parts of
Di-tert-butyl peroxide: 1.5 parts of
Sodium hypophosphite: 2.0 part by weight
A composition of bis (methacryloyloxyethyl) pyromellitic anhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1: 4 portions of
Diethanolamine: 1.5 parts of
Sodium bicarbonate: 2.5 parts of
The composition with the mass ratio of trifluoroethyl acrylate to perfluorooctyl ethyl acrylate being 1: 30 portions of
The remaining component was deionized water.
1) Preparing an emulsifier: directly adding 10 parts of deionized water, 3.5 parts of methyl allyl alcohol, 14.5 parts of 1-phenyl vinyl boric acid, 0.3 part of dicyclohexyl peroxydicarbonate and 0.5 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 2 hours at 80 ℃, preserving heat, curing for 1 hour, and cooling to obtain the emulsifier.
2) Preparation of an aqueous nuclear monomer solution: mixing 9 parts of a composition of 4- (ethyleneoxy) -1-butanol and isopentenol, 200 parts of 2-ethylhexyl acrylate and 1.0 part of sodium hypophosphite in a mass ratio of 1:1 to prepare a nuclear monomer aqueous solution with the mass fraction of 50%; 1.5 parts of benzoyl peroxide and 60 parts of deionized water are mixed to prepare an oxidant aqueous solution a, and the oxidant aqueous solution a is uniformly stirred for later use.
3) Preparing a shell monomer emulsion: mixing 230 parts of a composition of 1-phenyl vinyl boric acid and 4-methoxy-2-vinyl aniline in a ratio of 1:2, 1.0 part of sodium hypophosphite, 1/3 parts of a composition prepared in the step (1) and 30 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 1:1, stirring, dispersing and emulsifying at a rotating speed of 1000-1200rpm for 30min to prepare a shell monomer emulsion with a mass fraction of 50%; 1.5 parts of di-tert-butyl peroxide and 60-80 parts of deionized water are mixed to prepare an initiator aqueous solution b, and the initiator aqueous solution b is uniformly stirred for later use.
4) Adding 350 parts of deionized water and the rest of the emulsifying agent prepared in the step (1) 2/3 into a reaction container, uniformly stirring, heating to 45 ℃, adding 20% of nuclear monomer aqueous solution and 20% of oxidant aqueous solution a at one time, continuously stirring and preserving heat for 60min to obtain seed microemulsion; dropwise adding the rest 80% of the nuclear monomer aqueous solution and 80% of the oxidant aqueous solution a into the seed microemulsion at a constant speed for 80-120min, and stirring and preserving heat for 40min at the rotation speed of 600-800rpm after the dropwise adding is finished to obtain nuclear layer emulsion; cooling to about 40 ℃, adding 1.5 parts of diethanolamine, adjusting the pH value to 8-8.5, and slowly dripping the shell monomer emulsion and the oxidant aqueous solution b into the nuclear layer emulsion for 260 min; after the shell monomer emulsion is dripped for 30min, 4 parts of the composition of bis (methacryloyloxyethyl) pyromellitic dianhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1:1 are added at a time.
5) After the dropwise addition, adding 2.5 parts of sodium bicarbonate, adjusting the pH value of the solution to 9.5-10, adding deionized water to 1000 parts of the total mass of the solution, heating to about 50 ℃, adjusting to the rotation speed of 400-600rpm, preserving heat, curing for 3 hours, and naturally cooling to room temperature to obtain the 50 mass percent benzene ring core-shell emulsion polymer (waterproof coating) for cement.
Example 4
A preparation method of a benzene ring core-shell emulsion polymer for cement is prepared by polymerizing the following components, wherein the total mass of the raw materials is 1000 parts, and the components and process parameters are as follows:
methacrylic alcohol: 3.5 parts of
1-phenyl vinyl boronic acid: 14.5
Dicyclohexyl peroxydicarbonate: 0.3 part
Sodium methallyl sulfonate: 0.5 portion
Isopentenol: 9 portions of
2-ethylhexyl acrylate: 200 portions of
1:2 composition of 1-phenyl vinyl boronic acid and 4-methoxy-2-vinyl aniline: 230 portions of
Benzoyl peroxide: 1.0 part
Di-tert-butyl peroxide: 1.5 parts of
A composition of sodium dithionite and ascorbic acid in a mass ratio of 1: 3: 2.0 part by weight
A composition of bis (methacryloyloxyethyl) pyromellitic anhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1: 4 portions of
Diethanolamine: 1.4 parts of
Sodium bicarbonate: 2.6 parts of
The composition with the mass ratio of trifluoroethyl acrylate to perfluorooctyl ethyl acrylate being 1: 30 portions of
The remaining component was deionized water.
1) Preparing an emulsifier: directly adding 10 parts of deionized water, 3.5 parts of methyl allyl alcohol, 14.5 parts of 1-phenyl vinyl boric acid, 0.3 part of dicyclohexyl peroxydicarbonate and 0.5 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 2.5 hours at 80 ℃, preserving heat, curing for 1 hour, and cooling to obtain the emulsifier.
2) Preparation of an aqueous nuclear monomer solution: mixing 9 parts of prenol, 200 parts of 2-ethylhexyl acrylate, 1.0 part of a composition of sodium hydrosulfite and ascorbic acid in a mass ratio of 1:3 to prepare a nuclear monomer aqueous solution with the mass fraction of 50%; 1.0 part of benzoyl peroxide and 50 parts of deionized water are mixed to prepare an oxidant aqueous solution a, and the oxidant aqueous solution a is uniformly stirred for standby.
3) Preparing a shell monomer emulsion: mixing 230 parts of a composition of 1:2 1-phenyl vinyl boric acid and 4-methoxy-2-vinyl aniline, 1.0 part of a composition of sodium hydrosulfite and ascorbic acid in a mass ratio of 1:3, 1/3 parts of an emulsifier prepared in the step (1), and 30 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 1:1, stirring, dispersing and emulsifying at the rotation speed of 1000-; 1.5 parts of di-tert-butyl peroxide and 60 parts of deionized water are mixed to prepare an initiator aqueous solution b, and the initiator aqueous solution b is uniformly stirred for later use.
4) Adding 350 parts of deionized water and the rest of the emulsifying agent prepared in the step (1) 2/3 into a reaction container, uniformly stirring, heating to 45 ℃, adding 20% of nuclear monomer aqueous solution and 20% of oxidant aqueous solution a at one time, continuously stirring and preserving heat for 60min to obtain seed microemulsion; dropwise adding the rest 80% of the nuclear monomer aqueous solution and 80% of the oxidant aqueous solution a into the seed microemulsion at a constant speed for 80-120min, and stirring and preserving heat for 40min at the rotation speed of 600-800rpm after the dropwise adding is finished to obtain nuclear layer emulsion; cooling to about 40 ℃, adding 1.4 parts of diethanolamine, adjusting the pH value to 8-8.5, and slowly dripping the shell monomer emulsion and the oxidant aqueous solution b into the nuclear layer emulsion for 260 min; after the shell monomer emulsion is dripped for 30min, 4 parts of the composition of bis (methacryloyloxyethyl) pyromellitic dianhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1:1 are added at a time.
5) After the dropwise addition, adding 2.6 parts of sodium bicarbonate, adjusting the pH value of the solution to 9.5-10, adding deionized water to 1000 parts of the total mass of the solution, heating to about 50 ℃, adjusting to the rotation speed of 400-600rpm, preserving heat, curing for 3 hours, and naturally cooling to room temperature to obtain the 50 mass percent benzene ring core-shell emulsion polymer (waterproof coating) for cement.
Example 5
A preparation method of a benzene ring core-shell emulsion polymer for cement is prepared by polymerizing the following components, wherein the total mass of the raw materials is 1000 parts, and the components and process parameters are as follows:
methacrylic alcohol: 3.5 parts of
1-phenyl vinyl boronic acid: 14.5
The composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate with the mass ratio of 3:1 is as follows: 0.3 part
Sodium methallyl sulfonate: 0.5 portion
The composition of 4- (ethyleneoxy) -1-butanol and isopentenol with the mass ratio of 1:1 comprises the following components: 10 portions of
A composition of 2-ethylhexyl acrylate and butyl acrylate in a mass ratio of 1: 2: 200 portions of
1:2 composition of 1-phenyl vinyl boronic acid and 4-methoxy-2-vinyl aniline: 228 portions of
Benzoyl peroxide: 1.5 parts of
Di-tert-butyl peroxide: 1.5 parts of
A composition of sodium dithionite and ascorbic acid in a mass ratio of 1: 3: 2.0 part by weight
A composition of bis (methacryloyloxyethyl) pyromellitic anhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1: 4 portions of
Diethanolamine: 1.4 parts of
Sodium bicarbonate: 2.6 parts of
The composition with the mass ratio of trifluoroethyl acrylate to perfluorooctyl ethyl acrylate being 1: 30 portions of
The remaining component was deionized water.
1) Preparing an emulsifier: directly adding 10 parts of deionized water, 3.5 parts of methyl allyl alcohol, 14.5 parts of 1-phenyl vinyl boric acid, 0.3 part of a composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate with the mass ratio of 3:1 and 0.5 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react at 80 ℃ for 2.5 hours, preserving heat, curing for 1 hour, and cooling to obtain the emulsifier.
2) Preparation of an aqueous nuclear monomer solution: mixing 10 parts of a composition of 4- (ethyleneoxy) -1-butanol and isopentenol in a mass ratio of 1:1, 200 parts of a composition of 2-ethylhexyl acrylate and butyl acrylate in a mass ratio of 1:2, and 1.0 part of a composition of sodium hydrosulfite and ascorbic acid in a mass ratio of 1:3 to prepare a nuclear monomer aqueous solution with the mass fraction of 50%; 1.5 parts of benzoyl peroxide and 50 parts of deionized water are mixed to prepare an oxidant aqueous solution a, and the oxidant aqueous solution a is uniformly stirred for standby.
3) Preparing a shell monomer emulsion: 228 parts of a composition of 1:2 1-phenyl vinyl boric acid and 4-methoxy-2-vinyl aniline, 1.0 part of a composition of sodium hydrosulfite and ascorbic acid in a mass ratio of 1:3, 1/3 the emulsifier prepared in the step (1) and 30 parts of a composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in a mass ratio of 1:1 are mixed, stirred, dispersed and emulsified for 30min at the rotating speed of 1000-; 1.5 parts of di-tert-butyl peroxide and 60 parts of deionized water are mixed to prepare an initiator aqueous solution b, and the initiator aqueous solution b is uniformly stirred for later use.
4) Adding 350 parts of deionized water and the rest of the emulsifying agent prepared in the step (1) 2/3 into a reaction container, uniformly stirring, heating to 45 ℃, adding 20% of nuclear monomer aqueous solution and 20% of oxidant aqueous solution a at one time, continuously stirring and preserving heat for 60min to obtain seed microemulsion; dropwise adding the rest 80% of the nuclear monomer aqueous solution and 80% of the oxidant aqueous solution a into the seed microemulsion at a constant speed for 80-120min, and stirring and preserving heat for 40min at the rotation speed of 600-800rpm after the dropwise adding is finished to obtain nuclear layer emulsion; cooling to about 40 ℃, adding 1.4 parts of diethanolamine, adjusting the pH value to 8-8.5, and slowly dripping the shell monomer emulsion and the oxidant aqueous solution b into the nuclear layer emulsion for 260 min; after the shell monomer emulsion is dripped for 30min, 4 parts of the composition of bis (methacryloyloxyethyl) pyromellitic dianhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1:1 are added at a time.
5) After the dropwise addition, adding 2.6 parts of sodium bicarbonate, adjusting the pH value of the solution to 9.5-10, adding deionized water to 1000 parts of the total mass of the solution, heating to about 50 ℃, adjusting to the rotation speed of 400-600rpm, preserving heat, curing for 3 hours, and naturally cooling to room temperature to obtain the 50 mass percent benzene ring core-shell emulsion polymer (waterproof coating) for cement.
Example 6
A preparation method of a benzene ring core-shell emulsion polymer for cement is prepared by polymerizing the following components, wherein the total mass of the raw materials is 1000 parts, and the components and process parameters are as follows:
methacrylic alcohol: 3.5 parts of
1-phenyl vinyl boronic acid: 14.5
The composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate with the mass ratio of 3:1 is as follows: 0.3 part
Sodium methallyl sulfonate: 0.5 portion
Isopentenol: 10 portions of
A composition of 2-ethylhexyl acrylate and butyl acrylate in a mass ratio of 1: 2: 200 portions of
1:2 composition of 1-phenyl vinyl boronic acid and 4-methoxy-2-vinyl aniline: 228 portions of
Benzoyl peroxide: 1.5 parts of
Di-tert-butyl peroxide: 1.5 parts of
Sodium hypophosphite: 2.0 part by weight
A composition of bis (methacryloyloxyethyl) pyromellitic anhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1: 4 portions of
Diethanolamine: 1.6 parts of
Sodium bicarbonate: 2.4 parts of
The composition with the mass ratio of trifluoroethyl acrylate to perfluorooctyl ethyl acrylate being 1: 30 portions of
The remaining component was deionized water.
1) Preparing an emulsifier: directly adding 10 parts of deionized water, 3.5 parts of methyl allyl alcohol, 14.5 parts of 1-phenyl vinyl boric acid, 0.3 part of a composition of dicyclohexyl peroxydicarbonate and tert-butyl peroxypivalate with the mass ratio of 3:1 and 0.5 part of sodium methallyl sulfonate into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react for 2 hours at 80 ℃, preserving heat and curing for 1 hour, and cooling to obtain the emulsifier.
2) Preparation of an aqueous nuclear monomer solution: mixing 10 parts of prenol, 200 parts of a composition of 2-ethylhexyl acrylate and butyl acrylate in a mass ratio of 1:2 and 1.0 part of sodium hypophosphite to prepare a nuclear monomer aqueous solution with the mass fraction of 50%; 1.5 parts of benzoyl peroxide and 50 parts of deionized water are mixed to prepare an oxidant aqueous solution a, and the oxidant aqueous solution a is uniformly stirred for standby.
3) Preparing a shell monomer emulsion: 228 parts of 1:2 composition of 1-phenyl vinyl boric acid and 4-methoxy-2-vinyl aniline, 1.0 part of sodium hypophosphite, 1/3 composition prepared in the step (1) and 30 parts of composition of trifluoroethyl acrylate and perfluorooctyl ethyl acrylate in the mass ratio of 1:1 are mixed, stirred, dispersed and emulsified for 30min at the rotating speed of 1000-1200rpm to prepare shell monomer emulsion with the mass fraction of 50%; preparing 1.5 parts of di-tert-butyl peroxide and 60 parts of deionized water into an initiator aqueous solution b, and uniformly stirring for later use.
4) Adding 350 parts of deionized water and the rest of the emulsifying agent prepared in the step (1) 2/3 into a reaction container, uniformly stirring, heating to 45 ℃, adding 20% of nuclear monomer aqueous solution and 20% of oxidant aqueous solution a at one time, continuously stirring and preserving heat for 60min to obtain seed microemulsion; dropwise adding the rest 80% of the nuclear monomer aqueous solution and 80% of the oxidant aqueous solution a into the seed microemulsion at a constant speed for 80-120min, and stirring and preserving heat for 40min at the rotation speed of 600-800rpm after the dropwise adding is finished to obtain nuclear layer emulsion; cooling to about 40 ℃, adding 1.6 parts of diethanolamine, adjusting the pH value to 8-8.5, and slowly dripping the shell monomer emulsion and the oxidant aqueous solution b into the nuclear layer emulsion for 260 min; after the shell monomer emulsion is dripped for 30min, 4 parts of the composition of bis (methacryloyloxyethyl) pyromellitic dianhydride ester and pyromellitic dianhydride hydroxyethyl dimethacrylate in a mass ratio of 1:1 are added at a time.
5) After the dropwise addition, adding 2.4 parts of sodium bicarbonate, adjusting the pH value of the solution to 9.5-10, adding deionized water to 1000 parts of the total mass of the solution, heating to about 50 ℃, adjusting to the rotation speed of 400-600rpm, preserving heat, curing for 3 hours, and naturally cooling to room temperature to obtain the 50 mass percent benzene ring core-shell emulsion polymer (waterproof coating) for cement.
The performance tests of each example are as follows:
as can be seen from the above table, the carboxyl benzenoid core-shell emulsion polymer waterproof coating has better performance than the traditional market waterproof coating, and is suitable for the current market demand and the optimization of waterproof products. The combination of example 5 shows the excellent properties of the invention, and the final coating product has good stability, long storage time, good elongation, high tensile strength, wear resistance, impact resistance and no after tack under high temperature conditions. The paint has high bonding strength, contains a large amount of polymers with strong hydrophilic hydroxyl groups and rigid benzene rings, is very suitable for preventing the surfaces of steel products from rusting, aging and acid and alkali corrosion, and has the advantages of simple preparation method, low requirements on production process and equipment, convenient construction and environmental protection.
Claims (8)
1. The preparation method of the benzene ring core-shell emulsion polymer for cement is characterized by sequentially comprising the following operation steps of:
preparing an emulsifier in step (1): directly adding 8-12 parts of deionized water, 3.0-5.5 parts of hydroxyl hydrophilic small monomer for emulsification, 8.0-17.0 parts of benzene ring hydrophobic small monomer for emulsification, 0.2-0.45 part of emulsion initiator and 0.35-0.75 part of chain transfer agent into a three-neck flask with a stirring device, uniformly stirring, controlling the temperature to react at 70-90 ℃ for 2-3 hours, preserving heat and curing for 1-2 hours, and cooling to obtain an emulsifier; the hydroxyl hydrophilic small monomer for emulsification is monomer propylene alcohol and/or methyl propylene alcohol; the benzene ring hydrophobic small monomer for emulsification is 1-phenyl vinyl boric acid and/or 4-methoxy-2-vinylaniline;
preparing a nuclear monomer aqueous solution in step (2): mixing 8.2-12.0 parts of hydroxyl hydrophilic small monomer, 180-230 parts of acrylic soft monomer and 0.8-1.2 parts of reducing agent to prepare a nuclear monomer aqueous solution; mixing 1.0-2.1 parts of oxidant and 60-80 parts of deionized water to prepare an oxidant aqueous solution a, and uniformly stirring for later use;
preparing shell monomer emulsion in step (3): mixing 265 parts of benzene ring hydrophobic small monomer 200-265 parts, 23-40 parts of fluorine functional monomer, 0.5-1.0 part of reducing agent and 1/3 part of emulsifier prepared in the step (1), stirring, dispersing and emulsifying at the rotation speed of 1000-1200rpm for 30-60min to prepare shell monomer emulsion; mixing 1.0-2.1 parts of oxidant and 60-80 parts of deionized water to prepare an oxidant aqueous solution b, and uniformly stirring for later use; the fluorine functional monomer is trifluoroethyl acrylate and/or perfluorooctyl ethyl acrylate;
step (4) adding 300 and 450 parts of deionized water and the rest of 2/3 of the emulsifier prepared in the step (1) into a reaction vessel, uniformly stirring, heating to 45-50 ℃, adding 20% of nuclear monomer aqueous solution and 20% of oxidant aqueous solution a at one time, continuously stirring and preserving heat for 40-60min to obtain seed microemulsion; dropwise adding the rest 80% of the nuclear monomer aqueous solution and 80% of the oxidant aqueous solution a into the seed microemulsion at a constant speed for 80-120min, and stirring and preserving heat for 30-40min at the rotation speed of 600-800rpm after the dropwise adding is finished to obtain nuclear layer emulsion; cooling to 40-45 ℃, adding 1.2-2.5 parts of neutralizer, adjusting the pH to 8-8.5, and slowly dripping the shell monomer aqueous solution and the oxidant aqueous solution b into the core layer emulsion for 260 min; after the shell monomer aqueous solution is dripped for 60min, 2.8-6.5 parts of cross-linking agent is added at one time;
after the dropwise addition in the step (5), adding 2.1-4.0 parts of neutralizer, adjusting the pH of the solution to 9.5-10, adding deionized water to 1000 parts of the total mass of the solution, heating to 50-60 ℃, adjusting to the rotation speed of 400-600rpm, preserving heat, curing for 2-5 hours, and naturally cooling to room temperature to obtain the benzene ring core-shell emulsion polymer for cement;
in the step (2), the hydroxyl hydrophilic small monomer is any one or more of allyl alcohol, methyl allyl alcohol, isoamylene alcohol and 4- (ethyleneoxy) -1-butanol;
in the step (3), the benzene ring hydrophobic small monomer is any one or more of styrene, 1-allyl-2-fluorobenzene, 1-allyl-4-fluorobenzene, 1-phenyl vinyl boric acid and 4-methoxy-2-vinyl aniline.
2. The method for preparing a benzene ring-based core-shell emulsion polymer for cement according to claim 1, wherein: in the step (1), the emulsion initiator is any one or more of lauroyl peroxide, tert-butyl peroxypivalate and dicyclohexyl peroxydicarbonate.
3. The method for preparing a benzene ring-based core-shell emulsion polymer for cement according to claim 1, wherein: in the step (1), the chain transfer agent is sodium hypophosphite and/or sodium methallyl sulfonate.
4. The method for preparing a benzene ring-based core-shell emulsion polymer for cement according to claim 1, wherein: in the step (2), the oxidant is benzoyl peroxide and/or di-tert-butyl peroxide.
5. The method for preparing a benzene ring-based core-shell emulsion polymer for cement according to claim 1, wherein: in the step (4), the cross-linking agent is pyromellitic dianhydride hydroxyethyl dimethacrylate.
6. The method for preparing a benzene ring-based core-shell emulsion polymer for cement according to claim 1, wherein: in the step (2), the reducing agent is any one or more of sodium hydrosulfite, ascorbic acid, sodium formaldehyde sulfoxylate, maltodextrin, sodium bisulfite, sodium metabisulfite and sodium hypophosphite.
7. The method for preparing a benzene ring-based core-shell emulsion polymer for cement according to claim 1, wherein: in the step (2), the acrylate soft monomer is one or more of butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, ethyl acrylate and acrylic acid.
8. A benzene ring core-shell emulsion polymer for cement is characterized in that: prepared by the process of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910873932.XA CN110606918B (en) | 2019-09-17 | 2019-09-17 | Preparation method of benzene ring core-shell emulsion polymer for cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910873932.XA CN110606918B (en) | 2019-09-17 | 2019-09-17 | Preparation method of benzene ring core-shell emulsion polymer for cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110606918A CN110606918A (en) | 2019-12-24 |
| CN110606918B true CN110606918B (en) | 2022-02-01 |
Family
ID=68891384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910873932.XA Active CN110606918B (en) | 2019-09-17 | 2019-09-17 | Preparation method of benzene ring core-shell emulsion polymer for cement |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110606918B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234114B (en) * | 2020-03-17 | 2021-06-15 | 中国核工业中原建设有限公司 | Preparation method of polymer latex for improving impermeability of cement-based concrete |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2729150A1 (en) * | 1995-01-06 | 1996-07-12 | Rhone Poulenc Chimie | WATER REDISPERSABLE POWDERS OF FILMOGENIC POLYMERS HAVING A HEART / SKIN STRUCTURE |
| CN104530304B (en) * | 2014-11-03 | 2016-07-13 | 上海三瑞高分子材料有限公司 | A kind of concrete base building material low Tg acrylic acid ester emulsion and preparation method |
| CN106866869A (en) * | 2017-02-23 | 2017-06-20 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of core shell structure hydroxyl acrylic emulsion |
| CN109554054A (en) * | 2018-12-07 | 2019-04-02 | 东联北方科技(北京)有限公司 | Polymer cement waterproof paint and preparation method thereof |
-
2019
- 2019-09-17 CN CN201910873932.XA patent/CN110606918B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110606918A (en) | 2019-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101781390B (en) | Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall | |
| CN107118650B (en) | Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof | |
| CN103570881B (en) | A kind of polyacrylate grafting vinyl chloride composite resin and preparation method thereof | |
| CN109054570B (en) | Environment-friendly high-strength elastic coating and preparation method thereof | |
| CN101838371A (en) | Method for preparing high-solid-content and low-viscosity core-shell structure styrene-acrylic emulsion | |
| CN105622831A (en) | Preparation method of acrylic acid organic silicon soap-free copolymerization emulsion | |
| CN101735541A (en) | Environmental-friendly type emulsion for heat insulating material and preparation method thereof | |
| CN111138600B (en) | Butylbenzene-modified zero-ammonia acrylic waterproof mortar emulsion, preparation method thereof and waterproof mortar | |
| CN103626909B (en) | Weather-proof barrier coating and its application | |
| CN110669181A (en) | Preparation method of novel acrylate emulsion for wood paint | |
| CN110606918B (en) | Preparation method of benzene ring core-shell emulsion polymer for cement | |
| CN110627963B (en) | Preparation method of quaternary ammonium salt and quaternary phosphonium salt cation core-shell emulsion polymer | |
| CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN112940170B (en) | Real stone paint emulsion and preparation method thereof | |
| CN113563503A (en) | Preparation method of environment-friendly water-resistant yellowing-resistant copolymer emulsion | |
| CN110591008B (en) | Preparation method of cationic alkyl core-shell emulsion polymer | |
| CN110591009B (en) | Preparation method of graphene oxide reinforced waterproof polymer emulsion | |
| CN105802306A (en) | Preparation method of building fireproof coating | |
| CN110698603B (en) | Preparation method of core-shell type carboxyl benzene ring emulsion polymer for coating | |
| CN108424488B (en) | Anti-fouling and water-resistant silicone-acrylate emulsion and preparation method thereof | |
| CN105969250A (en) | Production technique of transparent EVA (ethylene-vinyl acetate) packaging adhesive film for double-glazed solar photovoltaic modules | |
| CN107556429B (en) | Silicone-acrylic emulsion and preparation method thereof | |
| CN110642982B (en) | Preparation method of high-tensile-strength amide benzene ring emulsion polymer with core-shell structure | |
| CN111978455B (en) | Hydrophobic fluorine modified acrylic emulsion and preparation method and application thereof | |
| CN104725570A (en) | Latex and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20191224 Assignee: Kunming Wangtianhong Printing Co.,Ltd. Assignor: HUBEI University OF TECHNOLOGY Contract record no.: X2023980036253 Denomination of invention: A preparation method of benzene ring core-shell lotion polymer for cement Granted publication date: 20220201 License type: Common License Record date: 20230607 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20191224 Assignee: Yunnan Kunzhong Environmental Engineering Co.,Ltd. Assignor: HUBEI University OF TECHNOLOGY Contract record no.: X2023420000278 Denomination of invention: A preparation method of benzene ring core-shell lotion polymer for cement Granted publication date: 20220201 License type: Common License Record date: 20230808 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20191224 Assignee: HUBEI JOYOUNG WATERPROOFING MATERIAL TECHNOLOGY Co.,Ltd. Assignor: HUBEI University OF TECHNOLOGY Contract record no.: X2023980041139 Denomination of invention: A preparation method of benzene ring core-shell lotion polymer for cement Granted publication date: 20220201 License type: Common License Record date: 20230904 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240409 Address after: 101200 room 205-211526, No. 40, Fuqian West Street, Pinggu town, Pinggu District, Beijing (cluster registration) Patentee after: BEIJING YONGBO TECHNOLOGY CO.,LTD. Country or region after: China Address before: 430068 1, Lijia 1 village, Nanhu, Wuchang District, Wuhan, Hubei Patentee before: HUBEI University OF TECHNOLOGY Country or region before: China |
|
| TR01 | Transfer of patent right |