CN115215972A - Preparation method of fast-dispersing polycarboxylate superplasticizer - Google Patents
Preparation method of fast-dispersing polycarboxylate superplasticizer Download PDFInfo
- Publication number
- CN115215972A CN115215972A CN202110412206.5A CN202110412206A CN115215972A CN 115215972 A CN115215972 A CN 115215972A CN 202110412206 A CN202110412206 A CN 202110412206A CN 115215972 A CN115215972 A CN 115215972A
- Authority
- CN
- China
- Prior art keywords
- fast
- polycarboxylate superplasticizer
- acid
- preparation
- initiator
- 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.)
- Granted
Links
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 46
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 claims abstract description 34
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 23
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 18
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 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
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 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 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000010526 radical polymerization reaction Methods 0.000 claims description 14
- 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
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 7
- 150000001732 carboxylic acid derivatives 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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- -1 amine salt Chemical class 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 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
- 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
- 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
- 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 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 4
- 238000005303 weighing Methods 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
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 238000004821 distillation Methods 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000000376 reactant Substances 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
- FJWZLXNYQPQPQG-UHFFFAOYSA-M sodium hydrogen peroxide hydrogen sulfite Chemical compound OO.S([O-])(O)=O.[Na+] FJWZLXNYQPQPQG-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 6
- 239000002244 precipitate Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 239000004567 concrete Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000002002 slurry 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
- 150000008065 acid anhydrides Chemical class 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
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 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
- 238000009826 distribution Methods 0.000 description 2
- 238000001595 flow curve 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000537371 Fraxinus caroliniana Species 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 241001374849 Liparis atlanticus Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 235000010891 Ptelea trifoliata Nutrition 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 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
- 239000002956 ash Substances 0.000 description 1
- 238000005452 bending Methods 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
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 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
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010998 test method Methods 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
Images
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 fast dispersion type polycarboxylate superplasticizer. The quick-dispersing polycarboxylate superplasticizer is obtained by converting the terminal reactive hydroxyl of terminal hyperbranched polyether into carboxyl adsorption groups and then copolymerizing the carboxyl adsorption groups with small carboxylic monomers; the terminal hyperbranched polyether is a terminal hyperbranched polyoxyethylene ether macromolecule generated in situ after ring-opening polymerization of glycidyl ether initiated by hydroxyl at the terminal of a polyether macromonomer. The method has the advantages of rich raw material sources, mild reaction conditions in each step and mature method; the active hydroxyl is adopted to initiate glycidyl anion polymerization reaction, so that a large number of polycarboxylic acid water reducing agents with adsorption groups can be obtained, and compared with conventional polycarboxylic acid, the polycarboxylic acid water reducing agent has high adsorption rate and high adsorption quantity; the fast dispersion type polycarboxylate superplasticizer prepared by the method can effectively improve the water reduction effect, has low mixing amount, high dispersion speed and good slump loss resistance, and also has a fast dispersion effect in a high admixture system.
Description
Technical Field
The invention belongs to the technical field of polycarboxylic acid water reducing agents for cement concrete, and particularly relates to a preparation method of a fast dispersion type polycarboxylic acid water reducing agent.
Background
The polycarboxylic acid high-performance water reducing agent (PCE) serving as a third-generation water reducing agent product has the advantages of low mixing amount, high dispersibility, good slump retaining property and the like, and has a strong designability of a molecular structure and a large space for further high-performance. Therefore, the concrete admixture becomes the most important product in the market of the concrete admixture at present.
The performance of PCE depends on the molecular structure, which is typically a comb copolymer consisting of a carboxylic acid backbone with anions and polyether side chains. The carboxylic acid groups can adsorb at the cement surface, thereby generating electrostatic repulsion forces between the cement particles. The hydrophilic polyether side chain is stretched to provide a larger steric hindrance effect in the cement paste, and the dispersion performance of the PCE is the combined action of electrostatic repulsion and steric hindrance.
The premise of the dispersibility of the polycarboxylate water reducer is that the polycarboxylate water reducer is adsorbed on the surfaces of cement particles, and the adsorption rate and the adsorption quantity of the polycarboxylate water reducer inevitably 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 polycarboxylic acid water reducing agent have been reported, and patent CN111377642A reports that the adsorption groups of the main chain of the polymer have multi-adsorption macromolecules of carboxylic acid groups, sulfonic acid groups and phosphonic acid groups, and the adaptability to different cements, aggregates and machine-made sands is obviously improved. In patent CN105754045a, a molecule containing siloxane structure functional groups is introduced into a main chain of a polycarboxylic acid molecule, and copolymerization reaction is performed with acrylic acid, unsaturated polyoxyethylene ether and the like, so as to obtain a novel polycarboxylic acid water reducing agent. The hydrolyzed silicic acid oligomer can be chemically bonded with the cementing material particles, the anchoring capability of interaction is strong, and the adaptability and slump retaining property of the water reducing agent can be obviously enhanced; in patent CN111518243A, organophosphorus is grafted at the main chain terminal of the polycarboxylic acid water reducing agent, so that phosphate groups are preferentially adsorbed on the clay surface, and the adsorption of clay to carboxylic acid groups is reduced, thereby having a slump retaining effect while maintaining a good water reducing effect in aggregates with high mud content.
In the construction process of the concrete, particularly in winter, the dispersing effect of the water reducing agent is generally slow, the initial water reduction is small, and in order to improve the initial water reduction and further improve the mixing amount, the adverse effects of bleeding and the like caused by the release of later-stage dispersing components are easily caused. 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 fast dispersion type polycarboxylate superplasticizer, aiming at solving the problem that the initial dispersion of concrete is too slow.
The invention provides a preparation method of a fast dispersion type polycarboxylate water reducer, which comprises the steps of converting terminal reactive hydroxyl of terminal hyperbranched polyether into carboxyl adsorption groups, and then copolymerizing the carboxyl adsorption groups with small carboxylic monomers to obtain the fast dispersion type polycarboxylate water reducer;
the terminal hyperbranched polyether is a terminal hyperbranched polyoxyethylene ether macromolecule generated in situ after initiating the ring-opening polymerization of glycidyl ether through hydroxyl at the terminal of a polyether macromonomer.
The rapid dispersion type polycarboxylate superplasticizer disclosed by the invention is modified polycarboxylate with a polycarboxyl adsorption group, has stronger binding capacity with a cementing material, is higher and more in adsorption rate, and can be used for remarkably improving the dispersion capacity of PCE on cement slurry, improving the dispersion speed and enhancing the slump retaining effect.
The invention relates to a preparation method of a fast dispersion type polycarboxylate superplasticizer, which comprises the following steps of:
(1) Weighing a polyether macromonomer, adding a catalyst in an organic solvent I at the temperature of 50-130 ℃, slowly dripping glycidyl ether with a 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 40-80 ℃, cooling and purifying to obtain a macromonomer product B;
(3) And (3) carrying out free radical polymerization on the macromonomer product B obtained in the step (2), a small carboxylic acid monomer, deionized water and a chain transfer agent under the action of an initiator to obtain the fast dispersion type polycarboxylate superplasticizer.
The molar ratio of the glycidyl ether to the polyether macromonomer in the step (1) is 1-50: 1; in the step (1), the dripping time of the glycidyl ether is controlled to be 2.0-6.0 h;
the mass ratio of the product A in the step (2) to the organic acid anhydride is controlled to be 0.1-1: 1, if the consumption of the acid anhydride is too low, the carboxylation degree is not enough, the performance is influenced, and if the consumption of the acid anhydride is too high, the raw material is wasted;
and (3) controlling the total weight concentration of the macromonomer B and the small carboxylic acid monomer in the polymerization process to be 20-60%.
The structural general formula of the polyether macromonomer in the step (1) is shown as (1):
r in the formula (1) 1 is-H or-CH 3 N =10 to 45, 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 of the above.
Preferably, the weight average molecular weight of the polyether macromonomer is 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 polyether macromonomer reacts with glycidyl ether and is carboxylated;
the macromonomer product B in the step (3) is represented by the general formula (2):
r in the formula (2) 1 is-H or-CH 3 M = an integer of 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 independently selected integers from 0 to 50.
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 any one of N, N-dimethylformamide, N-dimethylacetamide, toluene, xylene and N-methylpyrrolidone; the organic solvent I and the organic solvent II both need to be subjected to anhydrous treatment before use, and the conventional anhydrous treatment is to add CaH 2 Refluxing for 4-6 h, and then distilling or distilling under reduced pressure 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 mass of the reactants in the step (1); the catalyst is used for deprotonation of terminal hydroxyl of a polyether macromonomer to initiate ring-opening polymerization of glycidol, and the polymerization reaction has mild conditions, low dispersity and good molecular weight controllability.
The basic catalyst in the step (2) is triethylamine or 4-dimethylamino pyridine, and the dosage of the basic catalyst is 0.5 to 10 percent of the total reaction mass in the step (2);
the organic acid anhydride in the step (2) is preferably any one of succinic anhydride and glutaric anhydride;
and (3) removing the organic solvent by reduced pressure distillation, precipitating in acetone, centrifuging and drying in the purification method of the step (1) and the step (2).
The free radical polymerization mode in the step (3) is suitable to adopt redox free radical polymerization in aqueous solution, and an initiator of the free radical copolymerization reaction is selected from a single oxidation component I or a composition of an oxidation component II and a reduction component; when the initiator is a single oxidation component I, the initiator is selected from any one of sulfate and water-soluble azo compounds, preferably ammonium persulfate; when the initiator is a composition of an oxidation component II and a reduction component, the oxidation component II is selected from one of persulfate and peroxide, and the reduction component is selected from one or more of bisulfite, sulfite, thiosulfate, pyrosulfite, ferrous salt, sodium formaldehyde sulfoxylate and L-ascorbic acid; preferably hydrogen peroxide-sodium formaldehyde sulfoxylate, hydrogen peroxide-ascorbic acid, hydrogen peroxide-sodium bisulfite and hydrogen peroxide-sodium bisulfite-ferrous sulfate.
The total amount 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 selected from any one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and sodium methallyl sulfonate, and the using amount 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 fast dispersion type polycarboxylate superplasticizer needs to be kept the same as the general requirement of a common comb-shaped polycarboxylate superplasticizer, and preferably, the weight average molecular weight of the fast dispersion type polycarboxylate superplasticizer is 20000-50000. The side chains with too large molecular weight are intertwined with each other to influence the dispersion effect, and the side chains with too small molecular weight cannot play a role in rapid dispersion, so that the comprehensive performance of the polymer is weakened.
The invention is characterized in that the modified hyperbranched polyether macromonomer tail end contains a large amount of hydroxyl or carboxyl adsorption groups, thereby providing rapid adsorption capacity, and the hyperbranched structure has larger steric hindrance and dispersion capacity.
Because more adsorption groups exist after carboxylation, the calcium ion can be quickly adsorbed to the surface of Ca < 2+ > ions, and the macroscopic dispersion speed is driven to be increased.
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 rapid dispersion type polycarboxylate superplasticizer can be directly used as a cement dispersant, and can also be compounded with functional auxiliaries such as a defoaming agent, an air entraining agent, a retarder, a thickener, a shrinkage reducing agent and the like or other types of polycarboxylate superplasticizers according to a certain proportion for use, the specific compounding type and proportion are determined, and engineering technicians can preferably select the rapid dispersion type polycarboxylate superplasticizer after tests according to actual engineering requirements.
The invention has the beneficial effects that:
(1) The method has the advantages of rich raw material sources, mild reaction conditions in each step and mature method;
(2) The method of the invention adopts active hydroxyl to initiate glycidyl anion polymerization reaction, and can obtain a large amount of polycarboxylic acid water reducing agent with adsorption groups, and compared with the conventional polycarboxylic acid, the method has the advantages of high adsorption rate and high adsorption quantity.
(3) The fast dispersion type polycarboxylate superplasticizer prepared by the method can effectively improve the water reduction effect, has low mixing amount, high dispersion speed and good slump loss resistance, and also has a fast dispersion effect in a high admixture system.
Drawings
FIG. 1 is a GPC outflow curve of a polycarboxylic acid water reducing agent HPCA-1 obtained in example 1.
FIG. 2 is a GPC outflow curve of the polycarboxylic acid water-reducing agent obtained in comparative example 2.
Detailed Description
The technical solution of the present invention is further illustrated 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 dripping 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 the product A, 0.33 part of 4-dimethylaminopyridine and 15 parts of succinic anhydride were dissolved in 150 parts of dry N, N-dimethylformamide and the N content was maintained 2 Stirring for 6 hours at 40 ℃, cooling and purifying to obtain a macromonomer product B; prepared from 100 portions of macromonomer product B,10 portions of acrylic acid, 100 portions of deionized water and 1 portion ofAnd carrying out free radical polymerization on the mercaptoethanol under the action of an initiator ammonium persulfate to obtain the HPCA-1.
Synthesis example 2
50 parts of methyl allyl polyoxyethylene ether (in the general formula 1, -R) 1 is-CH 3 X is-CH 2 -, N is 50), dissolving in 150 parts of dry N, N-dimethylacetamide, adding 0.8 part of sodium methoxide catalyst at the temperature of 65 ℃, slowly dripping 30 parts of glycidyl ether, reacting for 12 hours at the temperature of 50 ℃, cooling and purifying to obtain a product A; 50 parts of the product A, 3 parts of 4-dimethylaminopyridine and 5 parts of glutaric anhydride obtained above were dissolved in 50 parts of dry N, N-dimethylacetamide and the solution was left to stand for N 2 Stirring for 2 hours at the temperature of 60 ℃, cooling and purifying to obtain a macromonomer product B; 50 parts of macromonomer product B,10 parts of methacrylic acid, 60 parts of deionized water and 0.5 part of mercaptopropionic acid are subjected to free radical polymerization under the action of hydrogen peroxide-sodium formaldehyde sulfoxylate to obtain HPCA-2.
Synthesis example 3
200 parts of butenyl polyoxyethylene ether (R in general formula 1) are weighed 1 Is H, X is-CH 2 CH 2 40) is dissolved in 500 parts of dry toluene, 15 parts of potassium ethoxide is added at the temperature of 90 ℃ to be used as a catalyst, 100 parts of glycidyl ether is slowly dropped to react for 48 hours at the temperature of 30 ℃, and the product A is obtained after cooling and purification; 200 parts of the product A, 25 parts of triethylamine and 50 parts of glutaric anhydride are dissolved in 300 parts of dry toluene, and N is kept 2 Stirring for 1 hour at the temperature of 80 ℃, cooling and purifying to obtain a macromonomer product B; HPCA-3 is obtained by free radical polymerization of 100 parts of macromonomer product B,10 parts of maleic acid, 100 parts of deionized water and 1 part of mercaptoethanol under the action of hydrogen peroxide-sodium formaldehyde sulfoxylate.
Synthesis example 4
Weighing 150 parts of vinyl polyoxyethylene ether (R in the general formula 1) 1 Is H, X is-OCH 2 CH 2 -, n is 30), dissolving in 300 portions of dried xylene, adding 5 portions of sodium ethoxide as catalyst at 100 deg.C, slowly dropping 50 portions of glycidyl ether, reacting at 40 deg.C for 36 hr, cooling and purifying to obtain the productA; 100 parts of the product A obtained above, 1.8 parts of triethylamine and 80 parts of succinic anhydride were dissolved in 200 parts of dry xylene, and N was maintained 2 Stirring for 3 hours at the temperature of 70 ℃, cooling and purifying to obtain a macromonomer product B; the HPCA-4 is obtained by free radical polymerization of 120 parts of macromonomer product B,25 parts of itaconic acid, 150 parts of deionized water and 4 parts of sodium methallyl sulfonate under the action of an initiator hydrogen peroxide-ascorbic acid system.
Synthesis example 5
250 parts of hydroxybutyl vinyl polyoxyethylene ether (R in the general formula 1) are weighed 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 the temperature of 90 ℃, slowly dropwise adding 80 parts of glycidyl ether, reacting for 24 hours at the temperature of 50 ℃, cooling and purifying to obtain a product A; dissolving 100 parts of the product A obtained in the step one, 8 parts of triethylamine and 100 parts of succinic anhydride in 300 parts of dry N, N-dimethylformamide, and keeping N 2 Stirring for 2 hours at the temperature of 80 ℃, cooling and purifying to obtain a macromonomer product B; 200 parts of macromonomer product B,40 parts of sodium methacrylate, 200 parts of deionized water and 10 parts of sodium methallyl sulfonate are subjected to free radical polymerization under the action of hydrogen peroxide, sodium bisulfite and ferrous sulfate to obtain HPCA-5.
Synthesis example 6
Weighing 100 parts of prenol polyoxyethylene ether (R in a general formula 1) 1 Is CH 3 X is-CH 2 CH 2 -N is 50), dissolving in 200 parts of dry N-methyl pyrrolidone, adding 3.8 parts of potassium ethoxide catalyst at the temperature of 130 ℃, slowly dripping 20 parts of glycidyl ether, reacting for 48 hours at the temperature of 35 ℃, cooling and purifying to obtain a product A; dissolving 100 parts of product A obtained in the step one, 2 parts of triethylamine and 100 parts of glutaric anhydride in 300 parts of dry N-methyl pyrrolidone, and keeping N 2 Stirring for 3 hours at the temperature of 70 ℃, cooling and purifying to obtain a macromonomer product B; is prepared by free radical polymerization of 300 parts of macromonomer product B,60 parts of sodium acrylate, 300 parts of deionized water and 15 parts of thioglycolic acid under the action of ammonium persulfateHPCA-6。
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 dripping 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 initiator ammonium persulfate.
Comparative example 2
300 parts of methyl allyl polyoxyethylene ether (in a general formula 1, -R) 1 is-CH 3 X is-CH 2 50 percent of n), 60 percent of acrylic acid, 300 percent of deionized water and 10 percent of thioglycolic 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
In order to examine the adsorption performance of all the synthesized samples in the cement slurry, 20g of cement is weighed and added into 10g of polycarboxylic acid solution prepared in each example and comparative example with the doping amount of 0.1% (folding solid), the mixture is stirred for a certain time, samples are regularly sampled and poured into a centrifuge tube, a high-speed centrifuge is adopted for separation (10000 r/min) for 2min, 2g of clear liquid at the upper part of the centrifuge tube is collected, 1g of HCl (1 mol/L) solution is used for acidification, and water is added for dilution to 20g. Respectively measuring the organic carbon content of clear liquid and blank sample (unblended cement) by using a Total organic carbon analyzer Multi N/C3100 produced by Germany Yale company, and calculating the adsorption amount of the surface of the cement particles by combining the concentration difference of the clear liquid and the blank sample (unblended cement) with the mixing amount of the high-efficiency fruit water reducing agent
TABLE 1 adsorption amount of sample with time
As seen from Table 1, the adsorption capacity of examples 1 to 6 in 4min is obviously higher than that of comparative example 1 and comparative example 2, and the adsorption capacity is basically close to the saturated adsorption capacity after 10min, which shows that the fast dispersion type water reducing agent synthesized by the invention has more adsorption and higher efficiency; by comparing comparative example 1 with comparative example 2, the adsorption capacity of comparative example 1 is high, which shows that the adsorption capacity of the carboxylated polyamide is remarkably improved.
Application example 2
Aqueous Gel Permeation Chromatography (GPC)
Relative molecular mass, molecular weight distribution, and conversion were determined by relative molecular mass, molecular weight distribution, using miniDAWNTristar aqueous gel permeation chromatography, produced by Wyatt technology corporation, USA: the flow rate of the mobile phase 0.01MNaNO3 aqueous solution is 1m L/min, and the mass concentration percentage of the sample is 0.5%.
The GPC flow curve of the polycarboxylate water reducer HPCA-1 prepared in example 1 is shown in FIG. 1, the GPC flow curve of the polycarboxylate water reducer prepared in comparative example 2 is shown in FIG. 2, and from FIG. 1 and FIG. 2, it is apparent that the application examples show an increase in the high molecular weight portion formed by the rapidly dispersing polycarboxylic acid of the present invention as compared with the comparative examples, thereby demonstrating the polymerization feasibility of the structure of the polycarboxylate water reducer prepared by the preparation method of the present invention.
Application example 3
The fluidity with time of the cement paste was measured in examples 1 to 6 and comparative examples 1 to 2 in accordance with GB/T8077-2012 "method for testing the homogeneity of concrete admixtures", respectively. The water cement ratio w/c is 0.22, the folding and fixing mixing amount of the polycarboxylate superplasticizer is 0.12-0.13% (by mass of cement), the test temperature is 20 +/-2 ℃, and the results are shown in Table 2.
TABLE 2 Cement neat paste fluidity results over time
Note: r = 4min stirring fluidity/1 min stirring fluidity
As can be seen from the data in Table 2, the rapid dispersion type polycarboxylate water reducer prepared by the invention has a rapid dispersion speed for cement at a low mixing amount, and the fluidity of the rapid dispersion type polycarboxylate water reducer in the examples 1-6 can reach 93% of that of 4min after being stirred for 1min by comparing the fluidity of the rapid dispersion type polycarboxylate water reducer in the examples 1-6 under stirring for 1min with the fluidity of the rapid dispersion type polycarboxylate water reducer in the examples 4 min. Whereas the conventional comparative example 2 can reach only 78% at higher loadings. And the samples of the examples 1 to 6 have large water reduction and good slump retaining property, while the comparative example has equivalent dispersing capacity and obviously faster loss with time under the condition of one higher mixing amount.
Through the comparative examples 1 and 2, it can be seen that the polyreactive hydroxyl derived from the polyether macromonomer also has a strong adsorption effect, the dispersion speed of the slurry is improved to a certain extent, but the adsorption capacity of the carboxyl is obviously more advantageous.
The concrete has the advantages of low water-cement ratio and is expected to be used for high-strength concrete systems.
Application example 4
The fluidity of the cement paste with time was measured in examples 1 to 6 and comparative example according to GB/T8077-2012 "test method for homogeneity of concrete admixture". The water-cement ratio w/c is 0.25, wherein the cementing material is mud + fly ash + slag =50% +35% +15%, the bending and fixing content of the polycarboxylate superplasticizer is 0.15% (by mass of cement), and the test temperature is 20 +/-2 ℃, and the results are shown in table 3.
TABLE 3 neat cement paste fluidity results over time
Note: r = stirring 4min fluidity/stirring 1min fluidity
In a 50% high admixture system, the fluidity of the examples 1-6 in 1 minute can reach more than 90% of that of 4min stirring under the low water-ash ratio of 0.25, while the fluidity of the common comb-shaped polymer comparative example 2 in 1min stirring under the higher doping amount is only less than 70%, which fully shows that the fast dispersion type polycarboxylate water reducer prepared by the invention has the advantage of fast dispersion in the high admixture system.
Application example 5
The application effect of the prepared fast-dispersing water reducing agent is further investigated through the fluidity of the mortar. Wherein the cement adopts two kinds of cement with different brands and specifications: P.II 52.5 cement and P.O 42.5 cement of river south small wild field; the test temperature is 20 ℃; the sand for the test adopts ISO standard sand, and the ratio of ash to sand is 1.8; the mixing amount is calculated according to the mass of the cement; the dispersing performance of the water reducing agent was examined by the initial fluidity of the mortar and the loss with time, and the test results were as follows.
TABLE 4 sample mortar Dispersion results
As can be seen from Table 4, two different cements showed different trends, with the cement loss continuing in the small field, and the sea snail cement mortar showed a significant rise in 30 min. Examples 1-6 the initial fluidity of the mortar in the small field cement was significantly greater than comparative examples 1 and 2, and the loss after 30min was significantly less, with the maximum loss being 26mm fluidity, whereas comparative example 2 lost 62mm fluidity after 30min, and comparative example 1 also lost 38mm fluidity.
Compared with the samples of comparative examples 1 and 2, the samples of examples 1 to 6 in the conch cement still have great advantages in initial water reduction, and the rapid 30-min reverse expansion shows that the fast-dispersing water reducing agent prepared by the invention has the advantages of high water reduction and high slump loss resistance.
Claims (13)
1. A preparation method of a fast dispersion type polycarboxylate superplasticizer is characterized by comprising the following steps: converting the terminal reactive hydroxyl of the terminal hyperbranched polyether into a carboxyl adsorption group, and then copolymerizing the carboxyl adsorption group with a small carboxylic monomer to obtain the fast-dispersing polycarboxylic acid water reducer;
the terminal hyperbranched polyether is a terminal hyperbranched polyoxyethylene ether macromolecule generated in situ after ring-opening polymerization of glycidyl ether initiated by hydroxyl at the terminal of a polyether macromonomer.
2. The preparation method of the fast-dispersing type polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps of:
(1) Weighing a polyether macromonomer, adding a catalyst in an organic solvent I at the temperature of 50-130 ℃, slowly dripping glycidyl ether with a 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 40-80 ℃, cooling and purifying to obtain a macromonomer product B;
(3) And (3) carrying out free radical polymerization on the macromonomer product B obtained in the step (2), a small carboxylic acid monomer, deionized water and a chain transfer agent under the action of an initiator to obtain the fast dispersion type polycarboxylate superplasticizer.
3. The preparation method of the fast dispersing type polycarboxylate superplasticizer according to claim 2, wherein the molar ratio of the glycidyl ether to the polyether macromonomer in the step (1) is 1-50: 1;
the mass ratio of the product A in the step (2) to the organic acid anhydride is controlled to be 0.1-1: 1;
the total weight concentration of the macromonomer B and the small carboxylic acid monomer in the polymerization process of the step (3) is controlled to be 20-60%.
4. The preparation method of the fast dispersing type polycarboxylate superplasticizer according to claim 2 or 3, wherein the polyether macromonomer in step (1) has a general structural formula shown in (1):
r in the formula (1) 1 is-H or-CH 3 N =10 to 45, 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 of;
the macromonomer product B in the step (3) is represented by the general formula (2):
r in the formula (2) 1 is-H or-CH 3 M = an integer of 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 independently selected integers from 0 to 50.
5. The preparation method of the fast dispersing type polycarboxylate superplasticizer according to claim 4, wherein the polyether macromonomer has a weight average molecular weight of 500-2000.
6. The preparation method of the fast dispersing type polycarboxylic acid water reducing agent according to claim 2 or 3, characterized in that the carboxylic acid small monomer in 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.
7. The preparation method of the fast dispersing type polycarboxylate superplasticizer according to claim 2, wherein the organic solvent in step (1)The solvent I 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 required to be subjected to anhydrous treatment before use, and the conventional anhydrous treatment is to add CaH 2 Refluxing for 4-6 h, and then distilling or distilling under reduced pressure to finish the anhydrous treatment;
the purification method in the step (1) and the purification method in the step (2) are both to remove the organic solvent by reduced pressure distillation, precipitate in acetone, centrifuge and dry;
in the step (1), the dropping time of the glycidyl ether is controlled to be 2.0-6.0 h.
8. The preparation method of the fast dispersing type polycarboxylate superplasticizer according to claim 3, wherein 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 mass of the reactants in the step (1);
the basic catalyst in the step (2) is triethylamine or 4-dimethylamino pyridine, and the dosage of the basic catalyst is 0.5-10% of the total reaction mass in the step (2).
9. The preparation method of the fast dispersing type polycarboxylate superplasticizer according to claim 4, wherein the organic acid anhydride in step (2) is preferably any one of succinic anhydride and glutaric anhydride.
10. The preparation method of the fast dispersing type polycarboxylate superplasticizer according to claim 3, wherein the radical polymerization method in the step (3) is redox radical polymerization, and the initiator 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; when the initiator is a composition of an oxidation component II and a reduction component, the oxidation component II is selected from one of persulfate and peroxide, and the reduction component is selected from one or more of bisulfite, sulfite, thiosulfate, pyrosulfite, ferrous salt, sodium formaldehyde sulfoxylate and L-ascorbic acid;
the total amount 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 selected from any one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and sodium methallyl sulfonate, 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 preparation method of the fast-dispersing polycarboxylate superplasticizer according to claim 10, wherein when the initiator is a single oxidation component I, the initiator is ammonium persulfate; when the initiator is a composition of the oxidation component II and the reduction component, the initiator is selected from any one of hydrogen peroxide-sodium formaldehyde sulfoxylate, hydrogen peroxide-ascorbic acid, hydrogen peroxide-sodium bisulfite and hydrogen peroxide-sodium bisulfite-ferrous sulfate.
12. The method for preparing a fast dispersing type polycarboxylate water reducer according to any one of claims 1 to 11, characterized in that the weight average molecular weight of the fast dispersing type polycarboxylate water reducer is 20000-50000.
13. The fast dispersing polycarboxylic acid water reducing agent prepared by the method of claim 12 is used as a cement dispersant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110412206.5A CN115215972B (en) | 2021-04-16 | 2021-04-16 | Preparation method of quick-dispersion polycarboxylate superplasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110412206.5A CN115215972B (en) | 2021-04-16 | 2021-04-16 | Preparation method of quick-dispersion polycarboxylate superplasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115215972A true CN115215972A (en) | 2022-10-21 |
| CN115215972B CN115215972B (en) | 2023-10-31 |
Family
ID=83604696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110412206.5A Active CN115215972B (en) | 2021-04-16 | 2021-04-16 | Preparation method of quick-dispersion polycarboxylate superplasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115215972B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117164770A (en) * | 2023-08-08 | 2023-12-05 | 长江三峡技术经济发展有限公司 | High-dispersion water reducer with shrinkage reducing function and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007112703A (en) * | 2005-09-22 | 2007-05-10 | Nippon Shokubai Co Ltd | Polycarboxylic acid polymer for cement admixture and cement admixture |
| CN102093520A (en) * | 2010-12-22 | 2011-06-15 | 江苏博特新材料有限公司 | Preparation method of hyperbranched polycarboxylic acid copolymer cement dispersant |
| CN105542147A (en) * | 2016-01-27 | 2016-05-04 | 江苏苏博特新材料股份有限公司 | Preparation method of water reducing agent with hyper-branched topological structure and application of water reducing agent |
| CN106674439A (en) * | 2016-12-29 | 2017-05-17 | 中科院广州化学有限公司南雄材料生产基地 | Low and slow coagulating hyperbranched polycarboxylic acid super-plasticizer, preparation method and application thereof |
| CN111978487A (en) * | 2020-09-01 | 2020-11-24 | 广州市建筑科学研究院有限公司 | Homograph arm star type polycarboxylate superplasticizer and preparation method and application thereof |
-
2021
- 2021-04-16 CN CN202110412206.5A patent/CN115215972B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007112703A (en) * | 2005-09-22 | 2007-05-10 | Nippon Shokubai Co Ltd | Polycarboxylic acid polymer for cement admixture and cement admixture |
| CN102093520A (en) * | 2010-12-22 | 2011-06-15 | 江苏博特新材料有限公司 | Preparation method of hyperbranched polycarboxylic acid copolymer cement dispersant |
| CN105542147A (en) * | 2016-01-27 | 2016-05-04 | 江苏苏博特新材料股份有限公司 | Preparation method of water reducing agent with hyper-branched topological structure and application of water reducing agent |
| CN106674439A (en) * | 2016-12-29 | 2017-05-17 | 中科院广州化学有限公司南雄材料生产基地 | Low and slow coagulating hyperbranched polycarboxylic acid super-plasticizer, preparation method and application thereof |
| CN111978487A (en) * | 2020-09-01 | 2020-11-24 | 广州市建筑科学研究院有限公司 | Homograph arm star type polycarboxylate superplasticizer and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "支化型聚羧酸减水剂的合成及其性能研究", 新型建筑材料, vol. 46, no. 10, pages 67 - 71 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117164770A (en) * | 2023-08-08 | 2023-12-05 | 长江三峡技术经济发展有限公司 | High-dispersion water reducer with shrinkage reducing function and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115215972B (en) | 2023-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111377642B (en) | Multi-element adsorption polycarboxylate superplasticizer and preparation method and application thereof | |
| JP6074517B2 (en) | Method for producing slump retention type polycarboxylate-based high performance fluidizing agent | |
| EP1767555B1 (en) | Novel polymer and cement admixture using the same | |
| KR100771024B1 (en) | Cement admixture and cement composition | |
| CN101333092B (en) | Cement concrete superplasticizer and method for preparing same | |
| CN105601839B (en) | The preparation method and application of the polycarboxylate water-reducer of phosphorous acidic groups | |
| JP5955386B2 (en) | Polycarboxylic acid copolymer, cement dispersant, cement admixture, and cement composition | |
| JP4233294B2 (en) | Cement admixture, cement composition, and method for producing cement admixture | |
| CN108864374B (en) | Preparation method of ether high-water-retention polycarboxylate superplasticizer | |
| CN101817657A (en) | Polycarboxylic acid slump retaining agent | |
| CN107652405B (en) | Polycarboxylate superplasticizer with amide/imide structure and preparation method thereof | |
| CN113683738B (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| CN109608594A (en) | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof | |
| EP1725509A1 (en) | Drying shrinkage-reducing agent | |
| WO2012083536A1 (en) | Preparation method of hyperbranched polycarboxylic acid type copolymer cement dispersant | |
| CN102153711A (en) | Preparation method of slow-setting polycarboxylic acid water reducing agent | |
| WO2022000306A1 (en) | Multifunctional superplasticizer for ultra-high performance concrete and preparation method therefor | |
| JP2003221266A (en) | Cement admixture | |
| CN102503221B (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| JP2012166978A (en) | Cement admixture and cement composition | |
| CN112358584B (en) | Sterically hindered mud-resistant polycarboxylate superplasticizer and preparation method thereof | |
| CN115215972B (en) | Preparation method of quick-dispersion polycarboxylate superplasticizer | |
| JP2012171819A (en) | Cement admixture and cement composition containing the same | |
| CN114873947B (en) | Slump loss resistant concrete water reducing agent and preparation method thereof | |
| JP4079589B2 (en) | Process for producing polycarboxylic acid copolymer |
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 |