CN109354654A - A kind of early strength polycarboxylate water reducer and preparation method thereof - Google Patents
A kind of early strength polycarboxylate water reducer and preparation method thereof Download PDFInfo
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- CN109354654A CN109354654A CN201811000732.5A CN201811000732A CN109354654A CN 109354654 A CN109354654 A CN 109354654A CN 201811000732 A CN201811000732 A CN 201811000732A CN 109354654 A CN109354654 A CN 109354654A
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- containing amine
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 51
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- 125000003277 amino group Chemical group 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000008030 superplasticizer Substances 0.000 claims description 40
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 32
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 18
- 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 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 235000019260 propionic acid Nutrition 0.000 claims description 16
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 9
- -1 amine group compound Chemical class 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical group O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 4
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 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
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 11
- 150000001408 amides Chemical class 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 17
- 239000004568 cement Substances 0.000 abstract description 14
- 125000003368 amide group Chemical group 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 5
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 239000012986 chain transfer agent Substances 0.000 abstract 1
- 229910001653 ettringite Inorganic materials 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- NOAAMORLQWOAEL-UHFFFAOYSA-N ethoxy-n,n-di(propan-2-yl)phosphonamidous acid Chemical compound CCOP(O)N(C(C)C)C(C)C NOAAMORLQWOAEL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical group CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 239000003643 water by type 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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明公开了一种早强型聚羧酸减水剂及其制备方法，该减水剂是不饱和聚醚、不饱和羧酸、含醇胺基团的不饱和酯以及不饱和含酰胺基团的化合物在氧化还原体系中和链转移剂作用下通过自由基聚合反应制得的，制备过程无需热源，绿色环保。所得减水剂采取具有长侧链的不饱和聚醚，对水泥及混凝土构件的早期强度有一定的增强作用；选择含醇胺基团的不饱和酯及不饱和含酰胺基团的化合物为不饱和早强单体，其中的醇胺基团和酰胺基团会促进C3A水化，生成钙矾石，加快进入水泥水化加速期，缩短水泥凝结时间，从而提高早期强度，提高水泥及混凝土构件的生产效率。同时，减水剂分子中的羧酸基团和酯基会使其具有良好的分散性以及分散保持性。The invention discloses an early-strength polycarboxylate water-reducing agent and a preparation method thereof. The water-reducing agent is an unsaturated polyether, an unsaturated carboxylic acid, an unsaturated ester containing an alcohol amine group, and an unsaturated amide group containing The compound of the group is prepared by free radical polymerization under the action of a redox system and a chain transfer agent, the preparation process does not require a heat source, and is environmentally friendly. The obtained water reducing agent adopts unsaturated polyether with long side chain, which has a certain strengthening effect on the early strength of cement and concrete components; Saturated early-strength monomer, in which the alcoholamine group and amide group will promote the hydration of C 3 A, generate ettringite, accelerate the entry into the accelerated period of cement hydration, shorten the setting time of cement, thereby improving the early strength and improving the efficiency of cement. Production efficiency of concrete elements. At the same time, the carboxylic acid group and ester group in the water reducing agent molecule will make it have good dispersibility and dispersion retention.
Description
Technical field
The present invention relates to a kind of Early-strength polycarboxylate superplasticizers and preparation method thereof, and in particular to arrives a kind of alcohol-containing amine groups
Beta-unsaturated esters and unsaturated phosphinylidyne-containing amine group compound be unsaturated early strong monomer Early-strength polycarboxylate superplasticizer and
Preparation method belongs to building material technical field.
Background technique
In building engineering field, concrete is a kind of maximum civil engineering material of dosage, build house, repair the dykes and build dams with
And railway construction is both needed to using concrete.With the development of the times, requirements at the higher level are proposed to the performance of concrete, also to poly- carboxylic
The functionality of sour water-reducing agent has higher requirement.Polycarboxylate water-reducer have volume is low, water-reducing rate is high, concrete mix and
The features such as easy property and good durability, have a vast market application prospect.
At low ambient temperatures, polycarboxylate water-reducer is unfavorable for hydrated cementitious, extends setting time, generates to early strength
Certain influence when preparing prefabricated components, if can be improved early strength, can greatly increase production efficiency.Therefore, needle
The problem weak to polycarboxylate water-reducer addition bring early strength, someone develops with early powerful poly- carboxylic at present
Sour water-reducing agent is conducive to improve the concrete slow problem of hydration rate and quickening construction and manufacture tubular pole system at low ambient temperatures
The speed of product, increases economic efficiency.
Currently, for the study on the synthesis of Early-strength polycarboxylate superplasticizer, there are mainly two types of approach: (1) compounding: in plain edition
Being added in polycarboxylate water-reducer has early powerful inorganic or organic ingredient, and the approach morning powerful ingredient volume is not easily-controllable
System, it is unfavorable to develop to concrete strength, and compound system is easily layered, and storage stability is deteriorated.(2) it synthesizes: with synthesis
Method, synthesize Early-strength polycarboxylate superplasticizer using the modifiable property of its molecule, and with Raolical polymerizable.
For example, patent CN201510736253.X discloses a kind of Early-strength polycarboxylate superplasticizer of carbon containing oxa- ring
Preparation method and products thereof, the patent are reacted with maleic anhydride under cryogenic by amido tetrahydrofuran, pass through acid anhydrides
Ring-opening reaction and amido tetrahydrofuran-compound form amide key connection, and then by it under the conditions of room temperature or low-temp reaction and not
Saturated carboxylic acid, unsaturated polyether carry out free radicals copolymerization reaction, so that preparation has the polycarboxylate water-reducer of carbon oxa- ring structure.
Though the Early-strength polycarboxylate superplasticizer of patent synthesis improves early strength of concrete, unsaturated tetrahydro to a certain extent
The requirement of furan compound preparation process is harsh, is not suitable for industrial production.
Patent 201410187323.6 discloses a kind of preparation of Early-strength polycarboxylate superplasticizer that triisopropanolamine is modified
Method, this method are modified water-reducing agent using maleic acid triisopropanolamine ester, obtain Early-strength polycarboxylate superplasticizer, this subtracts
Aqua to the effect of haveing a certain upgrade of concrete component early strength, but promoted it is limited, and the polycarboxylate water-reducer volume compared with
Greatly, at high cost, it is unfavorable for large-scale promotion application.
From the foregoing, the preparation of Early-strength polycarboxylate superplasticizer has certain problems at present, so search out one kind
Addition content is few, is remarkably improved early strength, the Early-strength polycarboxylate superplasticizer tool that preparation process is more easy compared with the prior art
There is important meaning.
Summary of the invention
A series of problems, such as insufficient for early strength of concrete caused by existing polycarboxylate water-reducer, the present invention provides
A kind of Early-strength polycarboxylate superplasticizer, the water-reducing agent is with the change of the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group
Closing object is unsaturated early strong monomer, and the modification by unsaturated early strong monomer to water-reducing agent can effectively facilitate cement minerals water
Solution effectively improves the early strength of cement, concrete structure, shortens setting time, improves production efficiency.
The present invention also provides the preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, this method safe operation is simple, nothing
It needs to heat, energy consumption is lower, environmentally protective.
It is unsaturated early that the present invention, which selects the beta-unsaturated esters of alcohol-containing amine groups and the compound of unsaturated phosphinylidyne-containing amine group,
Strong monomer is modified water-reducing agent, and being added into diminishing agent molecule has early powerful alcohol amine groups and amide group,
Both groups can promote C3A aquation forms entringite, effectively mineral aquation initial stage is inhibited to form loose structure, promotes water
The hydrolysis of mud mineral is accelerated to enter hydrated cementitious accelerated period, shortens setting time, improves early strength, efficiently solve in engineering
Stubborn problem.
Early-strength type polycarboxylate water-reducer be made from the following raw materials in parts by weight: unsaturated polyether 120 ~
160 parts, 8 ~ 20 parts of unsaturated carboxylic acid, 1 ~ 6 part of the beta-unsaturated esters of alcohol-containing amine groups, unsaturated phosphinylidyne-containing amine group compound 0.5 ~
4 parts, 2 ~ 4 parts of oxidant, 0.3 ~ 0.8 part of reducing agent, 0.6 ~ 1.5 part of chain-transferring agent.
Preferably, Early-strength polycarboxylate superplasticizer is to be made of raw material from the following weight: 120 parts of unsaturated polyether, no
10-11 parts of saturated carboxylic acid, 1 ~ 2 part of the beta-unsaturated esters of alcohol-containing amine groups, unsaturated phosphinylidyne-containing amine group 0.5 ~ 1 part of compound, oxygen
2-3 parts of agent, 0.3-0.5 parts of reducing agent, 0.7-0.75 parts of chain-transferring agent.
Further, the unsaturated polyether be relative molecular mass 3000 ~ 5000 isobutene alcohol polyoxyethylene ether or
Person's isoamyl alcohol polyoxyethylene ether.
Further, the unsaturated carboxylic acid is one of acrylic acid, maleic acid, methacrylic acid and itaconic acid or more
Kind.
Further, the compound of the unsaturated phosphinylidyne-containing amine group is acrylamide, 2- acrylamide -2- methyl-prop sulphur
Acid or N hydroxymethyl acrylamide.
Further, the oxidant is one of ammonium persulfate, sodium peroxydisulfate, hydrogen peroxide or a variety of.
Further, the reducing agent is one of bisulfites, sulphite, ascorbic acid and thiosulfate
Or it is several.
Further, the chain-transferring agent is thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acid or methacrylic sulfonic acid
Sodium.
Further, the beta-unsaturated esters of alcohol-containing amine groups of the present invention are that inventor obtains by itself research,
With preferable early strong effect, the beta-unsaturated esters of the alcohol-containing amine groups are by alcamine compound and unsaturated acid anhydride through esterification
And it obtains.
Further, the alcamine compound be diethanol monoisopropanolamine or monoethanol diisopropanolamine (DIPA), it is described not
Being saturated acid anhydrides is maleic anhydride or itaconic anhydride.Preferably, the molar ratio of alcamine compound and unsaturated acid anhydride be 0.8 ~
1.2:1.
Further, specific reaction step is as follows: alcamine compound being mixed with propionic acid, unsaturated acids is then added
Acid anhydride, catalyst and polymerization inhibitor carry out esterification, obtain the beta-unsaturated esters of alcohol-containing amine groups.
Further, the effect of propionic acid: 1, as solvent；2, inhibit the amidation process of alcamine compound and acid anhydrides；
3, be conducive to improve esterification yield.Preferably, the molar ratio of alcamine compound and propionic acid is 0.8 ~ 1.2:1.
Further, the catalyst is p-methyl benzenesulfonic acid or phosphorus pentoxide, and the polymerization inhibitor is hydroquinone or right
Hydroxyanisol.The dosage of catalyst is 2.5 ~ 3.5wt% of alcamine compound, and the dosage of polymerization inhibitor is alcamine compound
0.04 ~ 0.07wt%.
Further, alcamine compound is reacted at 50 ~ 60 DEG C with propionic acid.
Further, alcamine compound is reacted at 100 ~ 110 DEG C with unsaturated acid anhydride.After reaction, subtract
Propionic acid is distilled off in pressure, obtains the beta-unsaturated esters of alcohol-containing amine groups.
The present invention also provides the preparation method of above-mentioned Early-strength polycarboxylate superplasticizer, the water-reducing agent be unsaturated polyether,
The compound of unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group oxidant, reducing agent and
Chain-transferring agent effect is lower to carry out what Raolical polymerizable was prepared.
Further, Early-strength polycarboxylate superplasticizer of the present invention prepare when the following steps are included:
(1) compound of unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group is soluble in water, it obtains
A material, reducing agent is soluble in water with chain-transferring agent, obtain B material；
(2) unsaturated polyether is soluble in water, it stirs evenly, oxidant is then added, stir 5-15 minutes, then start simultaneously
A material and B material is added dropwise, after wherein A drop adds 1.5 ~ 3h, B drop that 2 ~ 4h, A material and B is added to expect equal completion of dropwise addition, curing 1 that the reaction was continued
~ 3h, then adjusting solid content is 35 ~ 45wt%, obtains Early-strength polycarboxylate superplasticizer.
Further, in step (1) and (2), each raw material is completely dissolved by the dosage satisfaction of water.
Further, the beta-unsaturated esters of the alcohol-containing amine groups are prepared using method disclosed above.
Further, water-reducing agent is prepared at normal temperature, and without heating, low energy consumption, environmentally protective.
Further, solid content is preferably 39 ~ 41wt% in gained Early-strength polycarboxylate superplasticizer.
Early-strength water-reducing agent of the present invention can be used in cement and concrete component, and addition content is few, addition content 1% with
Under good diminishing and early function can be realized (in terms of cement), have to the early strength of cement and concrete component very aobvious
The castering action of work.
The invention has the benefit that
1, water-reducing agent of the present invention takes the unsaturated polyether with long side chain, has one to the early strength of cement and concrete component
Fixed humidification；The compound of the beta-unsaturated esters and unsaturated phosphinylidyne-containing amine group that select alcohol-containing amine groups is unsaturated early strong single
Body, alcohol amine groups therein and amide group can promote C3A aquation generates entringite, accelerates to enter hydrated cementitious accelerated period, contracting
Short cement setting time improves the production efficiency of cement and concrete component to improve early strength.Meanwhile water-reducing agent point
Carboxylic acid group and ester group in son can make it have good dispersibility and dispersion retentivity, also have to the raising of early strength
Positive effect.
2, Early-strength polycarboxylate superplasticizer of the present invention by unsaturated polyether, unsaturated carboxylic acid, alcohol-containing amine groups unsaturation
The compound of ester and unsaturated phosphinylidyne-containing amine group passes through free radical polymerization in redox system and under chain-transferring agent effect
Reaction is prepared.The water-reducing agent preparation method is simple, and preparation process is easy to control, and yield is high, is not necessarily to heat source, at low cost, green
Colour circle is protected, and early strength of concrete can be improved compared with low-dosage, with good application prospect and large-scale promotion
Application value.
Specific embodiment
In the following, the present invention is further expalined and is illustrated by specific embodiment, following embodiments, which only play, to be shown
Example effect, is not defined protection scope.
The preparation of the beta-unsaturated esters of alcohol-containing amine groups
Embodiment 1
In equipped with stirring, temperature control and condensation reflux unit consersion unit, by the DEIPA(diethanol monoisopropanolamine of 16.3g)
Be placed in four-hole bottle, the propionic acid that 7.4g is added is neutralized, control temperature less than 55 DEG C, then be added 9.8g maleic anhydride,
0.47g catalyst p-methyl benzenesulfonic acid and 0.0094g hydroquinone of polymerization retarder, control reaction temperature is at 105 DEG C or so, the reaction time
It is no longer reduced to acid value, terminates reaction, vacuum distillation removes propionic acid to get the beta-unsaturated esters A of alcohol-containing amine groups, structural formula is arrived
It is as follows:
Embodiment 2
In equipped with stirring, temperature control and condensation reflux unit consersion unit, by the EDIPA(monoethanol diisopropanolamine (DIPA) of 17.7g)
It is placed in four-hole bottle, the propionic acid that 7.4g is added is neutralized, and controls temperature less than 58 DEG C, the maleic acid of 9.8g is then added
Acid anhydride, 0.50g catalyst p-methyl benzenesulfonic acid and 0.01g hydroquinone of polymerization retarder control reaction temperature at 110 DEG C or so, reaction
Between no longer reduced to acid value, terminate reaction, vacuum distillation remove propionic acid to get arrive alcohol-containing amine groups beta-unsaturated esters B, structure
Formula is as follows:
Embodiment 3
In equipped with stirring, temperature control and condensation reflux unit consersion unit, by the DEIPA(diethanol monoisopropanolamine of 16.3g)
Be placed in four-hole bottle, the propionic acid that 7.4g is added is neutralized, control temperature at 60 DEG C, then be added 13.1g itaconic anhydride,
0.52g catalyst phosphorus pentoxide and 0.01g polymerization inhibitor p-hydroxyanisole control reaction temperature at 105 DEG C or so, reaction
Between do not reduced to acid value, terminate reaction, vacuum distillation remove propionic acid to get arrive alcohol-containing amine groups beta-unsaturated esters C, structure
Formula is as follows:
The preparation of Early-strength polycarboxylate superplasticizer
Embodiment 4
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 10.4g, beta-unsaturated esters A 1.57g of the alcohol-containing amine groups of embodiment 1, acrylamide 0.71g, hydrogen peroxide 2.4g, Vitamin C
Sour 0.4g, thioacetic acid 0.72g.
120g isoamyl alcohol polyoxyethylene ether is added into the four-hole boiling flask for the 500mL being fixed on electric mixing device
(relative molecular mass 3000), deionized water 80g stirs to being completely dissolved, 2.4g hydrogen peroxide and 5.0g deionization is then added
The initiation liquid that water mixes, stir 10min after begin to use peristaltic pump be added dropwise A material and B material, A material by 10.4g acrylic acid,
Beta-unsaturated esters A, 0.71g acrylamide of alcohol-containing amine groups prepared by 1.57g embodiment 1 and the mixed solution of 40g deionized water
Composition, the at the uniform velocity completion of dropwise addition in 2 hours, B expect by 0.4g ascorbic acid, the mixing of 0.72g thioacetic acid and 50g deionized water
Solution composition, the at the uniform velocity completion of dropwise addition in 2.5 hours.After A material and B drop add, continue stirring curing 1.5 hours, then
Moisturizing to water-reducing agent solid content is 40%, i.e. synthesis Early-strength polycarboxylate superplasticizer.
Embodiment 5
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 10.4g, beta-unsaturated esters B 1.57g of the alcohol-containing amine groups of embodiment 2,2- acrylamide-2-methyl propane sulfonic 2.1g, dioxygen
Water 2.4g, ascorbic acid 0.4g, thioacetic acid 0.72g.
Preparation method is the same as embodiment 4.
Embodiment 6
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 10.4g, beta-unsaturated esters C 1.57g of the alcohol-containing amine groups of embodiment 3, N hydroxymethyl acrylamide 1.1g, hydrogen peroxide 2.4g,
Ascorbic acid 0.4g, thioacetic acid 0.72g.
Preparation method is the same as embodiment 4.
Embodiment 7
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 9.2g, beta-unsaturated esters B 1.8g of the alcohol-containing amine groups of embodiment 2,2- acrylamide-2-methyl propane sulfonic 2.1g, hydrogen peroxide
3.0g, ascorbic acid 0.4g, thioacetic acid 0.72g.
Preparation method is the same as embodiment 4.
Embodiment 8
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 120g, the propylene of relative molecular mass 3000
Sour 10.4g, beta-unsaturated esters C 1.6g of the alcohol-containing amine groups of embodiment 3, N hydroxymethyl acrylamide 1.1g, hydrogen peroxide 2.4g,
Ascorbic acid 0.4g, thioacetic acid 0.72g.
Preparation method is the same as embodiment 4.
Embodiment 9
The formula of Early-strength polycarboxylate superplasticizer are as follows: the isobutene alcohol polyoxyethylene ether 140g of relative molecular mass 3000, Malaysia
Sour 20g, beta-unsaturated esters A 3g of the alcohol-containing amine groups of embodiment 1, acrylamide 4g, ammonium persulfate 2g, sulphite 0.8g, first
Base sodium allylsulfonate 1g.
Preparation method is referring to embodiment 4.
Embodiment 10
The formula of Early-strength polycarboxylate superplasticizer are as follows: isoamyl alcohol polyoxyethylene ether 160g, the methyl of relative molecular mass 5000
Acrylic acid 8g, beta-unsaturated esters A 6g of the alcohol-containing amine groups of embodiment 1, acrylamide 0.5g, sodium peroxydisulfate 4g, thiosulfate
0.3g, 3- mercaptopropionic acid 1.5g.
Preparation method is referring to embodiment 4.
Comparative example 1
Early-strength polycarboxylate superplasticizer is prepared according to the method for embodiment 4, unlike: it is added without the unsaturation of alcohol-containing amine groups
Ester A.
Comparative example 2
In equipped with stirring, temperature control and condensation reflux unit consersion unit, the triethanolamine of 14.9g is placed in four-hole bottle, is added
The propionic acid for entering 7.4g is neutralized, and controls temperature at 60 DEG C, then the maleic anhydride of addition 9.8g, 0.45g catalyst are to first
Benzene sulfonic acid and 0.0085g hydroquinone of polymerization retarder control reaction temperature at 105 DEG C or so, and the reaction time to acid value is not reducing,
Reaction is terminated, vacuum distillation removes propionic acid to get the beta-unsaturated esters D of alcohol-containing amine groups is arrived.
Early-strength polycarboxylate superplasticizer is prepared according to the method for embodiment 4, unlike: by the unsaturation of alcohol-containing amine groups
Ester A replaces with the beta-unsaturated esters D of alcohol-containing amine groups, and acrylamide is replaced with n-isopropyl acrylamide.
For the performance for verifying Early-strength polycarboxylate superplasticizer of the present invention, following experiments are carried out:
Example and the water-reducing agent 2.25g of comparative example, experimental water 157g, 42.5 ordinary silicon of scenery with hills and waters Eastern Mountain board PO respectively
Acid salt cement 450g is operated referring to GB.T17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " standard, measurement
Mortar specimen intensity.Test result is as shown in table 1.
By above-mentioned experimental result it can be found that adding the pressure resistance of mortar 1d, 3d, 28d of water-reducing agent of the embodiment of the present invention
Degree is significantly greater than the mortar compression strength for adding comparative example water-reducing agent, it can be seen that, early-strength polycarboxylic acids incorporated in the present invention subtracts
Aqua can be obviously promoted the early strength of cement-based material at low dosage.
The foregoing is only a preferred embodiment of the present invention, it will be appreciated by those of skill in the art that
In the case where not departing from present inventive concept and range defined by claims, various modifications can be made to the present invention, are added
Adduction replacement.
Claims (10)
1. a kind of Early-strength polycarboxylate superplasticizer, it is characterized in that being made of raw material from the following weight: unsaturated polyether 120 ~ 160
Part, 1 ~ 6 part of the beta-unsaturated esters of 8 ~ 20 parts of unsaturated carboxylic acid, alcohol-containing amine groups, unsaturated phosphinylidyne-containing amine group compound 0.5 ~ 4
Part, 2 ~ 4 parts of oxidant, 0.3 ~ 0.8 part of reducing agent, 0.6 ~ 1.5 part of chain-transferring agent；The beta-unsaturated esters of the alcohol-containing amine groups are by alcohol
Aminated compounds and unsaturated acid anhydride are obtained through esterification.
2. Early-strength polycarboxylate superplasticizer according to claim 1, it is characterized in that being made of raw material from the following weight: no
It is saturated 120 parts of polyethers, 10-11 part of unsaturated carboxylic acid, 1 ~ 2 part of the beta-unsaturated esters of alcohol-containing amine groups, unsaturation phosphinylidyne-containing amine group
0.5 ~ 1 part of compound, 2-3 parts of oxidant, 0.3-0.5 parts of reducing agent, 0.7-0.75 parts of chain-transferring agent.
3. Early-strength polycarboxylate superplasticizer according to claim 1 or 2, it is characterized in that: the alcamine compound is two
Ethyl alcohol monoisopropanolamine or monoethanol diisopropanolamine (DIPA), the unsaturated acid anhydride are maleic anhydride or itaconic anhydride；Preferably, alcohol
The molar ratio of aminated compounds and unsaturated acid anhydride is 0.8 ~ 1.2:1.
4. Early-strength polycarboxylate superplasticizer according to claim 1,2 or 3, it is characterized in that: the unsaturation amide-containing
The compound of group is acrylamide, 2- acrylamide-2-methyl propane sulfonic or N hydroxymethyl acrylamide.
5. Early-strength polycarboxylate superplasticizer according to claim 1,2 or 3, it is characterized in that: the unsaturated polyether is phase
To the isobutene alcohol polyoxyethylene ether or isoamyl alcohol polyoxyethylene ether of molecular mass 3000 ~ 5000；The unsaturated carboxylic acid
For one of acrylic acid, maleic acid, methacrylic acid and itaconic acid or a variety of；The oxidant is ammonium persulfate, persulfuric acid
One of sodium and hydrogen peroxide are a variety of；The reducing agent is bisulfites, sulphite, ascorbic acid and thiosulfuric acid
One or more of salt；The chain-transferring agent is thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acid or methacrylic sulfonic acid
Sodium.
6. Early-strength polycarboxylate superplasticizer according to claim 1,2 or 3, it is characterized in that: the unsaturation of alcohol-containing amine groups
The preparation method of ester includes: to mix alcamine compound with propionic acid, be then added unsaturated acid anhydride, catalyst and polymerization inhibitor into
Row esterification obtains the beta-unsaturated esters of alcohol-containing amine groups.
7. Early-strength polycarboxylate superplasticizer according to claim 6, it is characterized in that: the catalyst be p-methyl benzenesulfonic acid or
Phosphorus pentoxide, the polymerization inhibitor are hydroquinone or p-hydroxyanisole；Preferably, mole of alcamine compound and propionic acid
Than being the 2.5 ~ 3.5% of alcamine compound for the dosage of 0.8 ~ 1.2:1, catalyst, the dosage of polymerization inhibitor is alcamine compound
0.04 ~ 0.07%.
8. Early-strength polycarboxylate superplasticizer according to claim 6, it is characterized in that: alcamine compound and propionic acid 50 ~
It is reacted at 60 DEG C；Then it is reacted at 100 ~ 110 DEG C with unsaturated acid anhydride again.
9. a kind of preparation method of Early-strength polycarboxylate superplasticizer described in claim 1, it is characterized in that: the poly- carboxylic of the early-strength
Sour water-reducing agent by unsaturated polyether, unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group chemical combination
Object carries out Raolical polymerizable under the effect of oxidant, reducing agent and chain-transferring agent and is prepared.
10. preparation method according to claim 9, it is characterized in that the following steps are included:
(1) compound of unsaturated carboxylic acid, the beta-unsaturated esters of alcohol-containing amine groups and unsaturated phosphinylidyne-containing amine group is soluble in water, it obtains
A material, reducing agent is soluble in water with chain-transferring agent, obtain B material；
(2) unsaturated polyether is soluble in water, it stirs evenly, oxidant is then added, stir 5-15 minutes, then start simultaneously
A material and B material is added dropwise, after wherein A drop adds 1.5 ~ 3h, B drop that 2 ~ 4h, A material and B is added to expect equal completion of dropwise addition, curing 1 that the reaction was continued
~ 3h, then adjusting solid content is 35 ~ 45wt%, obtains Early-strength polycarboxylate superplasticizer.
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