CN112759725B - Nano mud-resistant slump-retaining polycarboxylate superplasticizer and preparation method thereof - Google Patents
Nano mud-resistant slump-retaining polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN112759725B CN112759725B CN202110028650.7A CN202110028650A CN112759725B CN 112759725 B CN112759725 B CN 112759725B CN 202110028650 A CN202110028650 A CN 202110028650A CN 112759725 B CN112759725 B CN 112759725B
- Authority
- CN
- China
- Prior art keywords
- mud
- resistant
- slump
- nano
- retaining
- 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
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000008030 superplasticizer Substances 0.000 title abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 65
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 45
- 239000004567 concrete Substances 0.000 claims abstract description 40
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 30
- 229920000570 polyether Polymers 0.000 claims abstract description 30
- 150000003077 polyols Chemical group 0.000 claims abstract description 18
- 239000004576 sand Substances 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 239000000839 emulsion Substances 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 229920005862 polyol Polymers 0.000 claims description 17
- 229920000151 polyglycol Polymers 0.000 claims description 16
- 239000010695 polyglycol Substances 0.000 claims description 16
- -1 polyoxyethylene Polymers 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- BTVWZWFKMIUSGS-UHFFFAOYSA-N 2-methylpropane-1,2-diol Chemical compound CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 claims 1
- 239000004816 latex Substances 0.000 claims 1
- 229920000126 latex Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 17
- 239000004568 cement Substances 0.000 abstract description 7
- 239000000693 micelle Substances 0.000 abstract description 7
- 239000002002 slurry Substances 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 76
- 239000000203 mixture Substances 0.000 description 49
- 239000000243 solution Substances 0.000 description 44
- 238000003756 stirring Methods 0.000 description 33
- 239000012986 chain transfer agent Substances 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 18
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000502 dialysis Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000004574 high-performance concrete Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- AOAGVPIEEAAAOL-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrogen peroxide Chemical compound OO.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O AOAGVPIEEAAAOL-RXSVEWSESA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000007908 nanoemulsion Substances 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229920005614 potassium polyacrylate Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a nano mud-resistant slump-retaining polycarboxylic acid water reducer. The nanometer mud-resistant slump-retaining polycarboxylate superplasticizer is prepared by the following steps: (1) and preparing the anti-mud cross-linking agent. (2) And (4) carrying out polymerization reaction. The invention obtains the nanometer mud-resistant slump-retaining polycarboxylic acid water reducer with the cross-linking structure by carrying out emulsion polymerization on a polymerizable emulsifier with a sulfonate structure, a mud-resistant cross-linking agent with a polyether polyol structure and a plurality of monomers. Through crosslinking and hardening of the nano micelle structure, the dispersing performance of the water reducer molecule can be effectively improved, so that the slurry is thickened and thinned, the mud resistance of the water reducer is enhanced, and the adaptability to different sandstone aggregates and the workability of concrete are improved. The nano mud-resistant slump-retaining polycarboxylate water reducer can be gradually hydrolyzed in cement paste, on one hand, a plurality of mud-resistant small molecules are released to enable the cement paste to have long-term mud-resistant performance, and on the other hand, micelles are cracked through cross-linking structure fracture and hydrophilic and hydrophobic changes, so that linear polycarboxylate molecules are released to achieve a long-term slump-retaining effect. The water reducing agent can also be used as a regulator in machine-made sand concrete.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a nano mud-resistant slump-retaining polycarboxylic acid water reducer and a preparation method thereof.
Background
With the rapid increase of the current social development and various engineering construction requirements, the preparation technology and performance of concrete as one of the most important building engineering materials are continuously developed. The current construction requirements are high for the fluidity and the holding capacity of concrete, and the mineral admixture and the functional admixture which are used in large amount in high-performance concrete also make the fluidity and the holding for a long time more difficult. In addition, because of wide regions in China, obvious change of temperature and humidity along with seasons and large difference of raw materials used for concrete, the phenomenon of insufficient fluidity or over-quick loss often occurs in the processes of mixing and transporting the concrete.
The chemical admixture is one of important guarantees of the performance of high-performance concrete, wherein the polycarboxylic acid water reducing agent has the advantages of low mixing amount, high water reducing rate, good slump retaining performance, low shrinkage rate, large modification potential and the like, is widely applied to concrete configuration, and replaces the traditional lignosulfonate and naphthalene water reducing agents to become main products in the current water reducing agent market. In order to make up for the deficiency of slump retaining performance, a polycarboxylic acid slump retaining agent matched with the slump retaining agent is usually compounded into a polycarboxylic acid additive for use. Conventional polycarboxylic acid admixtures are mixtures of linear polymers with long comb-like branches, with a high amount of carboxylic acid, carboxylate groups and polyether long branches, which can effectively increase and maintain the flow properties of the concrete by dispersion, ionization and subsequent hydrolysis. However, the conventional polycarboxylic acid admixture easily reacts with clay due to its own molecular structure, because the clay has an aluminosilicate mineral with a large specific surface area and a multi-layered structure, which has strong adsorption and intercalation effects with respect to the long-chain branched structure of the polycarboxylic acid admixture. Therefore, the conventional polycarboxylic acid admixture is very sensitive to the mud content in the aggregate, and as the mud content increases, the dispersing performance and slump retaining performance of the polycarboxylic acid admixture are obviously reduced, so that the working performance of concrete is greatly reduced. Nowadays, natural sand resources in China are increasingly exhausted, and machine-made sand aggregate gradually replaces natural sand to become a main construction sand source. Because the production processes and raw material quality of different regions and enterprises are different, the quality fluctuation of the produced machine-made sand aggregate is large, and the problems of powder content, high mud content, more needle-shaped particles and the like are often attached, so that the working performance and the workability of the related concrete are influenced.
Research shows that some special structures or functional groups can be preferentially combined with soil, so that the influence of clay minerals on the polycarboxylic acid admixture is reduced. Patent CN109776742A discloses a phosphate ester-containing anti-mud type polycarboxylate water reducing agent, which can effectively improve the dispersibility in high mud content concrete by copolymerizing unsaturated phosphate ester monomers in a polycarboxylate molecular chain. Patent CN104961377B discloses a method for preparing a polycarboxylic acid water reducing agent by introducing a sacrificial agent containing a large amount of anions, such as a potassium polyacrylate aqueous solution or polyacrylic acid-sodium methallylsulfonate, which can improve the adaptability of the polycarboxylic acid water reducing agent to high-mud-content sand. Patent CN106517857A discloses a special polycarboxylic acid water reducer for high-mud-content system ultra-long slump retaining concrete, which synergistically resists mud by compounding slow-release, slow-setting, slump retaining and organic cationic polymers to prolong slump retaining time.
The mud-resistant admixture prepared by the prior art has unsatisfactory effect and mechanism when used for solving the problem of high mud content, is accompanied by the problems of cost increase, difficult use and unstable effect, and is difficult to produce and apply on a large scale. Therefore, the research of the mud-resistant polycarboxylic acid admixture with higher adaptability has important significance for the whole industry.
Disclosure of Invention
The invention aims to solve the problems and provides a nano mud-resistant slump-retaining polycarboxylic acid water reducer and a preparation method thereof.
The nanometer mud-resistant slump-retaining polycarboxylic acid water reducing agent is a polymer nanometer micelle which is synthesized by a polyether macromonomer, unsaturated carboxylic acid, unsaturated carboxylic ester, a styrene monomer, a mud-resistant crosslinking agent and a polymerizable mud-resistant emulsifier through emulsion polymerization and has a crosslinking structure, wherein the mud-resistant crosslinking agent is at least one of multifunctional monomers obtained by esterification reaction of polyether polyol and unsaturated anhydride, and the using amount of the mud-resistant crosslinking agent is 2-8% of the total amount of the monomers.
The polyether macromonomer: unsaturated carboxylic acid: unsaturated carboxylic acid ester: the molar ratio of the styrene monomers is 1: (1-5): (4-12): (1-8).
The polyether macromonomer is at least one of isobutylene polyglycol ether (HPEG), prenol polyglycol ether (TPEG), Allyl Polyglycol Ether (APEG) and ethylene glycol monovinyl Ether Polyoxyethylene Ether (EPEG) with the molecular weight of 1600-4000, the unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, fumaric acid and itaconic acid, the unsaturated carboxylic acid ester is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate, and the styrene monomer is at least one of styrene, p-chloro methyl styrene, 4-methyl styrene and alpha-methyl styrene.
The polymerizable anti-mud emulsifier has a molecular structure of
n is 7-15, and the dosage of n is 1-2% of the monomer.
The polyether polyol is at least one of polymer polyol, polyoxyethylene polyol, polyoxypropylene polyol, polytetrahydrofuran polyol and copolyether polyol with the molecular weight of 600-7000, and the unsaturated anhydride is at least one of acrylic anhydride, methacrylic anhydride, maleic anhydride and itaconic anhydride.
The preparation method of the nanometer mud-resistant slump-retaining polycarboxylate superplasticizer comprises the following steps:
(1) preparing an anti-mud cross-linking agent: and (2) carrying out esterification reaction on polyether polyol and unsaturated anhydride in a solvent added with a polymerization inhibitor under the action of a catalyst to obtain the multifunctional polyether anti-mud crosslinking agent.
(2) Polymerization reaction: adding most of initiator, polymerizable anti-mud emulsifier molecules and water into a reaction container, starting stirring to gradually dissolve an emulsifier, then adding part of mixed small monomers and a chain transfer agent, stirring to fully emulsify the mixture, then adding part of initiator solution, heating a reaction system to 75-85 ℃, dropwise adding the rest of mixed small monomers, chain transfer agent and all polyether large monomer solutions into the reaction container after reaction liquid is light blue, dropwise adding the rest of mixed small monomers, chain transfer agent and all polyether large monomer solutions into the reaction container for 1-3 hours, dropwise adding the cross-linking agent solution synthesized in the step (1) into the reaction container after dropwise adding is completed, keeping the temperature for 1 hour after the dropwise adding of the cross-linking agent is completed, slowly adding the rest of initiator, heating to 85-95 ℃, and reacting for 1-2 hours to obtain a polymerization product emulsion. And adding a proper amount of alkali into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
In the step (1), the molar ratio of the polyether polyol to the unsaturated anhydride is 1: (2.5-5), the reaction temperature is 40-60 ℃, the reaction time is 5-7 h, the solvent is one or a mixture of pyridine, N-dimethylformamide and dimethyl sulfoxide, the polymerization inhibitor is at least one of DPPH, hydroquinone, p-tert-butyl catechol or phenothiazine, the dosage is 0.1-2% of the total amount of reactants, and the catalyst is 4-dimethylaminopyridine, benzenesulfonic acid or p-toluenesulfonic acid, and the dosage is 0.5-5% of the mass of the reactants.
In the step (2), the chain transfer agent is at least one of mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, mercaptopropanol, sodium hypophosphite, trisodium phosphate and CTA1420, the dosage of the chain transfer agent is 0.2-2% of the dosage of the monomer, the initiator is at least one of potassium persulfate, ammonium persulfate, azodiisopropyl amidine hydrochloride, azodiisobutymidine dihydrochloride, a hydrogen peroxide-ascorbic acid initiation system, a hydrogen peroxide-rongalite initiation system and an ammonium persulfate-sodium sulfite initiation system, the dosage of the chain transfer agent is 0.3-3% of the dosage of the monomer, and the alkali is at least one of sodium hydroxide, potassium hydroxide, triethylamine and triethanolamine or an aqueous solution thereof.
The nanometer mud-resistant slump-retaining polycarboxylate superplasticizer and the preparation method thereof have the positive effects that:
compared with the existing polycarboxylic acid water reducing agent, the nano polycarboxylic acid water reducing agent prepared by the method has the advantages of good dispersing effect, high slump retaining effect, strong and lasting mud resisting effect, and good viscosity reducing and thickening effects on concrete with high viscosity, such as high-grade concrete, machine-made sand concrete with high powder content and the like. The nanometer polycarboxylate water reducer can be used independently, and can also be compounded with at least one of the existing known sulfamic acid, lignin and polycarboxylate water reducers for use, so that the slump retaining capability and the mud resistance of the existing water reducer product and the adaptability of machine-made sand aggregate are improved.
The nano water reducing agent is self-assembled into a nano micelle structure through amphiphilic polycarboxylic acid molecules, so that the steric effect is increased, the intercalation effect in the layered structure of clay minerals is effectively reduced, and the sensitivity of the nano water reducing agent to the mud content of aggregate is greatly reduced. Meanwhile, the soft nano-micelle is fixed to form hard nano-particles through the cross-linking structure, so that the condition that the micelle is dissolved and dissociated due to the fact that emulsion is stirred and diluted by water in a large quantity in the using process is avoided, and on the other hand, the hard nano-particles dispersed in the slurry in a large quantity can play a good internal lubricating role and can play a role in thickening, viscosity reduction, adjustment and workability. The ester group in the cross-linking agent and the amide group in the mud-resistant emulsifier can be gradually hydrolyzed and broken under the alkaline condition of concrete, so that the cross-linking structure is broken and the polyether polyol and sulfonate mud-resistant agent is released, thereby playing a role in resisting mud for a long time. And along with the fracture of the cross-linked structure and the gradual hydrolysis of ester groups in the polycarboxylic acid molecular chain into carboxylate radicals, the hydrophilicity and the dispersing performance of the polycarboxylic acid molecular chain are enhanced, the micelle is gradually dissociated, and a large number of linear polycarboxylic acid molecules are released to play a role in dispersing and reducing water, so that the long-time fluidity maintenance is realized. And the synergistic effect exists among different kinds of anti-mud crosslinking agents, the effects of inhibiting clay intercalation and resisting expansion in a long time can be achieved through the synergistic crosslinking adjustment of the crosslinking agents with the types and the dosage, and the continuous mud-resistant slump-retaining performance of the concrete can be effectively improved under special conditions of low temperature, high mud content and the like. Through the comprehensive effect of various reasons, the nano water reducing agent has excellent dispersing, slump retaining and mud resisting performances, and can effectively improve the continuous working performance of concrete in the mixing, transporting and pumping processes.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent A: 24g of polyoxyethylene glycol with the molecular weight of 600, 15g of acrylic anhydride, 0.3g of hydroquinone and 0.6g of p-toluenesulfonic acid are added into a reaction bottle containing 70g of pyridine to be stirred and dissolved, after the mixture is completely dissolved, the temperature is raised to 50 ℃ under the protection of nitrogen to carry out esterification reaction for 6 hours, and after the reaction is finished, the anti-mud crosslinking agent A is obtained through dialysis separation;
(2) polymerization reaction: adding 2g of polymerizable anti-mud emulsifier and 120g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40% of a mixture of small monomers and a chain transfer agent (containing 10g of acrylic acid, 10g of hydroxypropyl acrylate, 40g of butyl acrylate, 20g of styrene and 1.8g of mercaptoethanol) into the solution, stirring to fully emulsify the mixture, then adding 1.8g of ammonium persulfate, heating the reaction system to 75 ℃, dropwise adding the rest of the mixture of small monomers and the chain transfer agent and a polyether large monomer solution (containing 100g of isopentenol polyethylene glycol ether with the molecular weight of 2400 and 80g of water) into the reaction container after the reaction solution presents a light blue emulsion for 2 hours, dropwise adding water-soluble droplets containing 8g of anti-mud cross-linking agent A into the reaction container after dropwise adding is completed, dropwise adding for 30 minutes, then preserving heat for 1 hour, and slowly adding 0.5g of ammonium persulfate, heating to 85 ℃ and reacting for 1h to obtain the emulsion of the polymerization product. And then adding 30% sodium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to be required to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Example 2: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent B: adding 40g of polyoxypropylene diol with the molecular weight of 1000, 12g of maleic anhydride, 0.5g of phenothiazine and 1g of benzenesulfonic acid into a reaction bottle containing 80g N, N-dimethylformamide, stirring for dissolving, heating to 45 ℃ under the protection of nitrogen after completely dissolving, carrying out esterification reaction for 8 hours, and obtaining an anti-mud crosslinking agent B after the reaction is finished and dialysis separation;
(2) polymerization reaction: adding 1.8g of polymerizable anti-mud emulsifier and 120g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40 percent of a mixture of small monomers and a chain transfer agent (containing 4g of methacrylic acid, 12g of hydroxyethyl acrylate, 30g of methyl methacrylate, 30g of p-chloromethyl styrene and 2g of mercaptopropionic acid) into the solution, stirring to fully emulsify the mixture, then adding 1.5g of potassium persulfate, heating the reaction system to 80 ℃, after the reaction liquid presents light blue emulsion, dropwise adding the rest mixture of small monomers and the chain transfer agent and a polyether macromonomer solution (containing 100g of isobutenol polyglycol ether with the molecular weight of 2400 and 80g of water) into the reaction container for 1.5 hours, adding 4g of anti-mud crosslinking agent B into the reaction container after dropwise adding, dropwise adding for 40 minutes, and then keeping the temperature for 1 hour, then slowly adding 0.5g of potassium persulfate, heating to 85 ℃ and reacting for 1 hour to obtain a polymerization product emulsion. And then adding 30% potassium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to be required to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Example 3: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent B: same as example 2, step (1);
(2) polymerization reaction: adding 1.8g of polymerizable anti-mud emulsifier and 120g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40 percent of a mixture of small monomers and a chain transfer agent (containing 4g of methacrylic acid, 12g of hydroxyethyl acrylate, 30g of methyl methacrylate, 30g of p-chloromethyl styrene and 2g of mercaptopropionic acid) into the solution, stirring to fully emulsify the mixture, then adding 1.5g of potassium persulfate, heating the reaction system to 80 ℃, after the reaction liquid presents light blue emulsion, dropwise adding the rest mixture of small monomers and the chain transfer agent and a polyether macromonomer solution (containing 100g of isobutenol polyglycol ether with the molecular weight of 2400 and 80g of water) into the reaction container for 1.5 hours, adding 13g of anti-mud crosslinking agent B into the reaction container after dropwise adding, dropwise adding for 40 minutes, and then keeping the temperature for 1 hour, slowly adding 0.5g of potassium persulfate, heating to 85 ℃, and reacting for 1 hour to obtain a polymerization product emulsion. And then adding 30% of potassium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to the required value to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Example 4: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent C: adding 60g of polytetrahydrofuran diol with the molecular weight of 2400, 12g of methacrylic anhydride, 0.5g of DPPH and 0.6g of 4-dimethylaminopyridine into a reaction bottle containing 100g of pyridine, stirring for dissolving, heating to 55 ℃ under the protection of nitrogen after completely dissolving, carrying out esterification reaction for 6 hours, and obtaining the anti-mud crosslinking agent C after the reaction is finished and dialysis separation;
(2) polymerization reaction: adding 2.5g of polymerizable anti-mud emulsifier and 100g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40 percent of a mixture of small monomers and a chain transfer agent (containing 3g of acrylic acid, 5g of fumaric acid, 12g of butyl acrylate, 32g of methyl methacrylate, 30g of 4-methyl styrene and 1.3g of thioglycolic acid) into the solution, stirring to fully emulsify the mixture, then adding 2g of azodiisopropyl amidine hydrochloride, heating the reaction system to 82 ℃, after the reaction liquid presents light blue emulsion, dropwise adding the rest mixture of the small monomers and the chain transfer agent and a polyether type large monomer solution (containing 140g of prenol polyethylene glycol ether with the molecular weight of 3600 and 100g of water) into the reaction container for 2.5 hours, dropwise adding 10g of anti-mud crosslinking agent C into the reaction container after the dropwise adding is completed, and dropwise adding water for 45 minutes, then preserving the heat for 1h, slowly adding 0.6g of azodiisopropyl amidine oxazoline hydrochloride, heating to 90 ℃ and reacting for 1h to obtain the emulsion of the polymerization product. And then adding 30% sodium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to be required to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Example 5: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent D: adding 65g of polyoxyethylene triol with the molecular weight of 3000, 15g of itaconic anhydride, 0.6g of p-tert-butyl catechol and 1.4g of 4-dimethylaminopyridine into a reaction bottle containing 100g of dimethyl sulfoxide, stirring for dissolving, heating to 60 ℃ under the protection of nitrogen after complete dissolution, carrying out esterification reaction for 6h, and obtaining an anti-mud crosslinking agent D after the reaction is finished and through dialysis separation;
(2) polymerization reaction: adding 3g of polymerizable anti-mud emulsifier and 100g of water into a reaction vessel, starting stirring to dissolve the emulsifier, then adding 40% of a mixture of small monomers and a chain transfer agent (containing 4g of acrylic acid, 4g of itaconic acid, 10g of methyl acrylate, 30g of butyl acrylate, 10g of hydroxybutyl methacrylate, 25g of alpha-methylstyrene and 25g of CTA-14201.5 g) into the solution, stirring to fully emulsify the mixture, then adding 1.8g of potassium persulfate, heating the reaction system to 80 ℃, after the reaction liquid presents light blue emulsion, dropwise adding the rest mixture of the small monomers and the chain transfer agent and a polyether large monomer solution (containing 120g of methacrylate polyglycol ether with the molecular weight of 3000 and 100g of water) into the reaction vessel for 2 hours, dropwise adding water-soluble droplets containing 9g of anti-mud cross-linking agent D into the reaction vessel for 35 minutes after dropwise adding is completed, then preserving the heat for 1h, slowly adding 0.6g of potassium persulfate, heating to 85 ℃ and reacting for 1h to obtain a polymerization product emulsion. And then adding 30% potassium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to be required to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Example 6: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent D: same as example 5, step (1);
(2) polymerization reaction: adding 2g of polymerizable anti-mud emulsifier and 120g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40% of a mixture of small monomers and a chain transfer agent (containing 10g of acrylic acid, 10g of hydroxypropyl acrylate, 40g of butyl acrylate, 20g of styrene and 1.8g of mercaptoethanol) into the solution, stirring to fully emulsify the mixture, then adding 1.8g of ammonium persulfate, heating the reaction system to 75 ℃, dropwise adding the rest of the mixture of small monomers and the chain transfer agent and a polyether large monomer solution (containing 100g of isopentenol polyethylene glycol ether with the molecular weight of 2400 and 80g of water) into the reaction container after the reaction solution presents a light blue emulsion for 2 hours, dropwise adding water-soluble droplets containing 8g of anti-mud cross-linking agent A into the reaction container after dropwise adding is completed, dropwise adding for 30 minutes, then preserving heat for 1 hour, and slowly adding 0.5g of ammonium persulfate, heating to 85 ℃ and reacting for 1h to obtain the emulsion of the polymerization product. And then adding 30% sodium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to be required to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Example 7: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent A: same as example 1, step (1);
(2) preparing an anti-mud cross-linking agent D: same as example 5, step (1);
(3) polymerization reaction: adding 2g of polymerizable anti-mud emulsifier and 120g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40% of a mixture of small monomers and a chain transfer agent (containing 10g of acrylic acid, 10g of hydroxypropyl acrylate, 40g of butyl acrylate, 20g of styrene and 1.8g of mercaptoethanol) into the solution, stirring to fully emulsify the mixture, then adding 1.8g of ammonium persulfate, heating the reaction system to 75 ℃, dropwise adding the rest of the mixture of small monomers and the chain transfer agent and a polyether large monomer solution (containing 100g of isopentenol polyethylene glycol ether with the molecular weight of 2400 and 80g of water) into the reaction container after the reaction solution is in a light blue emulsion, dropwise adding water solution containing 4g of anti-mud cross-linking agent A and 4g of anti-mud cross-linking agent D into the reaction container for 2 hours, dropwise adding water solution containing 4g of anti-mud cross-linking agent A and 4g of anti-mud cross-linking agent D for 30 minutes, and then preserving the temperature for 1 hour, then 0.5g of ammonium persulfate is slowly added, and the temperature is raised to 85 ℃ to react for 1h, thus obtaining the emulsion of the polymerization product. And then adding 30% sodium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to be required to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Example 8: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent A: same as example 1 step (1)
(2) Preparing an anti-mud cross-linking agent E: adding 80g of polyoxypropylene triol with the molecular weight of 4000, 15g of acrylic anhydride, 0.7g of hydroquinone and 1.5g of p-toluenesulfonic acid into a reaction bottle containing 100g of pyridine, stirring for dissolving, heating to 60 ℃ under the protection of nitrogen after complete dissolution for esterification reaction for 8 hours, and obtaining the anti-mud crosslinking agent E through dialysis separation after the reaction is finished;
(3) polymerization reaction: adding 1.6g of polymerizable anti-mud emulsifier and 80g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40 percent of a mixture of a small monomer and a chain transfer agent (containing 3g of acrylic acid, 3g of methacrylic acid, 25g of butyl methacrylate, 25g of styrene and 3g of trisodium phosphate) into the solution, stirring to fully emulsify the mixture, then adding 1.5g of ammonium persulfate, heating the reaction system to 75 ℃, after the reaction solution presents light blue emulsion, dropwise adding the rest mixture of the small monomer and the chain transfer agent and a polyether large monomer solution (containing 20g of isobutenol polyglycol ether with the molecular weight of 1600, 80g of isopentenol polyglycol ether with the molecular weight of 3000 and 100g of water) into the reaction container for 2 hours, dropwise adding water-soluble liquid containing 6g of anti-mud cross-linking agent A and 6g of anti-mud cross-linking agent E into the reaction container after dropwise adding is finished, the dropping time is 45min, then the temperature is kept for 1h, 0.5g of ammonium persulfate is slowly added, the temperature is raised to 85 ℃ and the reaction is carried out for 1h, thus obtaining the emulsion of the polymerization product. And then regulating the pH value of triethanolamine to about 6, and then regulating the solid content to the required value to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Example 9: a nanometer anti-mud slump-retaining polycarboxylate superplasticizer and a preparation method thereof are as follows
(1) Preparing an anti-mud cross-linking agent C: same as example 3, step (1);
(2) preparing an anti-mud cross-linking agent F: adding 80g of polytetrahydrofuran triol with the molecular weight of 5000, 14g of acrylic anhydride, 0.3g of DPPH and 1.6g of 4-dimethylaminopyridine into a reaction bottle containing 100g of pyridine, stirring for dissolving, heating to 60 ℃ under the protection of nitrogen after completely dissolving, carrying out esterification reaction for 8 hours, and obtaining an anti-mud crosslinking agent F through dialysis separation after the reaction is finished;
(3) polymerization reaction: adding 1.8g of polymerizable anti-mud emulsifier and 100g of water into a reaction vessel, starting stirring to dissolve the emulsifier, then adding 40% of a mixture of a small monomer and a chain transfer agent (containing 4g of acrylic acid, 2g of fumaric acid, 2g of itaconic acid, 25g of methyl methacrylate, 26g of 4-methylstyrene and 1.5g of mercaptopropanol) into the solution, stirring to fully emulsify the mixture, then adding 2g of azobisisobutyramidine dihydrochloride, heating the reaction system to 82 ℃, dropwise adding the rest of the mixture of the small monomer and the chain transfer agent and a polyether type large monomer solution (containing 40g of allyl polyglycol ether with the molecular weight of 2400, 60g of isopentenol polyglycol ether with the molecular weight of 4000 and 100g of water) into the reaction vessel for 2.5 hours after the reaction solution is in a light blue emulsion, dropwise adding water solution containing 8g of anti-mud cross-linking agent C and 5g of anti-mud cross-linking agent F into the reaction vessel, the dropping time is 30min, then the temperature is kept for 1h, 0.6g of azobisisobutyramidine dihydrochloride is slowly added, the temperature is raised to 90 ℃ and the reaction is carried out for 1h, thus obtaining the emulsion of the polymerization product. And adding triethylamine into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to the required value to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Comparative example 1: conventional linear polycarboxylic acid water reducing agent
Adding 100g of isobutylene polyglycol ether with the molecular weight of 2400 into a reaction bottle containing 90g of water, uniformly stirring, adding 1g of hydrogen peroxide, uniformly stirring, dropwise adding a polymerization monomer solution (containing 10g of acrylic acid, 8g of hydroxypropyl acrylate and 20g of water) and a reducing agent solvent (containing 0.5g of ascorbic acid, 1g of mercaptopropionic acid and 30g of water) into the reaction container for reaction, wherein the reaction starting temperature is 25 ℃, the dropwise adding time is 2 hours and 2.5 hours respectively, and preserving heat for 2.5 hours after the dropwise adding is finished to obtain a copolymerization product. Adding 35 percent of sodium hydroxide aqueous solution by mass fraction to neutralize until the pH value is about 6, thus obtaining the conventional linear polycarboxylate superplasticizer.
Comparative example 2: synthesis of conventional nano emulsion water reducing agent
Adding 1.8g of sodium dodecyl benzene sulfonate and 100g of water into a reaction container, stirring to dissolve the sodium dodecyl benzene sulfonate and the water, then adding 40% of a mixture of a small monomer and a chain transfer agent (containing 12g of acrylic acid, 40g of butyl acrylate, 10g of styrene and 1.5g of mercaptopropanol) into the solution, stirring to fully emulsify the mixture, then adding 2g of potassium persulfate, heating the reaction system to 82 ℃, after the reaction liquid presents a light blue emulsion, dropwise adding the rest mixture of the small monomer and the chain transfer agent and a polyether large monomer solution (containing 105g of prenyl alcohol glycol ether with the molecular weight of 2400 and 80g of water) into the reaction container, dropwise adding the mixture for 2.5 hours, then keeping the temperature for 1.5 hours, slowly adding 0.6g of potassium persulfate, heating to 90 ℃ and reacting for 1 hour to obtain a polymerization product emulsion. And then adding 30% sodium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to the required value to obtain the nano polycarboxylic acid water reducing agent.
Comparative example 3: anti-mud nano polycarboxylic acid water reducing agent
(1) Preparing an anti-mud cross-linking agent B: same as example 2, step (1);
(2) polymerization reaction: adding 1.8g of polymerizable anti-mud emulsifier and 120g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40 percent of a mixture of small monomers and a chain transfer agent (containing 4g of methacrylic acid, 12g of hydroxyethyl acrylate, 30g of methyl methacrylate, 30g of p-chloromethyl styrene and 2g of mercaptopropionic acid) into the solution, stirring to fully emulsify the mixture, then adding 1.5g of potassium persulfate, heating the reaction system to 80 ℃, after the reaction liquid presents light blue emulsion, dropwise adding the rest mixture of small monomers and the chain transfer agent and a polyether macromonomer solution (containing 100g of isobutenol polyglycol ether with the molecular weight of 2400 and 80g of water) into the reaction container for 1.5 hours, adding 2g of water solution containing the anti-mud crosslinking agent B into the reaction container after dropwise adding is completed, dropwise adding for 40 minutes, and then keeping the temperature for 1 hour, slowly adding 0.5g of potassium persulfate, heating to 85 ℃, and reacting for 1 hour to obtain a polymerization product emulsion. And then adding 30% potassium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to be required to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Comparative example 4: anti-mud nano polycarboxylic acid water reducing agent
(1) Preparing an anti-mud cross-linking agent B: same as example 2, step (1);
(2) polymerization reaction: adding 1.8g of polymerizable anti-mud emulsifier and 120g of water into a reaction container, starting stirring to dissolve the emulsifier, then adding 40 percent of a mixture of small monomers and a chain transfer agent (containing 4g of methacrylic acid, 12g of hydroxyethyl acrylate, 30g of methyl methacrylate, 30g of p-chloromethyl styrene and 2g of mercaptopropionic acid) into the solution, stirring to fully emulsify the mixture, then adding 1.5g of potassium persulfate, heating the reaction system to 80 ℃, after the reaction liquid presents light blue emulsion, dropwise adding the rest mixture of small monomers and the chain transfer agent and a polyether macromonomer solution (containing 100g of isobutenol polyglycol ether with the molecular weight of 2400 and 80g of water) into the reaction container for 1.5 hours, adding 16g of water solution containing the anti-mud crosslinking agent B into the reaction container after dropwise adding is completed, dropwise adding for 40 minutes, and then keeping the temperature for 1 hour, then slowly adding 0.5g of potassium persulfate, heating to 85 ℃ and reacting for 1 hour to obtain a polymerization product emulsion. And then adding 30% potassium hydroxide solution into the emulsion, adjusting the pH value to be about 6, and adjusting the solid content to be required to obtain the nano mud-resistant slump-retaining polycarboxylic acid water reducer.
Description of the effects:
the pure slurry flow is measured by using the nano mud-resistant slump-retaining polycarboxylate water reducer and the conventional polycarboxylate water reducer according to GB/T8077-2012 'test method for homogeneity of concrete admixture', and cement is reference cement. The test results are shown in Table 1.
TABLE 1 Cement paste fluidity test results
"/" is no flow capability.
As can be seen from the data in Table 1, under the condition of the same water reducing agent and montmorillonite mixing amount, the initial fluidity and the fluidity retention performance of the example (the nano mud-resistant slump-retaining polycarboxylate water reducing agent in the invention) are better than those of the comparative example, especially the fluidity retention capacity under the condition of high mud content, and the neat pastes prepared in comparative examples 1-4 are greatly reduced along with time and lose the fluidity performance after 60min or 90 min. Compared with the above, the examples 1 to 9 all maintain good fluidity at 120min, which shows that the nanometer mud slump loss resistant polycarboxylate water reducer crosslinked by the mud resistant crosslinking agent in a proper dosage range has excellent dispersing performance and long-term mud slump loss resistance under the condition of high mud content, while the conventional linear polycarboxylate water reducer, the conventional nanometer polycarboxylate water reducer and the mud resistant nanometer polycarboxylate water reducer with the dosage exceeding the limited range have relatively poor performance.
It can be seen from the table that different crosslinking monomers have a certain synergistic effect, and the outgoing flow and the flow retention performance of example 7 using 50% of the anti-mud crosslinking agent a and 50% of the anti-mud crosslinking agent D are significantly better than those of example 1 using the anti-mud crosslinking agent a alone and example 6 using the anti-mud crosslinking agent D alone. This is caused by the multistage crosslinking of monomers of different functionality. It can be seen from the overall results that the use effect of the multiple cross-linked examples 7 to 9 is better than that of the single cross-linked examples 1 to 6.
To further study this synergistic effect, we measured the net slurry flow according to GB/T8077-. The test results are shown in Table 2.
TABLE 2 Net slurry test results at Low temperature conditions
It can be seen that under the condition of low temperature and high mud content, the effect of the embodiment 1 and the embodiment 6 which are independently crosslinked is obviously reduced, the fluidity at 120min is very small, while the embodiment 7 which is subjected to multi-stage crosslinking still has better performance, and the better fluidity can still be maintained at 120 min. It can thus be seen that this synergistic effect between the multiple cross-linking agents is more pronounced at low temperature conditions.
The test is carried out by respectively using the nano mud-resistant slump-retaining polycarboxylic acid water reducing agent and the conventional polycarboxylic acid water reducing agent in the montmorillonite-doped C30 concrete. The concrete mixture performance test is carried out according to GB/T50080-2002 Standard for Performance test methods of common concrete mixtures, and slump and expansion of the concrete mixture are tested for 60 min. The mixing proportion of the C30 concrete is shown in Table 3. The concrete test results are shown in Table 4.
TABLE 3C 30 concrete mixing ratio
| Cement | Fly ash | River sand | Crushing stone | Water (W) | Additive agent |
| 300 | 80 | 820 | 1086 | 165 | 1％ |
TABLE 4 concrete test results
As can be seen from the data in Table 4, the concrete used in C30 in the examples 1-8 has good fluidity and dispersibility, has long-term slump retaining and mud resisting performance, and the performance comparison is obviously superior to that of the comparative examples 1-4.
The nano mud-resistant slump-retaining polycarboxylate water reducer can not be completely used in the conventional machine-made sand concrete with higher powder content, and the flow property and slump-retaining property of the machine-made sand concrete can be effectively improved by compounding a small amount of the mud-resistant slump-retaining nano polycarboxylate water reducer with the conventional water reducer. The examples 1 and 7 and the commercially available slump loss resistant water reducer BT in the embodiment are compounded with the commercially available conventional water reducer PCE, and the obtained mixture is respectively used in C30 machine-made sand concrete to test the performance improvement of the conventional water reducer. The concrete mixture performance test is carried out according to GB/T50080-2002 standard of common concrete mixture performance test method, and slump and expansion of the concrete mixture are tested for 60min and 120 min. The mixing proportion of the C30 machine-made sand concrete is shown in a table 5. The fineness modulus of the machine-made sand was 2.9, the stone powder content was 9%, the MB value was 1.8, and the concrete test results are shown in Table 6.
TABLE 5C 30 machine-made Sand concrete mix proportion
| Cement | Fly ash | Mineral powder | Machine-made sand | Crushing stone | Water (W) | Conventional admixtures |
| 190 | 80 | 100 | 780 | 998 | 170 | 1％ |
TABLE 6 concrete test results
As can be seen from the data in Table 6, the effects of the three water reducing agents are better along with the increase of the mixing amount, the examples 1 and 7 have better effects under the mixing amount of 0.02 percent, the BT mother liquor has poorer effects under the mixing amount of 0.02 percent, and the concrete fluidity and the working performance of the examples 1 and 7 are obviously better than those of the commercial BT slump retaining agent under the same dosage.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the present invention without departing from the technical spirit of the present invention.
Claims (5)
1. A nano-class mud-resistant slump-retaining polycarboxylic acid water reducer is prepared from polyether macromonomer, unsaturated carboxylic acid, unsaturated carboxylic ester, styrene monomer, mud-resistant cross-linking agent and polymerizable mud-resistant emulsifier through emulsion polymerizationThe prepared polymer nano latex with a cross-linking structure is characterized in that the polyether macromonomer is at least one of isobutylene glycol polyglycol ether, isopentenol polyglycol ether, allyl polyglycol ether and ethylene glycol monovinyl ether polyoxyethylene ether with the molecular weight of 1600-4000, and the molecular structure of the polymerizable anti-mud emulsifier is
n is 7-15, and the using amount of n is 1-2% of the monomer amount; the anti-mud crosslinking agent is at least one of polyfunctional monomers obtained by esterification reaction of polyether polyol and unsaturated anhydride, and the dosage of the anti-mud crosslinking agent is 2-8% of the total amount of the monomers.
2. The nano mud and slump loss resistant polycarboxylate water reducer according to claim 1, wherein the polyether macromonomer: unsaturated carboxylic acid: unsaturated carboxylic acid ester: the molar ratio of the styrene monomers is 1: (1-5): (4-12): (1-8).
3. The nano mud and slump retaining polycarboxylic acid water reducing agent as claimed in claim 1, wherein the unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, fumaric acid and itaconic acid, the unsaturated carboxylic acid is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypropyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate, and the styrene monomer is at least one of styrene, p-chloromethylstyrene, 4-methylstyrene and alpha-methylstyrene.
4. The nano mud and slump loss resistant polycarboxylate water reducer as claimed in claim 1, wherein the polyether polyol is at least one of polymer polyol, polyoxyethylene polyol, polyoxypropylene polyol, polytetrahydrofuran polyol and copolyether polyol with a molecular weight of 600-7000, and the unsaturated anhydride is at least one of acrylic anhydride, methacrylic anhydride, maleic anhydride and itaconic anhydride.
5. The application of the nano-scale mud-resistant slump-retaining polycarboxylic acid water reducer as a water reducer, an additive, a mud-resistant clay component or a machine-made sand concrete regulator according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110028650.7A CN112759725B (en) | 2021-01-11 | 2021-01-11 | Nano mud-resistant slump-retaining polycarboxylate superplasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110028650.7A CN112759725B (en) | 2021-01-11 | 2021-01-11 | Nano mud-resistant slump-retaining polycarboxylate superplasticizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112759725A CN112759725A (en) | 2021-05-07 |
| CN112759725B true CN112759725B (en) | 2022-08-26 |
Family
ID=75701202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110028650.7A Active CN112759725B (en) | 2021-01-11 | 2021-01-11 | Nano mud-resistant slump-retaining polycarboxylate superplasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112759725B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248171B (en) * | 2021-05-12 | 2023-04-25 | 安徽建筑大学 | Preparation method of high-performance polycarboxylate superplasticizer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176591A (en) * | 1985-08-30 | 1986-04-19 | Neos Co Ltd | Water reducing agent for water slurry coal |
| CN100575295C (en) * | 2007-12-25 | 2009-12-30 | 南京瑞迪高新技术公司 | A kind of carboxylic acid polyalcohol water reducing agent of may command concrete slump loss |
| CN106519140A (en) * | 2016-11-15 | 2017-03-22 | 湖北工业大学 | Delayed-release alkali-resistant polycarboxylic acid slump retaining agent master batch |
| KR102129573B1 (en) * | 2016-12-26 | 2020-07-02 | 주식회사 엘지화학 | Cement additive composition comprising polycarboxylic acid-based copolymer |
| CN108192037B (en) * | 2017-12-28 | 2020-02-21 | 科之杰新材料集团有限公司 | Preparation method of ether high-dispersion high-slump-retaining polycarboxylate superplasticizer |
-
2021
- 2021-01-11 CN CN202110028650.7A patent/CN112759725B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112759725A (en) | 2021-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109312032B (en) | Rapid low-temperature preparation method of low-doping-amount sensitive polycarboxylic acid | |
| CN112694574B (en) | Polycarboxylate superplasticizer with high mud resistance and high slump loss resistance and preparation method thereof | |
| CN108794700B (en) | Carboxylic acid-based polymer, preparation method thereof and slow-release polycarboxylic acid water reducing agent | |
| CN109651566B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN108059697B (en) | Preparation method of polycarboxylate superplasticizer with regular sequence structure | |
| CN107652405B (en) | Polycarboxylate superplasticizer with amide/imide structure and preparation method thereof | |
| CH689118A5 (en) | Additional means of controlling the flow behavior of cementitious compositions. | |
| WO2014085996A1 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN109776742A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer of phosphate ester-containing and preparation method thereof | |
| CN100509683C (en) | Low molecular weight copolymer dispersant and preparing method thereof | |
| CN114213603B (en) | Mud-resistant slow-release polycarboxylate superplasticizer and preparation method and application thereof | |
| CN112661914B (en) | Polycarboxylate superplasticizer special for machine-made sand and preparation method thereof | |
| CN109824835B (en) | Polycarboxylic acid water reducing agent and preparation method thereof | |
| CN107793447B (en) | P2O5Method for preparing phosphate functional monomer by dispersion method and application | |
| CN112759725B (en) | Nano mud-resistant slump-retaining polycarboxylate superplasticizer and preparation method thereof | |
| CN112897929B (en) | Slow-release polycarboxylate superplasticizer microsphere and preparation method thereof | |
| CN111234131A (en) | Gluconolactone-based polycarboxylic acid water reducing agent and preparation method thereof | |
| CN113336902B (en) | Tea saponin modified compound water reducing agent and preparation method and application thereof | |
| CN114044856A (en) | Mud-blocking type polycarboxylate superplasticizer and preparation method thereof | |
| CN114249555A (en) | Viscosity-reducing slow-release polycarboxylate superplasticizer and application thereof | |
| CN107880226B (en) | Method for preparing phosphate functional monomer in vinyl pyrrolidone medium and application | |
| CN111961148B (en) | Reaction air-entraining type polycarboxylate superplasticizer and preparation method thereof | |
| CN111019064A (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| CN113683736B (en) | Viscosity-reducing polycarboxylate superplasticizer for high-strength concrete and preparation method thereof | |
| CN114195953B (en) | Low-sensitivity high-water-retention polycarboxylate superplasticizer 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 |