CN115215972B - Preparation method of quick-dispersion polycarboxylate superplasticizer - Google Patents
Preparation method of quick-dispersion polycarboxylate superplasticizer Download PDFInfo
- Publication number
- CN115215972B CN115215972B CN202110412206.5A CN202110412206A CN115215972B CN 115215972 B CN115215972 B CN 115215972B CN 202110412206 A CN202110412206 A CN 202110412206A CN 115215972 B CN115215972 B CN 115215972B
- Authority
- CN
- China
- Prior art keywords
- quick
- initiator
- dispersing
- polycarboxylate superplasticizer
- water reducer
- 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.)
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 49
- 239000006185 dispersion Substances 0.000 title claims abstract description 34
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 18
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 229920002521 macromolecule Polymers 0.000 claims abstract description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000004568 cement Substances 0.000 claims description 39
- 239000003999 initiator Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- -1 amine salt Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 5
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 5
- 229940014800 succinic anhydride Drugs 0.000 claims description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 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 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 239000002211 L-ascorbic acid Substances 0.000 claims description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- KBTJYNAFUYTSNN-UHFFFAOYSA-N [Na].OO Chemical compound [Na].OO KBTJYNAFUYTSNN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000001603 reducing effect Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- NZELWFGWQQDXHT-UHFFFAOYSA-M OO.[Na+].S(=O)(=O)(O)[O-] Chemical compound OO.[Na+].S(=O)(=O)(O)[O-] NZELWFGWQQDXHT-UHFFFAOYSA-M 0.000 claims 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 22
- 238000010526 radical polymerization reaction Methods 0.000 description 10
- 239000004567 concrete Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000021523 carboxylation Effects 0.000 description 4
- 238000006473 carboxylation reaction Methods 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- BGPLHMAJJNBWGQ-UHFFFAOYSA-L [Na+].[Na+].O=C.OO.[O-]S[O-] Chemical compound [Na+].[Na+].O=C.OO.[O-]S[O-] BGPLHMAJJNBWGQ-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
- 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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
- 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
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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
- C04B2103/302—Water reducers
-
- 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)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a preparation method of a quick-dispersing polycarboxylate superplasticizer. The quick dispersion type polycarboxylate water reducer is obtained by converting terminal reactive hydroxyl of terminal hyperbranched polyether into carboxyl adsorption groups and copolymerizing the carboxyl adsorption groups with carboxylic acid monomers; the terminal hyperbranched polyether is a terminal hyperbranched polyoxyethylene ether macromolecule generated in situ after the ring-opening polymerization of glycidyl ether is initiated by hydroxyl at the terminal of a polyether macromonomer. The method has the advantages that the sources of the raw materials utilized by the method are rich, the reaction conditions of each step are mild, and the method is mature; the active hydroxyl is adopted to initiate the glycidol anion polymerization reaction, so that a polycarboxylic acid water reducer with a large number of adsorption groups can be obtained, and compared with the conventional polycarboxylic acid, the polycarboxylic acid water reducer has the advantages of high adsorption rate and high adsorption quantity; the quick dispersion type polycarboxylate water reducer prepared by the method can effectively improve the effects of large water reduction, low mixing amount, high dispersion speed, slump retention and quick dispersion in a high admixture system.
Description
Technical Field
The invention belongs to the technical field of polycarboxylic acid water reducers for cement concrete, and particularly relates to a preparation method of a quick-dispersing polycarboxylic acid water reducer.
Background
The polycarboxylic acid high-performance water reducer (PCE) is used as a third-generation water reducer product, has the advantages of low mixing amount, high dispersibility, good slump retaining property and the like, and has strong designability of molecular structure and large space for further improving the performance. Therefore, the additive is the most important product in the current concrete additive market.
The performance of PCEs depends on the molecular structure, which is typically a comb copolymer composed of a carboxylic acid backbone with anions and polyether side chains. The carboxylic acid groups may adsorb on the cement surface, thereby generating electrostatic repulsive forces between the cement particles. The stretching of the hydrophilic polyether side chains provides a larger steric hindrance effect in the cement slurry, and the dispersion performance of the PCE is the result of the combined action of electrostatic repulsion and steric hindrance.
On the premise that the polycarboxylate water reducer has dispersibility, the adsorption rate and the adsorption amount of the polycarboxylate water reducer on the surface of cement particles necessarily influence the contact state of the cement particles and water, so that the hydration process of cement is influenced, and the compatibility of the polycarboxylate water reducer and the cement is directly related.
In recent years, a plurality of novel additives for changing the adsorption groups of the polycarboxylate water reducer have been reported, and patent CN111377642A reports that the adsorption groups of the polymer main chain have a plurality of adsorption macromolecules of carboxylic acid groups, sulfonic acid groups and phosphonic acid groups, and the adaptability of the polymer main chain to different cements, aggregates and machine-made sand is obviously improved. The patent CN105754045A introduces a functional group molecule containing a siloxane structure into a main chain of a polycarboxylic acid molecule, and carries out copolymerization reaction with acrylic acid, unsaturated polyoxyethylene ether and the like to obtain the novel polycarboxylic acid water reducer. The hydrolyzed silicic acid oligomer can be chemically bonded with the cementing material particles, and the anchoring capacity of strong interaction can promote the adaptability and slump retention of the water reducer to be obviously enhanced; the patent CN111518243A has the advantages that the main chain terminal of the polycarboxylate superplasticizer is grafted with the organic phosphorus, so that the phosphoric acid group is preferentially adsorbed on the surface of clay, the adsorption of the clay to the carboxylic acid group is weakened, and the slump retaining effect is realized besides the good water reducing effect in the aggregate with higher mud content.
In the construction process of concrete, particularly in winter, the dispersing effect of the water reducer is generally slower, the initial water reduction is small, and the water reducer is easy to cause the release of later-stage dispersing components to cause bleeding and other adverse effects after the initial water reduction is improved so as to improve the mixing amount. Most of the patents relate to the replacement or modification of carboxylic acid groups, and the problem of rapid dispersion in the concrete construction process is difficult to solve.
Disclosure of Invention
The invention provides a preparation method of a quick-dispersion type polycarboxylate superplasticizer, which aims to solve the problem of over-slow initial dispersion of concrete.
The invention provides a preparation method of a quick-dispersing type polycarboxylate superplasticizer, which is characterized in that the quick-dispersing type polycarboxylate superplasticizer is obtained by converting terminal reactive hydroxyl of terminal hyperbranched polyether into carboxyl adsorption groups and copolymerizing the carboxyl adsorption groups with carboxylic acid monomers;
the terminal hyperbranched polyether is a terminal hyperbranched polyoxyethylene ether macromolecule generated in situ after the ring-opening polymerization of glycidyl ether is initiated by hydroxyl at the terminal of a polyether macromonomer.
The quick dispersion type polycarboxylate water reducer is modified polycarboxylic acid with a polycarboxylic adsorption group, has stronger binding capacity with a cementing material, has quicker adsorption rate and more adsorption rate, can obviously improve the dispersion capacity of PCE on cement paste, improves the dispersion speed and enhances the slump retaining effect.
The invention relates to a preparation method of a quick dispersion type polycarboxylate superplasticizer, which comprises the following specific steps of:
(1) Weighing polyether macromonomer, adding a catalyst into an organic solvent I at the temperature of 50-130 ℃, slowly dripping glycidyl ether with corresponding molar ratio, reacting for 6-48 hours at the temperature of 30-50 ℃, cooling, and purifying to obtain a product A, namely polyoxyethylene ether macromolecules;
(2) Dissolving the product A obtained in the step (1), an alkaline catalyst and organic acid anhydride in an organic solvent II, and keeping N 2 Stirring for 1-6 hours at the temperature of 40-80 ℃ in the atmosphere, cooling and purifying to obtain a macromonomer product B;
(3) And (3) polymerizing the macromonomer product B, carboxylic acid monomer, deionized water and chain transfer agent obtained in the step (2) under the action of an initiator by free radicals to obtain the quick-dispersion polycarboxylate superplasticizer.
The mol ratio of the glycidyl ether to the polyether macromonomer in the step (1) is 1-50: 1, a step of; the dropwise adding time of the glycidyl ether in the step (1) is controlled to be 2.0-6.0 h;
the mass ratio of the product A to the organic anhydride in the step (2) is controlled to be 0.1-1: 1, the carboxylic acid anhydride is too little, so that the carboxylation degree is insufficient, the performance is influenced, and the waste of raw materials is caused by too much acid anhydride;
and (3) controlling the total weight concentration of the large monomer B and the small carboxylic acid monomer in the polymerization process in the step (3) to be 20-60%.
The structural general formula of the polyether macromonomer in the step (1) is shown as (1):
r in formula (1) 1 is-H or-CH 3 N=10 to 45, and x is selected from-CH 2 -、-CH 2 OCH 2 CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 -、-OCH 2 CH 2 -、-OCH 2 CH 2 OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-C 6 H 4 -、-C 6 H 4 CH 2 -any one of the following.
The weight average molecular weight of the polyether macromonomer is preferably 500-2000, the molecular weight is not too large, otherwise, the double bond concentration is too low and the activity is poor in the polymerization process of the hyperbranched macromonomer B obtained after the reaction with glycidyl ether and carboxylation;
the macromonomer product B in the step (3) is shown in a general formula (2):
r in formula (2) 1 is-H or-CH 3 M=an integer from 1 to 50, wherein R 2 Is represented by the general formula (3):
in the formula (3), R 3 ，R 4 ，R 5 ，R 6 Independently selected from-COCH 2 CH 2 COOH，-COCH2CH 2 CH 2 COOH, or-H, but not simultaneously-H; wherein p and q are integers of 0 to 50 independently selected.
The carboxylic acid small monomer in the step (3) is selected from any one of acrylic acid, methacrylic acid, maleic acid, itaconic acid and sodium salt, potassium salt, calcium salt, ammonium salt and organic amine salt thereof.
The organic solvent I in the step (1) and the organic solvent II in the step (2) are respectively and independently selected from N,any one of N-dimethylformamide, N-dimethylacetamide, toluene, xylene and N-methylpyrrolidone; the organic solvent I and the organic solvent II are subjected to anhydrous treatment before use, and the conventional anhydrous treatment is CaH addition 2 Refluxing for 4-6 h, and then distilling or decompressing and distilling to finish the anhydrous treatment.
The catalyst in the step (1) is selected from any one of sodium ethoxide, potassium ethoxide, sodium methoxide and potassium methoxide; the dosage is 0.1 to 5 percent of the total reactant mass in the step (1); the catalyst is used for deprotonation of terminal hydroxyl of a polyether macromonomer to initiate glycidol ring-opening polymerization, and the polymerization reaction has the advantages of mild condition, low dispersity and good molecular weight controllability.
The alkaline catalyst in the step (2) is triethylamine or 4-dimethylaminopyridine, and the dosage is 0.5-10% of the total reactant in the step (2);
the organic acid anhydride in the step (2) is preferably any one of succinic anhydride and glutaric anhydride;
the purification methods in the step (1) and the step (2) are all to remove the organic solvent by reduced pressure distillation, precipitate in acetone, and dry after centrifugation.
The free radical polymerization mode in the step (3) is suitably redox free radical polymerization in an aqueous solution, and the initiator of the free radical copolymerization reaction is selected from a single oxidation component I or a combination of an oxidation component II and a reduction component; wherein when the initiator is a single oxidation component I, the initiator is selected from any one of sulfate and water-soluble azo compounds, and ammonium persulfate is preferred; when the initiator is a composition of an oxidation component II and a reduction component, the oxidation component II is selected from any one of persulfate and peroxide, and the reduction component is selected from any one or a mixture of more than one of bisulfite, sulfite, thiosulfate, metabisulfite, ferrous salt, sodium formaldehyde sulfoxylate and L-ascorbic acid; preferably hydrogen peroxide-sodium formaldehyde sulfoxylate, hydrogen peroxide-ascorbic acid, hydrogen peroxide-sodium bisulfite-ferrous sulfate.
The total consumption of the oxidation components in the initiator accounts for 0.1-2% of the total mass of the reaction monomers in the step (3); when the initiator is a composition of an oxidation component and a reduction component, the mass ratio of the oxidation component to the reduction component is 0.4-4:1.
The chain transfer agent in the step (3) is any one of thioglycollic acid, mercaptopropionic acid, mercaptoethanol and sodium methacrylate, and the dosage of the chain transfer agent in the polymerization process is 0-5.0% of the total weight of the reaction monomers in the step (3).
The weight average molecular weight range of the quick dispersion type polycarboxylate superplasticizer is required to be kept the same as the general requirements of the common comb-shaped polycarboxylate superplasticizer, and preferably, the weight average molecular weight of the quick dispersion type polycarboxylate superplasticizer is 20000-50000. The side chains with too large molecular weight are mutually entangled to influence the dispersing effect, and the molecular weight is too small to play a role in rapid dispersion, so that the comprehensive performance of the polymer is weakened.
The modified hyperbranched polyether macromonomer terminal contains a large number of hydroxyl or carboxyl adsorption groups, provides rapid adsorption capacity, and has larger steric hindrance and dispersion capacity.
As more adsorption groups exist after carboxylation, the catalyst can be rapidly adsorbed on the surface of Ca < 2+ > ions, and the macroscopic dispersion speed is driven to be high.
According to a second aspect of the present invention there is provided the use of the fast dispersing polycarboxylic acid as a cement dispersant.
The quick dispersion type polycarboxylate water reducer can be directly used as a cement dispersant, can also be compounded with functional assistants such as a defoaming agent, an air entraining agent, a retarder, a thickening agent, a shrinkage reducing agent and the like or other types of polycarboxylate superplasticizers according to a certain proportion, is particularly compounded in type and proportion, and can be optimized after passing a test according to actual engineering requirements by engineering technicians.
The invention has the beneficial effects that:
(1) The method has the advantages that the sources of the raw materials utilized by the method are rich, the reaction conditions of each step are mild, and the method is mature;
(2) The method adopts active hydroxyl to initiate glycidol anion polymerization reaction, and can obtain a polycarboxylic acid water reducer with a large number of adsorption groups.
(3) The quick dispersion type polycarboxylate water reducer prepared by the method can effectively improve the effects of large water reduction, low mixing amount, high dispersion speed, slump retention and quick dispersion in a high admixture system.
Drawings
FIG. 1 is a GPC outflow curve of the polycarboxylate superplasticizer HPCA-1 prepared in example 1.
FIG. 2 is a GPC outflow curve of the polycarboxylate superplasticizer prepared in comparative example 2.
Detailed Description
The technical scheme of the invention is further described in detail by the following examples
The amounts described in the examples and comparative examples are by mass;
synthesis example 1
100 parts of allyl polyoxyethylene ether (in the general formula 1-R 1 is-H, X is-CH 2 -, N is 50), dissolving in 250 parts of dry N, N-dimethylformamide, adding 0.15 part of sodium ethoxide as a catalyst at the temperature of 50 ℃, slowly dropwise adding 50 parts of glycidyl ether, reacting for 6 hours at the temperature of 50 ℃, cooling, and purifying to obtain a product A; 50 parts of product A, 0.33 part of 4-dimethylaminopyridine, 15 parts of succinic anhydride are dissolved in 150 parts of dried N, N-dimethylformamide, and N is maintained 2 Stirring for 6 hours at 40 ℃ in the atmosphere, cooling and purifying to obtain a macromonomer product B; the HPCA-1 is prepared by free radical polymerization of 100 parts of a large monomer product B,10 parts of acrylic acid, 100 parts of deionized water and 1 part of mercaptoethanol under the action of an initiator ammonium persulfate.
Synthesis example 2
50 parts of methallyl polyoxyethylene ether (in the general formula 1-R 1 is-CH 3 X is-CH 2 -, N is 50), dissolving in 150 parts of dried N, N-dimethylacetamide, adding 0.8 part of sodium methoxide catalyst at 65 ℃, slowly dropwise adding 30 parts of glycidyl ether, reacting for 12 hours at 50 ℃, cooling and purifying to obtain a product A; 50 parts of the product A obtained above, 3 parts of 4-dimethylaminopyridine and 5 parts of glutaric anhydride are dissolved in 50 parts of dried N, N-dimethylacetamide, and N is maintained 2 Stirring for 2 hours at the temperature of 60 ℃ in the atmosphere, cooling and purifying to obtain a macromonomer product B; the HPCA-2 is prepared by free radical polymerization of 50 parts of a macromonomer product B,10 parts of methacrylic acid, 60 parts of deionized water and 0.5 part of mercaptopropionic acid under the action of hydrogen peroxide-formaldehyde sodium bisulphite.
Synthesis example 3
200 parts of butenyl polyoxyethylene ether (R in the general formula 1 1 Is H, X is-CH 2 CH 2 -, n is 40), dissolving in 500 parts of dry toluene, adding 15 parts of potassium ethoxide as a catalyst at 90 ℃, slowly dropwise adding 100 parts of glycidyl ether, reacting for 48 hours at 30 ℃, cooling, and purifying to obtain a product A; 200 parts of the product A obtained above, 25 parts of triethylamine, 50 parts of glutaric anhydride, were dissolved in 300 parts of dry toluene, and N was maintained 2 Stirring for 1 hour under the condition of 80 ℃ in atmosphere, cooling and purifying to obtain a macromonomer product B; the HPCA-3 is prepared by free radical polymerization of 100 parts of a macromonomer product B,10 parts of maleic acid, 100 parts of deionized water and 1 part of mercaptoethanol under the action of hydrogen peroxide-formaldehyde sodium bisulphite.
Synthesis example 4
150 parts of a vinyl polyoxyethylene ether (R in the formula 1 1 Is H, X is-OCH 2 CH 2 -, n is 30), dissolving in 300 parts of dried xylene, adding 5 parts of sodium ethoxide as a catalyst at a temperature of 100 ℃, slowly dropwise adding 50 parts of glycidyl ether, reacting for 36 hours at a temperature of 40 ℃, cooling, and purifying to obtain a product A; 100 parts of the product A obtained above, 1.8 parts of triethylamine, 80 parts of succinic anhydride, were dissolved in 200 parts of dried xylene, and N was maintained 2 Stirring for 3 hours at 70 ℃ in the atmosphere, cooling and purifying to obtain a macromonomer product B; 120 parts of a macromonomer product B,25 parts of itaconic acid, 150 parts of deionized water and 4 parts of sodium methacrylate are subjected to free radical polymerization under the action of an initiator hydrogen peroxide-ascorbic acid system to obtain HPCA-4.
Synthesis example 5
250 parts of hydroxybutyl vinyl polyoxyethylene ether (R in the formula 1 1 is-H, X is-OCH 2 CH 2 CH 2 CH 2 -, N is 30), dissolving in 500 parts of dry N, N-dimethylformamide, adding 15 parts of potassium methoxide as a catalyst at 90 ℃, slowly dropwise adding 80 parts of glycidyl ether, reacting for 24 hours at 50 ℃, cooling, and purifying to obtain a product A; 100 parts of the product A obtained in the step one, 8 parts of triethylamine and 100 parts of succinic anhydride are dissolved in 300 parts of dry N, N-dimethylformamide, and N is maintained 2 Stirring for 2 hours at 80 ℃ in atmosphere, cooling and purifying to obtain a macromonomer product B; the HPCA-5 is prepared by free radical polymerization of 200 parts of a large monomer product B,40 parts of sodium methacrylate, 200 parts of deionized water and 10 parts of sodium methacrylate under the action of hydrogen peroxide, sodium bisulphite and ferrous sulfate.
Synthesis example 6
100 parts of isopentenyl alcohol polyoxyethylene ether (R in the general formula 1) 1 Is CH 3 X is-CH 2 CH 2 -, N is 50), dissolving in 200 parts of dry N-methylpyrrolidone, adding 3.8 parts of potassium ethoxide catalyst at 130 ℃, slowly dropwise adding 20 parts of glycidyl ether, reacting for 48 hours at 35 ℃, cooling and purifying to obtain a product A; 100 parts of the product A obtained in the step one, 2 parts of triethylamine and 100 parts of glutaric anhydride are dissolved in 300 parts of dry N-methylpyrrolidone, and N is maintained 2 Stirring for 3 hours at 70 ℃ in the atmosphere, cooling and purifying to obtain a macromonomer product B; the HPCA-6 is prepared by free radical polymerization of 300 parts of a large monomer product B,60 parts of sodium acrylate, 300 parts of deionized water and 15 parts of thioglycollic acid under the action of ammonium persulfate.
Comparative example 1
100 parts of allyl polyoxyethylene ether (in the general formula 1-R 1 is-H, X is-CH 2 -, N is 50), dissolving in 250 parts of dry N, N-dimethylformamide, adding 0.15 part of sodium ethoxide as a catalyst at the temperature of 50 ℃, slowly dropwise adding 50 parts of glycidyl ether, reacting for 6 hours at the temperature of 50 ℃, cooling, and purifying to obtain a product A; the water reducer product of comparative example 1 is obtained by free radical polymerization of 100 parts of product A,10 parts of acrylic acid, 100 parts of deionized water and 1 part of mercaptoethanol under the action of an initiator ammonium persulfate.
Comparative example 2
From 300 parts of methallyl polyoxyethylene ether (in the general formula 1-R 1 is-CH 3 X is-CH 2 -, n is 50), 60 parts of acrylic acid, 300 parts of deionized water and 10 parts of thioglycollic acid are subjected to free radical polymerization under the action of a hydrogen peroxide-ascorbic acid system to obtain the water reducer product of the comparative example 2.
Application examples
Application example 1
To examine the adsorption properties of all the synthetic samples in the cement paste, 20g of cement was weighed and added to 10g of the polycarboxylic acid solutions prepared in each example and comparative example with an amount of 0.1% (folded solid), stirred for a certain period of time, sampled at regular time and poured into a centrifuge tube, separated by a high-speed centrifuge (10000 r/min) for 2min, 2g of supernatant of the centrifuge tube was collected, acidified with 1g of HCl (1 mol/L) solution, and diluted to 20g with water. The total organic carbon analyzer Multi N/C3100 produced by the Germany Yes company is adopted to respectively measure the organic carbon content of clear liquid and blank sample (not mixed with cement), and the adsorption quantity of the cement particle surface can be calculated by combining the concentration difference of the clear liquid and the blank sample and the mixing quantity of the high-efficiency water reducer
TABLE 1 adsorption amount of samples with time
As can be seen from table 1, the adsorption amounts of examples 1 to 6 at 4min are significantly higher than those of comparative examples 1 and 2, and after 10min, the adsorption amounts are substantially close to the saturated adsorption amounts, which indicates that the rapid dispersion type water reducer synthesized by the invention has more adsorption and higher efficiency; by comparing comparative example 1 with comparative example 2, the adsorption amount of comparative example 1 is high, which indicates that the adsorption capacity is remarkably improved after carboxylation.
Application example 2
Aqueous Gel Permeation Chromatography (GPC)
The experiment adopts miniDAWNTristar aqueous gel permeation chromatography produced by Wyatt technology corporation in the United states to measure relative molecular mass, molecular weight distribution and conversion rate: the mass concentration percentage of the sample was 0.5% by mass of an aqueous solution of mobile phase 0.01M NaNO3 at a flow rate of 1m L/min.
The GPC flow out curve of the polycarboxylate water reducer HPCA-1 prepared in example 1 is shown in FIG. 1, the GPC flow out curve of the polycarboxylate water reducer prepared in comparative example 2 is shown in FIG. 2, and it is apparent from FIGS. 1 and 2 that the application example shows an increase in the high molecular weight fraction formed by the rapidly dispersing type polycarboxylate of the present invention as compared with the comparative example, so that the polymerization feasibility of the polycarboxylate water reducer structure prepared by the preparation method of the present invention can be demonstrated.
Application example 3
The fluidity of cement paste with time was measured in accordance with GB/T8077-2012 test method for homogeneity of concrete admixture in examples 1-6 and comparative examples 1-2. The water-cement ratio w/c is 0.22, the folding and solidifying mixing amount of the polycarboxylate water reducer is 0.12% -0.13% (calculated by cement mass), the test temperature is 20+/-2 ℃, and the result is shown in Table 2.
TABLE 2 cement paste fluidity time results
Note that: r=stirring 4min fluidity/stirring 1min fluidity
As can be seen from the data in Table 2, the quick-dispersing polycarboxylate water reducer prepared by the invention has a quick dispersing speed on cement at a low mixing amount, and the fluidity of the quick-dispersing polycarboxylate water reducer can reach more than 93% of the fluidity of 4min after stirring for 1min in examples 1-6 by comparing the fluidity of the quick-dispersing polycarboxylate water reducer under stirring for 1min in each example. Whereas conventional comparative example 2 can only reach 78% at higher levels. And samples of examples 1 to 6 have large water reduction and good slump loss resistance, while the comparative examples have equivalent dispersing ability and significantly faster time loss at one doping amount higher.
Through the comparison example 1 and the comparison example 2, the multi-reactive hydroxyl derived from the polyether macromonomer has a strong adsorption effect, the dispersion speed of the slurry is improved to a certain extent, but the adsorption capacity of carboxyl is obviously more advantageous.
The advantages of the concrete under the condition of low water-cement ratio are expected to be applied to high-strength concrete systems.
Application example 4
The fluidity of cement paste was measured with time in accordance with GB/T8077-2012, concrete admixture homogeneity test method, respectively, for examples 1 to 6 and comparative example. The cement ratio w/c was 0.25, the cement + fly ash + slag = 50% +35% +15% for the cement, the polycarboxylic acid water reducer was added in an amount of 0.15% (based on the mass of cement) and the test temperature was 20.+ -. 2 ℃ and the results are shown in Table 3.
TABLE 3 cement paste fluidity time results
Note that: r=stirring 4min fluidity/stirring 1min fluidity
In a 50% high admixture system, the fluidity of 1 minute of examples 1-6 can reach more than 90% of that of 4 minutes of stirring at a low water-cement ratio of 0.25, while the fluidity of 1 minute of stirring of the common comb-shaped polymer of comparative example 2 is less than 70% at a higher admixture amount, which fully shows that the quick dispersion type polycarboxylate water reducer prepared by the invention has the advantage of quick dispersion in a high admixture system.
Application example 5
The application effect of the prepared quick-dispersing water reducer is further examined through the fluidity of mortar. Wherein the cement adopts two kinds of cement with different brands and specifications: 52.5 cement for field P.II in the south of the Yangtze river and 42.5 cement for conch P.O; the test temperature is 20 ℃; the test sand adopts ISO standard sand, and the ash-sand ratio is 1:1.8; the mixing amount is calculated by the mass of cement; the dispersibility of the water reducer was examined by the initial fluidity and the loss with time of mortar, and the test results were as follows.
Table 4 sample mortar dispersion results
As can be seen from Table 4, the two different cements showed different trends, the field cement was continuously lost, while the conch cement mortar was significantly rising for 30 min. Examples 1 to 6 have significantly greater initial fluidity of mortar in field cements than comparative examples 1 and 2, and the loss after 30min is significantly smaller, the maximum loss being 26mm fluidity, whereas comparative example 2 has lost 62mm fluidity after 30min, and comparative example 1 also has lost 38mm fluidity.
The samples of examples 1-6 in conch cement still have great advantages compared with the initial water reduction of comparative examples 1 and 2, and 30 minutes of reverse swelling is rapid, which shows that the quick dispersion type water reducer prepared by the invention has the advantages of high water reduction and high slump retention.
Claims (13)
1. A preparation method of a quick dispersion type polycarboxylate superplasticizer is characterized by comprising the following steps of: the terminal reactive hydroxyl of the terminal hyperbranched polyether is converted into a carboxyl adsorption group and then copolymerized with a carboxylic acid monomer to obtain the quick dispersion type polycarboxylate superplasticizer;
the terminal hyperbranched polyether is a terminal hyperbranched polyoxyethylene ether macromolecule generated in situ after the ring-opening polymerization of glycidyl ether is initiated by hydroxyl at the terminal of a polyether macromonomer.
2. The preparation method of the quick-dispersing polycarboxylate superplasticizer as claimed in claim 1, wherein the preparation method comprises the following specific steps of:
(1) Weighing polyether macromonomer, adding a catalyst into an organic solvent I at the temperature of 50-130 ℃, slowly dripping glycidyl ether with corresponding molar ratio, reacting for 6-48 hours at the temperature of 30-50 ℃, cooling, and purifying to obtain a product A, namely polyoxyethylene ether macromolecules;
(2) Dissolving the product A obtained in the step (1), an alkaline catalyst and organic acid anhydride in an organic solvent II, and keeping N 2 Stirring at 40-80 deg.C in the atmosphere to 1% in the presence of waterCooling for 6 hours, and purifying to obtain a macromonomer product B;
(3) And (3) polymerizing the macromonomer product B, carboxylic acid monomer, deionized water and chain transfer agent obtained in the step (2) under the action of an initiator by free radicals to obtain the quick-dispersion polycarboxylate superplasticizer.
3. The method for preparing the quick-dispersing polycarboxylate superplasticizer as claimed in claim 2, wherein the molar ratio of the glycidyl ether to the polyether macromonomer in the step (1) is 1-50: 1, a step of;
the mass ratio of the product A to the organic anhydride in the step (2) is controlled to be 0.1-1: 1, a step of;
and (3) controlling the total weight concentration of the large monomer product B and the small carboxylic acid monomer in the polymerization process in the step (3) to be 20-60%.
4. The method for preparing a rapidly dispersing polycarboxylate superplasticizer according to claim 2 or 3, wherein the polyether macromonomer in the step (1) has a structural formula shown in (1):
r in formula (1) 1 is-H or-CH 3 N=10 to 45, and x is selected from-CH 2 -、-CH 2 OCH 2 CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 -、-OCH 2 CH 2 -、-OCH 2 CH 2 OCH 2 CH 2 -、-OCH 2 CH 2 CH 2 CH 2 -、-C 6 H 4 -、-C 6 H 4 CH 2 -any one of the following.
5. The method for preparing a rapidly dispersing polycarboxylate superplasticizer as claimed in claim 4, wherein the polyether macromonomer has a weight average molecular weight of 500-2000.
6. The method for preparing a rapidly dispersing polycarboxylate superplasticizer as claimed in claim 2 or 3, wherein the small carboxylic acid monomer in step (3) is selected from any one of acrylic acid, methacrylic acid, maleic acid, itaconic acid, sodium salt, potassium salt, calcium salt, ammonium salt and organic amine salt thereof.
7. The method for preparing a quick-dispersing polycarboxylate water reducer according to claim 2, wherein the organic solvent I in the step (1) and the organic solvent II in the step (2) are respectively and independently selected from any one of N, N-dimethylformamide, N-dimethylacetamide, toluene, xylene and N-methylpyrrolidone; the organic solvent I and the organic solvent II are subjected to anhydrous treatment before use, wherein the anhydrous treatment is CaH addition 2 Reflux for 4-6 h, and then distillation or reduced pressure distillation to complete the anhydrous treatment;
the purification methods in the step (1) and the step (2) are all that the organic solvent is removed by reduced pressure distillation, the organic solvent is precipitated in acetone, and the organic solvent is dried after centrifugation;
and (3) controlling the dropwise adding time of the glycidyl ether in the step (1) to be 2.0-6.0 h.
8. The method for preparing a quick-dispersing polycarboxylate water reducer according to claim 3, wherein the catalyst in the step (1) is any one selected from sodium ethoxide, potassium ethoxide, sodium methoxide and potassium methoxide; the dosage is 0.1 to 5 percent of the total reactant mass in the step (1);
the alkaline catalyst in the step (2) is triethylamine or 4-dimethylaminopyridine, and the dosage is 0.5-10% of the total reactant in the step (2).
9. The method for preparing a rapidly dispersing polycarboxylate superplasticizer as recited in claim 4, wherein the organic acid anhydride in the step (2) is selected from any one of succinic anhydride and glutaric anhydride.
10. A process for the preparation of a fast dispersing polycarboxylate water reducer according to claim 3, characterized in that the initiator of step (3) is selected from the group consisting of single oxidizing component i or a combination of oxidizing component ii and reducing component; wherein when the initiator is a single oxidation component I, the initiator is selected from any one of sulfate and water-soluble azo compounds; when the initiator is a composition of an oxidation component II and a reduction component, the oxidation component II is selected from any one of persulfate and peroxide, and the reduction component is selected from any one or a mixture of more than one of bisulfite, sulfite, thiosulfate, metabisulfite, ferrous salt, sodium formaldehyde sulfoxylate and L-ascorbic acid;
the total consumption of the oxidation components in the initiator accounts for 0.1-2% of the total mass of the reaction monomers in the step (3); when the initiator is a composition of an oxidation component and a reduction component, the mass ratio of the oxidation component to the reduction component is 0.4-4:1;
the chain transfer agent in the step (3) is any one of thioglycollic acid, mercaptopropionic acid, mercaptoethanol and sodium methacrylate, and the dosage of the chain transfer agent in the polymerization process is 0-5.0% of the total weight of the reaction monomers in the step (3).
11. The method for preparing a quick dispersion type polycarboxylate superplasticizer as claimed in claim 10, wherein, when the initiator is a single oxidation component i, the initiator is ammonium persulfate; when the initiator is a composition of an oxidation component II and a reduction component, the initiator is selected from any one of hydrogen peroxide-formaldehyde sodium bisulfate, hydrogen peroxide-ascorbic acid, hydrogen peroxide-sodium bisulfate and hydrogen peroxide-sodium bisulfate-ferrous sulfate.
12. A method of preparing a rapidly dispersing polycarboxylate superplasticizer as claimed in any one of claims 1 to 3, characterized in that the weight average molecular weight of the rapidly dispersing polycarboxylate superplasticizer is 20000-50000.
13. The use of the fast dispersing polycarboxylate water reducer prepared by the method of claim 12 as a cement dispersant.
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