CN100381387C - Amphoteric carboxylic acid comb grafted copolymer as concrete super-plasticizing agent - Google Patents
Amphoteric carboxylic acid comb grafted copolymer as concrete super-plasticizing agent Download PDFInfo
- Publication number
- CN100381387C CN100381387C CNB2005100378711A CN200510037871A CN100381387C CN 100381387 C CN100381387 C CN 100381387C CN B2005100378711 A CNB2005100378711 A CN B2005100378711A CN 200510037871 A CN200510037871 A CN 200510037871A CN 100381387 C CN100381387 C CN 100381387C
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- Prior art keywords
- monomer
- concrete
- graft copolymer
- general formula
- reaction
- Prior art date
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- 239000004567 concrete Substances 0.000 title claims abstract description 76
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 40
- 229920001577 copolymer Polymers 0.000 title claims description 24
- 239000003795 chemical substances by application Substances 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 11
- 150000003254 radicals Chemical class 0.000 claims abstract description 9
- 239000008030 superplasticizer Substances 0.000 claims description 29
- -1 hydroxypropyl Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 4
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- JAIPMKVUHGVBFU-UHFFFAOYSA-N benzyl-dimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)CC1=CC=CC=C1 JAIPMKVUHGVBFU-UHFFFAOYSA-N 0.000 claims description 2
- ZGQOVGXPFYKMRS-UHFFFAOYSA-M benzyl-dimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)CC1=CC=CC=C1 ZGQOVGXPFYKMRS-UHFFFAOYSA-M 0.000 claims description 2
- QBZPCMKUFMJWAN-UHFFFAOYSA-N benzyl-dimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C=CC(=O)NCCC[N+](C)(C)CC1=CC=CC=C1 QBZPCMKUFMJWAN-UHFFFAOYSA-N 0.000 claims description 2
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical group C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 claims description 2
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 claims description 2
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 2
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 claims description 2
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 239000006185 dispersion Substances 0.000 abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 13
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- 230000000996 additive effect Effects 0.000 abstract description 3
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- 241000047703 Nonion Species 0.000 abstract 1
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- 239000004568 cement Substances 0.000 description 29
- 230000014759 maintenance of location Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 108010043158 Trypanosoma Variant Surface Glycoproteins Proteins 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011372 high-strength concrete Substances 0.000 description 4
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- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 101000822677 Clostridium perfringens (strain 13 / Type A) Small, acid-soluble spore protein 1 Proteins 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 101000576806 Protobothrops flavoviridis Small serum protein 1 Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
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- 238000005886 esterification reaction Methods 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- 239000004971 Cross linker Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to an amphoteric carboxylic acid combing graft copolymer super plasticization agent for concrete, which is prepared by the following steps: 1) hydrophilic free radical copolymerization reaction: 8 to 40% of monomer a represented in a general formula 1, 55 to 85% of monomer b represented in a general formula 2, 2 to 20% of cationic monomer c and 0 to 15% of non-ion monomer d represented in a general formula (7) are copolymerized in a free radical way in a hydrophilic medium; 2) cross-linking reaction: a crosslinking agent shown in a general formula (8) is directly added to react in a crosslinking way after the polymerization reaction is finished. The present invention firstly provides that the saturation mixed amount of the super plasticization agent for concrete can be increased by an amphoteric ionic polymer and an amphoteric ion conception is introduced in the molecule structure design of a concrete additive, so the amphoteric carboxylic acid combing graft copolymer super plasticization agent for concrete in high water reducing rate is synthesized, the pollution of the production technology of a traditional water reducing agent for concrete to the environment is thoroughly eliminated, and the present invention can still indicates the outstanding dispersion performance and slump constant holding capacity under the lower mixed amount.
Description
Technical Field
The invention relates to a high water-reducing superplasticizer for cement, concrete and mortar, in particular to an amphoteric carboxylic acid comb-shaped graft copolymer concrete superplasticizer, belonging to the technical field of concrete additives in building materials.
Background
The cement concrete is the most used building material in the world, but the cement concrete has the defects of self weight, low strength, brittleness and the like. With the rapid development of the construction industry, new requirements are continuously provided for various performances of concrete, such as improving the strength of the concrete, improving the slump loss of the concrete in the transportation process and the like. The admixture, especially the high efficiency water reducing agent, is added into the concrete, which is an effective, simple and economic method for reducing the water-cement ratio, improving the concrete strength and improving various performances of the concrete. The current materials mainly comprise a modified lignin water reducing agent, a naphthalene sulfonate formaldehyde condensate high-efficiency water reducing agent, a melamine sulfonate formaldehyde condensate and a novel carboxylic acid graft copolymer superplasticizer.
The slump of the traditional condensation polymerization type water reducing agents such as naphthalene sulfonate formaldehyde condensate high-efficiency water reducing agents, melamine sulfonate formaldehyde condensate and the like is greatly changed with time, the production process pollutes the environment and is not beneficial to sustainable development. And because of the restriction of the molecular structure and the action mechanism, the problem of slump loss cannot be fundamentally solved, the performance cannot be greatly improved, and the requirements of the development of low water-cement ratio, high-strength and ultrahigh-strength concrete cannot be met.
Researchers have turned their attention to carboxylic acid-based graft polymers, also known as third generation novel polymer superplasticizers, which have: firstly, the content of the additive is low (0.2-0.5%) so as to exert high dispersion performance; good slump retaining performance, and basically no loss of slump of fresh concrete within 90 minutes; the freedom degree of the molecular structure is large, the controllable parameters of the additive manufacturing technology are more, and the potential of high performance is large; fourthly, the concrete superplasticizer is widely used in the synthesis without using formaldehyde which is a strong irritant substance and causing any pollution to the environment, and the like, and becomes a worldwide research hotspot.
CN1058474 reported a novel dispersion composition for cement excellent in slump loss inhibition property, which is obtained by polymerizing alkenyl ether, dialkenyl ether and maleic anhydride as monomers in a toluene solvent using azo-bis-isobutyronitrile as an initiator, and which has good slump retention ability but unsatisfactory dispersibility and is environmentally unfavorable in production process.
EP0924174 synthesizes different polymers with two side chains of different lengths, wherein the polymer with the long side chain has good dispersibility but poor slump retention due to large steric hindrance, and the copolymer with the short side chain has good slump retention but poor dispersibility. When two different copolymers are compounded in different proportions, the compound has both a certain dispersibility and slump-retaining ability, but the dispersibility and slump-retaining ability are far from sufficient.
EP1138697 and US570317 report that the expensive primary amine terminated monomethyl polyether is used as raw material, and active primary amine and carboxyl are used for grafting reaction, but the product price is expensive and is not favorable for strong popularization.
In addition, in order to solve the slump loss of concrete, the synthesis of ester cross-linked body is reported in US5362324 and US5661206, and the ester cross-linked body is subjected to chain scission in an alkaline medium of cement, so that the molecular weight is reduced, and the ester cross-linked body has good slump retention capacity, but the dispersibility is not very excellent, and the ester cross-linked body is not suitable for preparing low water-cement ratio and ultra-high strength concrete.
With the development of concrete technology towards low water-cement ratio, high strength, ultrahigh strength, high fluidity and high durability, efficient superplasticizers with more excellent water reducing rate and slump retaining performance must be further developed, and a great deal of research and attempt is made by many scholars.
US2002/0193547A1 describes a method for preparing a polycarboxylic superplasticizer, which comprises the steps of adopting an adduct of polyethyleneimine with a certain molecular weight and ethylene oxide, carrying out a grafting reaction with glycidyl methacrylate at a low temperature to prepare a macromonomer with polymerization activity, and then carrying out a copolymerization reaction with methacrylic acid and methoxy polyethylene glycol methacrylic acid monoester in an aqueous medium to obtain a target product, wherein the product has good dispersibility and dispersion retention performance.
US6680348B1 also describes a method for preparing a water-soluble amphoteric carboxylic acid superplasticizer, which comprises the steps of carrying out a condensation reaction between excess diethylenetriamine or polyethylene polyamine and adipic acid to prepare a polycondensate with active amine groups, carrying out a grafting reaction with equal moles of methacrylic acid to prepare a macromonomer containing amine groups, carrying out a ring-opening polymerization reaction between the remaining amine groups on the macromonomer and ethylene oxide in a high-pressure reaction kettle to prepare a cationic macromonomer component capable of participating in a polymerization reaction, and finally carrying out a copolymerization reaction with a methacrylic acid sodium salt and methoxy polyethylene glycol methacrylic acid monoester in an aqueous solution reaction medium to obtain a target product. The product has good dispersibility and dispersion retention property.
However, the copolymers described in US2002/0193547A1 and US6680348B1 have complicated preparation process, difficult control of operation, and high admixture content in high strength concrete.
Therefore, there are many problems with the current polycarboxylic acid superplasticizers, the synthesis process of these products is unsatisfactory, unclean and uneconomical, and the application properties are not completely satisfactory, some products have good dispersibility but poor dispersibility retention ability, and some products have slump retention ability but poor dispersibility. And the prior polycarboxylic admixture product has low saturation point, the water reducing rate is difficult to reach more than 35 percent, the water reducing performance is difficult to be further improved even if the mixing amount is increased, and the requirements of the development of low water-cement ratio, high-strength and high-performance concrete can not be met.
Disclosure of Invention
The object of the present invention was to develop amphoteric carboxylic acid comb graft copolymers which are usable as superplasticizers for concrete, which do not have the disadvantages described in the background, are relatively simple in production technology and have good application-technical properties.
Through a large number of experimental researches, researchers of the invention find that the comb-shaped copolymer with the short grafted side chain has low dispersion performance and good dispersion retention due to weak steric hindrance effect, and the copolymer with the longer grafted side chain has good early flowing performance and poor flowing retention due to strong steric hindrance effect. Therefore, in order to improve the dispersion performance, a large amount of long polyether side chains must be introduced into the main chain to provide steric hindrance, so that good dispersion performance can be provided.
Through a large number of experimental researches, researchers of the invention find that a cement system is a high-salt and high-pH-value system, and the molecular conformation of the traditional carboxylic acid graft copolymer is influenced by the salt concentration, particularly Ca2+The influence of (2) is great, if the conformation is relatively shrunk in a cement system, the adsorption is relatively slow, and the steric hindrance provided is relatively low, so that the concrete is not favorably dispersed. The carboxylic acid graft copolymer main chain is designed into a zwitterionic polymer, so that the sensitivity of the carboxylic acid graft copolymer main chain to inorganic salt ions is reduced, the stretching conformation of the carboxylic acid graft copolymer main chain is maintained, and electrostatic repulsive force can be provided, so that the dispersing performance of the carboxylic acid graft copolymer main chain is improved.
The researchers of the invention also find that when the main chain of the carboxylic acid graft copolymer is designed into an amphoteric polymer, the saturated doping amount of the carboxylic acid graft copolymer serving as a concrete superplasticizer can be greatly improved, and the water-cement ratio of concrete can be greatly reduced.
Researchers found that amphoteric carboxylic acid comb-shaped graft copolymers can be copolymerized by an aqueous solution copolymerization method by directly introducing a cationic monomer, and the synthesized copolymers show excellent dispersing performance and high saturation doping amount.
Researchers find that the proportion of long side chains is increased in the copolymer, which inevitably causes the slump retention capacity of the copolymer to be reduced, and the researchers find that the carboxylic acid polymer is subjected to partial crosslinking reaction by introducing the polymer or monomer capable of performing crosslinking reaction, the partially crosslinked carboxylic acid copolymer is hydrolyzed in the alkaline environment of cement slurry and gradually converted into a low molecular polymer with a dispersing function, so that the purpose of improving the slump retention performance is achieved, and meanwhile, the adsorption state of the graft copolymer on cement particles can be changed by adjusting the relative proportion of anions and cations, so that the slump retention performance of the graft copolymer is also favorably improved.
According to the research, the amphoteric carboxylic acid comb copolymer concrete superplasticizer provided by the invention is prepared by the following steps:
1) aqueous radical copolymerization: carrying out free radical copolymerization on 8-40% of monomer a, 55-85% of monomer b unit, 2-20% of cationic monomer c and 0-15% of nonionic monomer d in an aqueous medium; wherein,
the monomer a is represented by the general formula (1):
wherein R is hydrogen atom or methyl, M is hydrogen atom, alkali metal ion, alkaline earth metal ion, ammonium ion or organic amine group;
the monomer b is represented by the general formula (2):
wherein R is a hydrogen atom or a methyl group, R1Is an alkyl group of 1 to 22 carbon atoms, AO is an oxyalkylene group of 2 to 4 carbon atoms or a mixture of two or more such oxyalkylene groups, and if AO is a mixture of two or more such oxyalkylene groups, these groups may be added in a block or random form, and n is an average addition mole number of the oxyalkylene groups and is 10 to 150;
the cationic monomer c is represented by general formula (4), or general formula (5) or chemical formula (6):
wherein: r is a hydrogen atom or a methyl group;
R2，R3，R1: h or C1～C10R5: h or C1～C4Alkyl groups of (a);
R6，R7：C1～C1alkyl or hydroxyethyl or hydroxypropyl of (a);
a: f, Cl, Br, I, or BF1；
X: o or NH; p, q: a positive integer of 0 to 3
The nonionic monomer d is represented by the general formula (7):
wherein: r is a hydrogen atom or a methyl group, R8：C1～C4Alkyl or hydroxyethyl or hydroxypropyl of
2) And (3) crosslinking reaction: after the polymerization reaction is finished, directly adding a cross-linking agent shown in a general formula (8) to carry out cross-linking reaction,
the compound represented by the general formula (2) is generated by esterification reaction of monoalkyl polyether represented by the general formula (3) and unsaturated carboxylic acid represented by the general formula (1) under the conditions of a small amount of solvent medium, acid catalyst and a small amount of polymerization inhibitor.
R1O(AO)nH (3)
In the context of the present invention, the monomers a (formula 1) include predominantly acrylic acid, methacrylic acid and their corresponding acrylates or methacrylates, these monomers being used either individually or in the form of mixtures of two or more components.
Monomer b (formula 2) suitable polyether monoacrylates or polyether monomethacrylates, the branched polyether macromolecules (formula 3) being alkylene oxide polymers having a weight average molecular weight of about 200 to 8000, suitable alkylene oxides including ethylene oxide, propylene oxide, butylene oxide, and the like, and mixtures thereof. They may be linear or branched polymers, homopolymers or copolymers, random or block copolymers, diblock or multiblock copolymers. Preferred monomers b are polyethylene glycol alkyl ether acrylate, polyethylene glycol alkyl ether methacrylate, alkyl ether acrylate or alkyl ether methacrylate of a block or random copolymer of ethylene oxide and propylene oxide, which are generated by the esterification reaction of monoalkyl polyether shown in a general formula (3) and unsaturated carboxylic acid shown in a general formula (1) under the conditions of a small amount of solvent medium, acid catalyst and a small amount of polymerization inhibitor. n is the average addition mole number of the oxyalkylene group, and is 10 to 150, preferably 12 to 130, and more preferably 15 to 60.
As typical ions of the cationic monomer c, there may be mentioned methacryloyloxyethyltrimethyl ammonium chloride, methacryloyloxyethyldimethylbenzyl ammonium chloride, methacryloyloxypropyltrimethyl ammonium chloride, methacryloyloxypropyldimethylbenzyl ammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyldimethylbenzyl ammonium chloride, acrylamidopropyltrimethyl ammonium chloride, acrylamidopropyldimethylbenzyl ammonium chloride, methacrylamidopropyltrimethyl ammonium chloride, methacrylamidopropyldimethylbenzyl ammonium chloride, dimethylaminoethyl methacrylate, dimethylaminopropylmethacrylamide, N, N-dimethylaminomethylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, dimethylaminoethylacrylamide, dimethyldiallylammonium chloride.
As the nonionic monomer d, mainly acrylic ester or methacrylic ester monomers are mentioned, and typical examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyalkyl acrylate and hydroxyalkyl methacrylate, with methyl acrylate, methyl methacrylate, hydroxyalkyl acrylate and hydroxyalkyl methacrylate being preferred, and methyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate being more preferred, and these components may be used alone or in combination.
As typical examples of the crosslinking agent f which participates in the crosslinking reaction, there may be mentioned diglycidyl phthalate, diglycidyl adipate, various types of polyethylene glycol diglycidyl esters having different molecular weights, various types of polypropylene glycol diglycidyl esters having different molecular weights, and polyethylene-polypropylene glycol diglycidyl esters.
In the scope of the present invention, the monomer a (formula 1) is essential, the monomer a accounts for 8-40% of the total monomer amount, the content of the monomer a is too low, and the synthesized superplasticizer cannot be sufficiently adsorbed on cement particles, and thus cannot exert a dispersing effect. If the content is too high, resulting in too rapid adsorption of the copolymer, the loss of fluidity of fresh concrete or mortar incorporating the copolymer is also rapid.
The monomer b is polyether monoacrylate or polyether monomethacrylate with long chain as shown in the general formula (2) copolymerized into the main chain, and the long chain branch provides steric hindrance mainly, so that the dispersing capacity and the dispersion maintaining capacity of the comb-shaped graft copolymer to cement are improved. The monomer b accounts for 55-85% of the total amount of the monomers, the content of the monomer c is too low, the dispersing effect of the synthesized copolymer is weak, and if the content is too high, the slump loss of the produced copolymer is large.
The cationic monomer c is represented by a general formula (3) and accounts for 2-20%, preferably 4-15% of the total monomer amount, the monomer c content is too low to play a role of an amphoteric polymer, the saturated doping amount of the synthesized copolymer is not high, and if the monomer c content is too high, the synthesized copolymer can generate precipitates and has poor dispersibility and dispersion retentivity.
The monomer d is optional, but is generally about 0 to 15% of the total amount of the monomers.
The free radical copolymerization itself is relatively unimportant and suitable water-soluble initiators for the process of the present invention are conventional free radical water-soluble initiators and mixtures thereof, including water-soluble ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and the like. The total amount of initiator added to the reaction mixture should be about 0.1 to 15.0%, preferably about 0.2 to 12% by weight based on the total amount of monomer added, the actual amount added being dependent on the type of initiator used.
The concentration of the copolymerization monomer is preferably controlled to be 15-40%, and the reaction time is controlled to be about 5-10 hours. The monomer mixture and the initiator solution are separately and simultaneously dripped to control the distribution uniformity of the chain links of the copolymer and the stability of the polymerization reaction, and the dripping time of the monomer mixture and the initiator is preferably controlled within 1.5-5.0 hours. The polymerization temperature itself is preferably in the range from 60 to 100 ℃ and is dependent primarily on the decomposition temperature of the initiator used.
After the copolymerization reaction is finished, a certain amount of cross-linking agent is directly added at the temperature, the structure of the cross-linking agent is shown in a general formula (8), when the molecular weight is fixed before cross-linking, the larger the cross-linking agent is, the larger the viscosity after cross-linking is, the poorer the dispersion performance is, the larger the cross-linking agent is, the too high cross-linking density between two polymer molecules is, the copolymer can become water-insoluble gel, and the copolymer does not have the dispersion any more. The amount of crosslinking agent must therefore be controlled to a suitable level, up to one crosslinking point per two molecules, so that the initial flowability of the polymer is not affected by the crosslinking and the flow-holding properties are improved. The dosage of the cross-linking agent is controlled to be 0.5-3% of the total weight of the polymerization monomers, the mixture is stirred for reaction for 1-3 h, and the cross-linking reaction is finished.
After the crosslinking reaction is finished, carboxylic acid or anhydride can be converted into a salt form through a reaction with alkali, the finished product is named SSP, the pH value is preferably adjusted to 7.0-8.5, and if the pH value is too low or too high, the storage stability of the polymer is not good.
In the present invention, the comb-shaped graft copolymer SSP used as a concrete superplasticizer is not particularly limited in weight average molecular weight, and is generally 5,000-500,000, but is preferably 10,000-100,000 in view of slump retaining ability and dispersing ability, and if the molecular weight is too small, not only the water-reducing ability but also the slump retaining ability are greatly reduced, and if the molecular weight is too large, not only the water-reducing ability but also the slump retaining ability are greatly reduced.
When the concrete superplasticizer is used, the conventional mixing amount of the concrete superplasticizer is 0.2-0.5% of the total glue material, and if the water reducing rate is higher, the mixing amount can be increased, even can be up to 1.0% of the total glue material. Of course, if the addition amount is less than 0.20%, the slump-retaining ability of fresh concrete is unsatisfactory.
Of course, the concrete superplasticizer of the present invention may be mixed with at least one selected from the group consisting of sulfamic acid-based water-reducing agents known in the art, lignin-based ordinary water-reducing agents, and existing polycarboxylic acid-based superplasticizers.
In addition, in addition to the above-mentioned known water reducing agents for concrete, air entraining agents, expanding agents, retarders, early strength agents, tackifiers, shrinkage reducing agents, defoaming agents and the like may also be added thereto.
Compared with the prior art, the invention has the advantages that:
the method adopts an environment-friendly aqueous solution copolymerization mode, does not use toxic substances such as formaldehyde, strong corrosive fuming sulfuric acid and concentrated sulfuric acid, can realize zero emission in the reaction process, does not produce any waste gas, waste water or waste residue, and realizes the clean production of the concrete water reducer; the pollution of the traditional concrete water reducing agent production process to the environment is thoroughly eliminated;
the invention firstly provides that the saturated doping amount of the concrete superplasticizer can be improved by the zwitterionic polymer, and introduces the zwitterionic concept into the molecular structure design of the concrete admixture, so as to synthesize the amphoteric carboxylic acid graft copolymer concrete superplasticizer with high water-reducing rate;
compared with the conventional water reducing agent, the concrete superplasticizer prepared by the invention has outstanding dispersion performance and slump retention capacity under very low mixing amount, and the water reducing rate can be continuously increased along with the increase of the mixing amount, the saturation point is very high, and the product reinforcing effect is good. When the admixture is detected according to the standard of JC473-2001 concrete pumping aid, when the admixture is cement amount and the admixture amount is 0.3 percent, the water reducing rate can reach 38 percent, the admixture amount is increased, the water reducing rate can reach 45 percent at most, the strength of the admixture can be stably increased in both early and middle and later periods, and the preparation of C80 strength grade concrete can be realized by using 390kg of low cement;
the concrete superplasticizer prepared in the invention has good adaptability to cement and admixture, has good slump retaining capacity, basically does not lose slump within 90 minutes of fresh concrete, and if the addition amount is less than 0.20%, the slump retaining capacity of the fresh concrete is unsatisfactory;
the concrete superplasticizer prepared by the invention has extremely high water reducing performance, the water reducing rate can reach 45 percent at most, and the concrete superplasticizer is relatively suitable for preparing high-strength and ultrahigh-strength concrete, self-compacting high-strength concrete and active powder concrete.
The concrete superplasticizer prepared by the invention can be used in the dispersion of various cements, can greatly improve the mixing amount (up to 70 percent at most) of mineral admixtures (such as slag, fly ash and silica fume) in the concrete, is beneficial to environmental protection and sustainable development, and can also be used in the dispersion of gypsum, coal dust, ceramics, other powdery materials and other hydraulic materials which are not cement.
Detailed Description
Production examples
The following examples describe in more detail the preparation of amphoteric carboxylic acid comb graft copolymers according to the process of the present invention and are given by way of illustration, but in no way limit the scope of the invention. "parts" means "parts by weight" if not otherwise specified.
The monomers used in the following examples are shown in Table 1, the crosslinking agent f used in the examples is shown in Table 2, and the synthesized amphoteric carboxylic acid comb graft copolymer concrete superplasticizer is abbreviated as SSP.
In the examples of the present invention, the weight average molecular weight M of the polymerwDetermined using a Wyatt technology corporation gel permeation chromatograph (miniDAWN Tristar laser light Scattering Detector).
Table 1 monomers used in the examples
Table 2 crosslinking agent f used in the examples
Production example 1 (Synthesis of SSP-1)
Adding 150ml of deionized water into a glass reactor provided with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet pipe and a reflux condenser, blowing a reaction container with nitrogen while stirring, raising the temperature to 95 ℃, then mixing 24g (A1) with 164g (B1) with 12g (C-2) and 200 parts of water to prepare a mixed monomer aqueous solution, dropwise adding the mixed monomer aqueous solution into the reactor for 2 hours, dropwise adding 80 parts of initiator solution containing ammonium persulfate at the same time for 5 hours, keeping the temperature for reaction for 1 hour after dropwise adding, further adding 20 parts of hydrogen peroxide initiator solution with the concentration of 35 percent into the reaction bottle, keeping the temperature for 2 hours, cooling to the room temperature, adding 2.6g (F-1) of cross-linking agent, stirring for reaction for 1 hour, adding alkali for neutralization to the pH value of 7.5, adding 30.7 percent brown transparent liquid with the solid content and the molecular weight of 39,000(SSP-1), results are shown in Table 3.
Production examples 2 to 10 (Synthesis of SSP-2-10)
SSP-2-10 of the present invention was prepared according to the procedure of example 1, but with varying specific monomer weights and types, and was dosed according to the ratios described in Table 3, wherein the crosslinker (F) was present in weight percent F/(A + B + C + D).
Comparative example 1
As production example 4, except that no crosslinking component was added after completion of the polymerization, the pH was neutralized to 7.5 with an alkali to obtain a brown transparent liquid having a solid content of 30.5% and a molecular weight of 13,000, results are shown in Table 3.
Comparative example 2
The procedure of production example 1 was followed by charging the monomers in the proportions shown in Table 3, except that no cationic monomer was added to the monomer proportions, and after completion of the polymerization, the mixture was neutralized to pH 8.1 with an alkali to give a brown transparent liquid having a solid content of 31.7% and a molecular weight of 55,000.
TABLE 3
Application examples
In the application example, the adopted cement is 425R.P.II of Jinningyang and the sand is fineness modulus MxThe medium sand is 2.6, and the stones are crushed stones with the grain size of 5-20 mm in continuous gradation.
In the present embodiment, the test methods of the bleeding rate, the gas content and the setting time are performed with reference to the relevant regulations of 6B8076-97 concrete admixture.
The slump constant and the slump loss are executed according to related regulations of JC473-2001 concrete pumping aid, the mixing ratio C to S to G adopted by the test is 390 to 733 to 967, the slump constant is 20 +/-2 cm by adjusting the water adding amount of the reference concrete without admixture and the tested concrete with admixture, the slump constant and the expansion retention value after 60min and 90min are measured, the water reducing rate and the strength development change value of the test piece in different ages of maintenance are measured, and the concrete compressive strength and the compressive strength ratio are executed according to related regulations of GB/T50081-2002 common concrete mechanical property test method standard.
Application example 1
The properties of the carboxylic acid-based graft copolymers synthesized in the production examples and comparative examples were evaluated, and the results are shown in Table 4, in which the amount of the copolymer was fixed to 0.3% by weight based on the total weight of cement.
TABLE 4
From the results, the amphiprotic carboxylic acid graft copolymer synthesized in the scope of the invention has good dispersion performance and slump-retaining performance, slump and expansion of fresh concrete are not lost basically for 90min, the strength is increased greatly, the 28d compressive strength reaches above 70MPa basically with low cement consumption of 390kg, and the amphiprotic carboxylic acid graft polymer of the invention does not affect the setting time of concrete, but when the chain length of a grafting side is too long, although the dispersion performance is excellent, the slump retaining capability is poor (such as SSP-8), and in addition, when the content of a carboxylic acid adsorption group is too high, the adsorption is too fast, not only the initial dispersion performance is poor, but also the slump loss is fast. It can also be seen from the comparative examples that the slump retaining property of the amphoteric carboxylic acid-based graft polymer which is not crosslinked is poor.
Application example 2
The impact of different copolymer contents on the fresh concrete performance was examined by taking the amphoteric carboxylic acid graft copolymer SSP-4 as an example, and the slump of the fresh concrete was set to 20 + -2 cm at the beginning by adjusting the water consumption by comparing the anionic graft copolymer of comparative example 2, and the test results are shown in Table 5.
The test result shows that the water reducing rate of the amphoteric carboxylic acid graft copolymer SSP-4 synthesized by direct copolymerization is improved along with the increase of the doping amount, when the dosage of the doping cement is 0.2 percent, the water reducing rate is close to 30 percent, when the doping amount is improved to 0.3 percent, the water reducing rate of concrete is more than 38 percent, the slump loss is basically not lost in 90min, when the doping amount is improved to 0.4 percent, the water reducing rate is 42.8 percent, and along with the increase of the doping amount, the strength is increased rapidly, the 3d compressive strength ratio is basically more than 250 percent, and the 28d compressive strength ratio is basically more than 200 percent. In contrast, comparative example 2 is an anionic graft copolymer, and when the amount of the admixture is 0.2% of the amount of the cement, the dispersibility is substantially saturated, and the water-reducing rate is increased little, sometimes even slightly, by increasing the admixture amount. However, when the content of the amphoteric carboxylic acid graft copolymer is less than 0.30%, slump loss of fresh concrete is large.
TABLE 5
Application example 3
Taking the amphoteric carboxylic acid graft copolymer SSP-4 as an example to prepare reactive Powder concrete RPC (reactive Powder concrete), the most critical measure for preparing RPC is to reduce the water-cement ratio as much as possible, so a large amount of superplasticizer needs to be added to improve the working degree of the concrete. Table 6 shows the RPC mixing ratio, wherein the steel wire cut-off type superfine fiber has the length of 13mm, the diameter of 0.175mm, the tensile strength of 1800MPa, the mixing amount of the high-efficiency water reducing agent is calculated by the mass percent of the cementing material, and the slurry fluidity is 180 mm-200 mm.
TABLE 6
Table 7 shows the mechanical properties of RPC prepared by using the amphoteric carboxylic acid graft copolymer SSP-4 as an example, and from the test results, the amphoteric carboxylic acid graft copolymer synthesized by the present invention can meet the requirements for preparing RPC.
TABLE 7
The amphoteric carboxylic acid graft copolymer synthesized in the invention can greatly reduce the water consumption of concrete and has high fluidity, good construction performance and excellent slump retaining capability, and the product is mainly used for preparing low water-cement ratio, high strength, high performance, high flow state and active powder concrete.
Claims (9)
1. An amphoteric carboxylic acid comb-shaped graft copolymer concrete superplasticizer is characterized by being prepared by the following steps:
1) aqueous radical copolymerization: carrying out free radical copolymerization on 8-40% of monomer a, 55-85% of monomer b, 2-20% of cationic monomer c represented by a general formula (4), a general formula (5) or a chemical formula (6) and 0-15% of nonionic monomer d in an aqueous medium; wherein,
the monomer a is represented by the general formula (1):
wherein R is a hydrogen atom or a methyl group, and M is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion or an organic amine group;
the monomer b is represented by the general formula (2):
wherein R is a hydrogen atom or a methyl group, R1Is an alkyl group of 1 to 22 carbon atoms, AO is an oxyalkylene group of 2 to 4 carbon atoms or a mixture of two or more such oxyalkylene groups, these groups are added in a block or random form if AO is a mixture of two or more such oxyalkylene groups, and n is an average addition mole number of the oxyalkylene groups and is 10 to 150;
the cationic monomer c is represented by general formula (4), or general formula (5) or chemical formula (6):
wherein: r is a hydrogen atom or a methyl group
R2，R3，R4: h or C1～C10R5: h or C1～C4Alkyl of (2)
R6，R7：C1～C4Alkyl or hydroxyethyl or hydroxypropyl of
A: F. cl, Br, I or BF4
X: o or NH
p, q: a positive integer of 0 to 3
The nonionic monomer d is represented by the general formula (7):
wherein: r is a hydrogen atom or a methyl group, R8：C1～C4Alkyl or hydroxyethyl or hydroxypropyl of
2) And (3) crosslinking reaction: and after the polymerization reaction is finished, directly adding a cross-linking agent to carry out cross-linking reaction, wherein the cross-linking agent is selected from diglycidyl phthalate, diglycidyl adipate, various polyethylene glycol diglycidyl esters with different molecular weights, various polypropylene glycol diglycidyl esters with different molecular weights and polyethylene glycol-polypropylene glycol diglycidyl esters.
2. The amphoteric carboxylic acid comb graft copolymer concrete superplasticizer of claim 1, wherein the weight average molecular weight is 5,000-500,000.
3. The comb-graft copolymer with amphoteric carboxylic acids concrete superplasticizer according to claim 1 or 2, wherein the monomer a is selected from acrylic acid, methacrylic acid, acrylate or methacrylate, and these monomers are used alone or in a mixture of two or more thereof.
4. The comb-type graft copolymer with amphoteric carboxylic acids concrete superplasticizer of claim 1 or 2, wherein the monomer b is polyether monoacrylate or polyether monomethacrylate, and the branched polyether macromolecules thereof are oxyalkylene polymers having a weight-average molecular weight of 200 to 8000.
5. The comb graft copolymer concrete superplasticizer of claim 1 or 2, wherein the cationic monomer c is selected from the group consisting of methacryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl dimethyl benzyl ammonium chloride, methacryloyloxypropyl trimethyl ammonium chloride, methacryloyloxypropyl dimethyl benzyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl dimethyl benzyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl dimethyl benzyl ammonium chloride, methacrylamidopropyl trimethyl ammonium chloride, methacrylamidopropyl dimethyl benzyl ammonium chloride, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, N-dimethylaminomethyl methacrylamide, N-dimethylacrylamide, N-isopropylacrylamide, N-dimethylacrylamide, and mixtures thereof, N, N-diethylacrylamide, dimethylaminoethylacrylamide or dimethyldiallylammonium chloride.
6. The comb-type graft copolymer with amphoteric carboxylic acids as claimed in claim 1 or 2, wherein the nonionic monomer d is an acrylic or methacrylic ester monomer selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyalkyl acrylate and hydroxyalkyl methacrylate, and these components are used alone or in combination.
7. The amphoteric carboxylic acid type comb graft copolymer concrete superplasticizer of claim 1 or 2, wherein the water-soluble initiator used in step 1) is a conventional persulfate or peroxide type radical initiator selected from water-soluble ammonium persulfate, potassium persulfate, sodium persulfate or hydrogen peroxide, alone or in combination; the total amount of initiator added to the reaction mixture is from 0.1 to 15.0% of the total amount of monomer added.
8. The comb-shaped graft copolymer with amphoteric carboxylic acids as claimed in claim 1 or 2, wherein the concentration of the copolymerization monomer is controlled to 15-40%, and the reaction time is controlled to 5-10 hours; the monomer mixture and the initiator solution are separately and simultaneously dripped to control the distribution uniformity of copolymer chain links and the stability of polymerization reaction, the dripping time of the monomer mixture and the initiator is controlled to be 1.5-5.0 hours, and the copolymerization reaction is carried out at 60-100 ℃.
9. The comb-shaped graft copolymer with amphoteric carboxylic acids as claimed in claim 1 or 2, wherein the amount of the cross-linking agent used in step 2) is 0.5-3% of the total weight of the monomer a, the monomer b, the monomer c and the monomer d, and the cross-linking reaction is completed after the stirring reaction for 1-3 h.
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| CN107777910A (en) * | 2017-09-28 | 2018-03-09 | 湖北工业大学 | A kind of prefabricated components normal temperature Early-strength polycarboxylate superplasticizer and preparation method |
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| CN101475670B (en) * | 2009-01-12 | 2010-08-25 | 江苏博特新材料有限公司 | Comb-shaped graft copolymer cement dispersant |
| CN102558411B (en) * | 2011-10-20 | 2014-03-26 | 中国日用化学工业研究院 | Preparation method of ether ester copolymer water reducer |
| CN102910856B (en) * | 2012-10-18 | 2014-07-02 | 江苏苏博特新材料股份有限公司 | Super plasticizer for precast concrete component |
| CN102910855B (en) * | 2012-10-18 | 2014-10-29 | 江苏苏博特新材料股份有限公司 | Super plasticizer for precast concrete component |
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| CN106188418B (en) * | 2016-07-18 | 2018-07-17 | 江苏中铁奥莱特新材料股份有限公司 | A kind of preparation method of amphoteric polycarboxylate water-reducer |
| CN109776021A (en) * | 2019-01-16 | 2019-05-21 | 湖北大学 | A kind of low entraining type clear-water concrete additive and preparation method thereof |
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