CN103613306A - Hyperbranched poly(amine-ester) structure-containing polycarboxylic water reducer and preparation method thereof - Google Patents
Hyperbranched poly(amine-ester) structure-containing polycarboxylic water reducer and preparation method thereof Download PDFInfo
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- CN103613306A CN103613306A CN201310574242.7A CN201310574242A CN103613306A CN 103613306 A CN103613306 A CN 103613306A CN 201310574242 A CN201310574242 A CN 201310574242A CN 103613306 A CN103613306 A CN 103613306A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 87
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000004567 concrete Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 22
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 19
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- -1 alkali metal cation Chemical class 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 11
- 229940014800 succinic anhydride Drugs 0.000 claims description 11
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 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
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 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
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 22
- 238000002156 mixing Methods 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 37
- 238000010438 heat treatment Methods 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 18
- 229940043237 diethanolamine Drugs 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 12
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 239000006072 paste Substances 0.000 description 6
- 229920005646 polycarboxylate Polymers 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HCITUYXHCZGFEO-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.N=C1NC(=N)NC(=N)N1 HCITUYXHCZGFEO-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 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 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a novel hyperbranched poly(amine-ester) structure-containing polycarboxylic concrete water reducer. Hyperbranched monomers D contain a plurality of terminal carboxyl groups, a plurality of amino groups and ester groups exist in molecules, and the hyperbranched monomers D, unsaturated carboxylic acid, unsaturated sulfonic acid and unsaturated polyether are copolymerized in an aqueous solution to obtain the novel polycarboxylic concrete water reducer. By the water reducer, the defects of poor flowability, high collapse degree loss, poor cement adaptability and the like of an existing water reducer are improved to a certain extent. The water reducer has the beneficial effects that (1) the water reducer is novel in molecular structure, and contains multiple effective groups; (2) the water reducer is small in mixing amount, high in water reduction rate, dispersity and flowability and strong in compressive strength, and can be widely applied to multiple kinds of concrete; (3) a synthesis process is simple and easy to control and pollution-free.
Description
Technical Field
The invention relates to the technical field of concrete water reducing agents, in particular to a polycarboxylic acid water reducing agent containing a hyperbranched polyamine-ester structure, and a preparation method thereof.
Background
At present, the field of infrastructure construction in China is continuously and rapidly developed, and the demand for concrete is huge. As one of the additives with the largest dosage in concrete, the water reducing agent is applied to various engineering constructions. The water reducing agent can keep the workability of cement paste, mortar and concrete unchanged, obviously reduce the mixing water consumption, obviously improve the strength of the concrete, improve the frost resistance and impermeability of the concrete or reduce the cement consumption. According to the development process of the water reducing agent, the method comprises the following steps: the first generation of common water reducing agent (the water reducing rate is more than or equal to 8%): a second generation high-efficiency water reducing agent (the water reducing rate is more than or equal to 12%); the third generation of high-performance water reducing agent. Wherein, the common water reducing agent mainly comprises lignosulfonate, molasses and the like; the high-efficiency water reducing agent mainly comprises a naphthalene sulfonate formaldehyde condensate, a polycyclic aromatic hydrocarbon sulfonate formaldehyde condensate, a melamine (melamine) water reducing agent sulfamate water reducing agent, an aliphatic hydroxyl sulfonate water reducing agent and the like. In China, the two types of water reducing agents are still used in large quantities. However, the water reducing agents have many defects and limitations, such as low water reducing rate, too fast slump loss of concrete, high alkali content and the like, and the performance of the compound product is very unstable, which often affects the construction and performance of concrete and is difficult to meet the construction requirements of high-performance concrete. The third generation high-performance water reducing agent is a polycarboxylic acid water reducing agent, and has the advantages of low mixing amount, high water reducing rate, good dispersibility, low slump loss, strong later reinforcing effect, environment-friendly and pollution-free production process and the like, and is widely researched, popularized and applied.
In Japan and developed countries in Europe and America, the polycarboxylic acid high-performance water reducing agent has extremely high market share, and the market share in China is relatively low. Meanwhile, the research of China is started later, and compared with the research result of developed countries, the researched polycarboxylic acid water reducing agent still has great gap in the aspects of structure and performance. Therefore, the method has more important significance for the research of the polycarboxylic acid high-performance water reducing agent.
The polycarboxylic acid water reducing agent has excellent performance, but the types of raw materials used for synthesizing the polycarboxylic acid water reducing agent are limited, the water reducing mechanism is not clear, the polycarboxylic acid water reducing agent has poor adaptability to different types of cement, and the relationship between the structure and the performance is unclear. Therefore, the modification and new structure of the polycarboxylic acid water reducing agent are being researched.
CN102002134A discloses a hyperbranched polymer and a hyperbranched polycarboxylic acid water reducer, wherein methyl acrylate, ethanolamine, 2-bromoethanol and malonic acid are used as raw materials to synthesize a bromine-terminated hyperbranched polyamine-ester core molecule, cuprous bromide and 2.3-bipyridine are used as a catalyst and a coordination agent, and acrylic acid and monomethoxy-terminated allyl polyethylene glycol are respectively grafted onto the bromine-terminated hyperbranched polyamine ester by an atom transfer radical polymerization method to obtain the hyperbranched polymer.
CN101580353A discloses a water reducing agent which is prepared by polymerizing one of tert-butyl acrylate and tert-butyl methacrylate with sodium methacrylate and allyl polyoxyethylene ether to form a copolymer main chain, and then polycondensing one of acrylic acid and methacrylic acid with ethylenediamine to form a hyperbranched polyamide structure and grafting the hyperbranched polyamide structure to two ends of the main chain. Has the advantages of low mixing amount, high water reducing rate, small slump loss, good compatibility with cement, no corrosion to reinforcing steel bars, strong freezing resistance and the like.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a polycarboxylic acid water reducer containing a hyperbranched polyamine-ester structure (having a plurality of effective functional groups such as carboxyl, amino and ester groups). Under the same folding and fixing mixing amount and water-cement ratio, the water reducing agent has different degrees of improvement on water reducing rate, dispersion performance, slump retaining performance and adaptability to cement.
The invention also provides a preparation method of the polycarboxylic acid water reducing agent.
A polycarboxylic acid water reducing agent containing a hyperbranched polyurethane structure has the following structural formula:
wherein a, b, c and d are natural numbers,
n is a natural number from 8 to 100;
R1、R2、R3are each a hydrogen atom or a methyl group,
m is a hydrogen atom or an alkali metal cation,
x=；y=2gwherein g is a natural number from 1 to 4, representing the generation number of the hyperbranched polymer.
The polycarboxylic acid water reducing agent is characterized in that a: b: c: d = 3.0 to 7.0: 0.5-1.5: 1.0-2.0: 0.5 to 1.0.
The water reducing agent is prepared by copolymerizing unsaturated carboxylic acid (A), unsaturated sulfonic acid (B), unsaturated polyether (C) and a novel hyperbranched monomer (D);
the molar ratio of the polycarboxylic water reducer monomer A, B, C, D is 3.0-7.0: 0.5-1.5: 1.0-2.0: 0.5 to 1.0.
The hyperbranched monomer has a general structural formula of
Wherein, x =；y=2g ；
g is a natural number from 1 to 4, representing the generation number of the hyperbranched polymer.
Preferred unsaturated carboxylic acids have the formula
Wherein R is1Is H atom or methyl, M is H atom or alkali metal cation.
Preferred unsaturated sulfonic acids have the formula
Wherein R is2Is H atom or methyl, M is H atom or alkali metal cation.
Preferred unsaturated polyethers have the formula
Wherein R is2Is H atom or methyl, and has molecular weight of 400-3000.
The hyperbranched monomer is obtained by the following steps: diethanolamine and methyl acrylate react to generate AB2Monomer, AB2The monomer reacts with propylene alcohol to obtain a hydroxyl-terminated hyperbranched polymer, and succinic anhydride is used for carrying out end group modification to obtain a hyperbranched monomer.
The preparation method of the hyperbranched monomer preferably selects allyl alcohol and AB2The molar ratio of the monomers is 1:1 to 15.
The preparation method of the water reducing agent preferably comprises the following steps:
(1) preparing a novel hyperbranched monomer: reacting diethanol amine with methyl acrylate under the protection of nitrogenTo AB2A monomer; AB under the catalysis of p-toluenesulfonic acid2Reacting the monomer with allyl alcohol to obtain a hydroxyl-terminated hyperbranched polymer; performing end group modification on the prepared hydroxyl-terminated hyperbranched monomer by succinic anhydride to obtain a hyperbranched monomer;
(2) respectively preparing monomer unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated polyether and hyperbranched monomer into aqueous solution, dropwise adding mixed solution of initiator, unsaturated sulfonic acid, unsaturated polyether and hyperbranched monomer into the aqueous solution of unsaturated carboxylic acid in batches at 60-80 ℃, stirring for reaction, keeping the temperature at 85-90 ℃ for 4 hours after dropwise adding, and adjusting the pH to 7-7.5 to obtain the polycarboxylate-type water reducer containing a hyperbranched polyurethane structure;
the mixed solution of the initiator, the unsaturated sulfonic acid, the unsaturated polyether and the hyperbranched monomer is dripped once every half hour for three times;
the initiator is ammonium persulfate, potassium persulfate or sodium persulfate, and the dosage of the initiator is 2.0-3.0% of the total mass of the monomers.
The folding and fixing amount of the polycarboxylic acid water reducing agent in concrete is 0.2-1.0%.
The following is a detailed description of the preparation of a polycarboxylic acid water reducing agent, which mainly comprises the following steps:
(1) preparation of novel hyperbranched monomers
And introducing nitrogen into the three-neck flask for 10 min, adding a proper amount of diethanolamine and methanol, and magnetically stirring at room temperature under the continuous nitrogen protection until the diethanolamine is completely dissolved. Slowly dropwise adding a certain amount of methyl acrylate, heating in water bath to 40 ℃ after dropwise adding, keeping for 4h, and then distilling under reduced pressure to remove methanol to obtain AB2A monomer. Putting an appropriate amount of AB2 monomer into a three-neck flask filled with nitrogen, adding a certain amount of allyl alcohol (as nuclear molecule) and an appropriate amount of catalyst p-toluenesulfonic acid, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, distilling under reduced pressure,obtaining the hydroxyl-terminated hyperbranched polymer. Respectively dissolving a proper amount of hydroxyl-terminated hyperbranched monomer and succinic anhydride in tetrahydrofuran, mixing the two after dissolving, performing reflux reaction to 1/2 with the system acid value as an initial value by taking DMAP as a catalyst, and removing the solvent by reduced pressure distillation to obtain the hyperbranched monomer.
Control of nuclear molecules with AB2The hyperbranched monomers with different generations can be obtained according to the molar ratio of the monomers, and when the molar ratio of the hyperbranched monomers to the monomers is 1:1, the product is G1; when the molar ratio of the two is 1:3, the product is G2; when the molar ratio of the two is 1:7, the product is G3; when the molar ratio of the two is 1:15, the product is G4. Wherein the formula of G2 is shown as follows:
(2) preparation of polycarboxylic acid water reducing agent
Preparing the monomer B into aqueous solution with a certain proportion; mixing the residual A, C, D monomers to prepare an aqueous solution with a certain mass fraction; and preparing an initiator accounting for 2.0-3.0% of the total mass of the four monomers into an aqueous solution in a certain proportion. And (3) placing the aqueous solution of the B into a reactor, stirring and heating to 60-80 ℃, then respectively dropwise adding the mixed solution of the initiator and the monomer in batches, separating for half an hour, finishing dropwise adding for four times in total, heating to 85-90 ℃ after dropwise adding, continuously stirring and reacting for 4-6 hours, and then adjusting the pH to = 7-7.5 by using a NaOH solution with the mass fraction of 25% -40%, thereby obtaining the novel polycarboxylate-type water reducer containing the hyperbranched structure.
The polycarboxylic acid water reducing agent containing the G2-substituted hyperbranched structure has the following structural formula:
wherein,
is composed of
；
a. b, c, d and n are natural numbers.
During the cement hydration process, the coagulation is generated due to the influence of Van der Waals force between particles and other different charges, so that the concrete generates a flocculation structure. The water reducing agent is a surfactant, and after the water reducing agent is added into a cement dispersion system, wetting and adsorption actions are generated on a solid-liquid interface to form an adsorption layer or an electric double layer, so that the dispersion action is generated on the system. The dispersion stability thereof is mainly determined by a balance between electrostatic repulsion and van der waals attraction. When the water reducing agent is added into a cement system, one part of polar groups are anchored on the surfaces of cement particles, and the other part of polar groups extend into an aqueous solution to provide electrostatic repulsion; longer polyalkoxy side chains increase steric hindrance effects; the ionic group in the water reducing agent structure is dissociated into ions in water and the ions are adsorbed on cement particles, so that the cement particles are charged to generate electrostatic repulsion. Thereby destroying the flocculation structure in the cement paste, releasing the water in the cement paste, increasing the free water amount and leading the cement particles to have better dispersibility and fluidity.
The invention has the beneficial effects that:
the polycarboxylic acid water reducing agent has a comb-shaped structure, the molecular skeleton is composed of a main chain and more side chains, the water reducing rate is high, the dispersibility is good, and the like, so that cement particles have better dispersibility, and the agglomeration phenomenon of the cement particles can be effectively prevented; the preparation method is simple to operate, green and pollution-free.
Detailed Description
Example 1
(1) After nitrogen was purged into the three-necked flask for 10 min, 105.14g of diethanolamine and 50mL of methanol were added, and the mixture was magnetically stirred at room temperature under continuous nitrogen protection until the diethanolamine was completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, heating the mixture to 40 ℃ in a water bath after dropwise adding, keeping the temperature for 4 hours, and then distilling the mixture under reduced pressure to remove methanol to obtain AB2A type monomer. 57.37g of AB are taken2Adding 5.81G of propylene alcohol and 0.32G of p-toluenesulfonic acid into a three-necked flask filled with nitrogen gas, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G2-substituted hydroxyl-terminated hyperbranched polymer. Dissolving 53.57g G2 substituted hydroxyl-terminated hyperbranched monomer and 40.03g succinic anhydride in 100mL and 300mL of tetrahydrofuran respectively, mixing the two after dissolving, dissolving 0.56g of DMAP in 20mL of tetrahydrofuran, then slowly dropwise adding the mixture into a mixed system, carrying out reflux reaction until the acid value of the system is 1/2 of the initial value, and removing the solvent by reduced pressure distillation to obtain the hyperbranched monomer D1.
(2) Preparing 0.79g of sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; 1.26g of acrylic acid, 18.00g of TPEG-2400 and 4.68g of hyperbranched monomer D1 are respectively prepared into 25 mass percent aqueous solutions and then mixed; 0.74g of ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 initiator and monomer mixed solution, then heating to 80 ℃, dropwise adding the initiator and monomer mixed solution once every half hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding is finished, continuing stirring and reacting for 4 hours, then adjusting the pH to = 7-7.5 by using a NaOH solution with the mass fraction of 40%, and obtaining a novel polycarboxylate-based water reducing agent containing a hyperbranched structure, which is recorded as G2-PC 1.
Example 2
(1) Introducing nitrogen into a three-neck flask for 10 min, adding 105.14g diethanolamine and 50mL methanol, and keeping under nitrogen protection at room temperatureNext, magnetically stir until diethanolamine is completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, heating the mixture to 40 ℃ in a water bath after dropwise adding, keeping the temperature for 4 hours, and then distilling the mixture under reduced pressure to remove methanol to obtain AB2A type monomer. 57.37g of AB are taken2Adding 5.81G of propylene alcohol and 0.32G of p-toluenesulfonic acid into a three-necked flask filled with nitrogen gas, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G2-substituted hydroxyl-terminated hyperbranched polymer. Dissolving 53.57g G2 substituted hydroxyl-terminated hyperbranched monomer and 40.03g succinic anhydride in 100mL and 300mL of tetrahydrofuran respectively, mixing the two after dissolving, dissolving 0.56g of DMAP in 20mL of tetrahydrofuran, then slowly dropwise adding the mixture into a mixed system, carrying out reflux reaction until the acid value of the system is 1/2 of the initial value, and removing the solvent by reduced pressure distillation to obtain the hyperbranched monomer D2.
(2) Preparing 0.40g of sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; 2.16g of acrylic acid, 18.00g of TPEG-2400 and 4.68g of hyperbranched monomer D2 are respectively prepared into 25 mass percent aqueous solutions and then mixed; 0.76g of ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 initiator and monomer mixed solution, then heating to 80 ℃, dropwise adding the initiator and monomer mixed solution once every half hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding is finished, continuing stirring and reacting for 4 hours, then adjusting the pH to = 7-7.5 by using a NaOH solution with the mass fraction of 40%, and obtaining a novel polycarboxylate-based water reducing agent containing a hyperbranched structure, which is recorded as G2-PC 2.
Example 3
(1) After nitrogen was purged into the three-necked flask for 10 min, 105.14g of diethanolamine and 50mL of methanol were added, and the mixture was magnetically stirred at room temperature under continuous nitrogen protection until the diethanolamine was completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, heating the mixture to 40 ℃ in a water bath after dropwise adding, keeping the temperature for 4 hours, and then distilling the mixture under reduced pressure to remove methanol to obtain AB2A type monomer. 66.93g of AB are taken2Monomer in-tubeAdding 2.90G of propylene alcohol and 0.35G of p-toluenesulfonic acid into a three-neck flask with nitrogen, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G3 hydroxyl-terminated hyperbranched polymer. And (2) respectively dissolving 58.62g of 58.62g G3-substituted hydroxyl-terminated hyperbranched monomer and 40.03g of succinic anhydride in 100mL and 300mL of tetrahydrofuran, mixing the two after dissolving, dissolving 0.59g of DMAP in 20mL of tetrahydrofuran, slowly dropwise adding the DMAP into a mixed system, carrying out reflux reaction until the acid value of the system is 1/2 of the initial value, and removing the solvent by reduced pressure distillation to obtain the hyperbranched monomer D3.
(2) Preparing 0.79g of sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; 1.26g of acrylic acid, 18.00g of TPEG-2400 and 9.86g of hyperbranched monomer D3 are respectively prepared into 25 mass percent aqueous solutions and then mixed; 0.90g of ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 initiator and monomer mixed solution, then heating to 80 ℃, dropwise adding the initiator and monomer mixed solution once every half hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding is finished, continuing stirring and reacting for 4 hours, then adjusting the pH to = 7-7.5 by using a NaOH solution with the mass fraction of 40%, and obtaining a novel polycarboxylate-based water reducing agent containing a hyperbranched structure, which is recorded as G3-PC 1.
Example 4
(1) After nitrogen was purged into the three-necked flask for 10 min, 105.14g of diethanolamine and 50mL of methanol were added, and the mixture was magnetically stirred at room temperature under continuous nitrogen protection until the diethanolamine was completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, heating the mixture to 40 ℃ in a water bath after dropwise adding, keeping the temperature for 4 hours, and then distilling the mixture under reduced pressure to remove methanol to obtain AB2A type monomer. 66.93g of AB are taken2Adding 2.90G of propylene alcohol and 0.35G of p-toluenesulfonic acid into a three-necked flask filled with nitrogen gas, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G3-substituted hydroxyl-terminated hyperbranched polymer. 58.62g G3 generationRespectively dissolving hydroxyl-terminated hyperbranched monomer and succinic anhydride 40.03g in tetrahydrofuran 100mL and tetrahydrofuran 300mL, mixing the two after dissolving, dissolving DMAP 0.59g in tetrahydrofuran 20mL, then slowly dropwise adding the mixture into a mixed system, carrying out reflux reaction until the acid value of the system is 1/2 of the initial value, and removing the solvent by reduced pressure distillation to obtain the hyperbranched monomer D4.
(2) Preparing 0.79g of sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; 1.26g of acrylic acid, 9.00g of APEG-1200 and 9.86g of hyperbranched monomer D4 are respectively prepared into 25 mass percent aqueous solutions and then mixed; 0.63g of ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 initiator and monomer mixed solution, then heating to 80 ℃, dropwise adding the initiator and monomer mixed solution once every half hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding is finished, continuing stirring and reacting for 4 hours, then adjusting the pH to = 7-7.5 by using a NaOH solution with the mass fraction of 40%, and obtaining a novel polycarboxylate-based water reducing agent containing a hyperbranched structure, which is recorded as G3-PC 2.
Example 5
(1) After nitrogen was purged into the three-necked flask for 10 min, 105.14g of diethanolamine and 50mL of methanol were added, and the mixture was magnetically stirred at room temperature under continuous nitrogen protection until the diethanolamine was completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, heating the mixture to 40 ℃ in a water bath after dropwise adding, keeping the temperature for 4 hours, and then distilling the mixture under reduced pressure to remove methanol to obtain AB2A type monomer. 57.37g of AB are taken2Adding 1.16G of propylene alcohol and 0.29G of p-toluenesulfonic acid into a three-necked flask filled with nitrogen gas, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G4-substituted hydroxyl-terminated hyperbranched polymer. Respectively dissolving 61.15g of 61.15g G4 substituted hydroxyl-terminated hyperbranched polymer and 40.03g of succinic anhydride in 100mL and 300mL of tetrahydrofuran, mixing the two after dissolving, dissolving 0.61g of DMAP in 20mL of tetrahydrofuran, slowly dropwise adding the mixture into a mixed system, carrying out reflux reaction until the acid value of the system is 1/2 of the initial value, and carrying out reduced pressure distillationThe solvent was distilled off to obtain hyperbranched monomer D5.
(2) Preparing 0.79g of sodium methallyl sulfonate into an aqueous solution with the mass fraction of 25%; 1.26g of acrylic acid, 18g of TPEG-2400 and 20.24g of hyperbranched monomer D5 are respectively prepared into 25 mass percent aqueous solutions and then mixed; 1.21g of ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 initiator and monomer mixed solution, then heating to 80 ℃, dropwise adding the initiator and monomer mixed solution once every half hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding is finished, continuing stirring and reacting for 4 hours, then adjusting the pH to = 7-7.5 by using a NaOH solution with the mass fraction of 40%, and obtaining a novel polycarboxylate-based water reducing agent containing a hyperbranched structure, which is recorded as G4-PC 1.
Example 6
(1) After nitrogen was purged into the three-necked flask for 10 min, 105.14g of diethanolamine and 50mL of methanol were added, and the mixture was magnetically stirred at room temperature under continuous nitrogen protection until the diethanolamine was completely dissolved. Then slowly dropwise adding 86.09g of methyl acrylate, heating the mixture to 40 ℃ in a water bath after dropwise adding, keeping the temperature for 4 hours, and then distilling the mixture under reduced pressure to remove methanol to obtain AB2A type monomer. 57.37g of AB are taken2Adding 1.16G of propylene alcohol and 0.29G of p-toluenesulfonic acid into a three-necked flask filled with nitrogen gas, stirring until all solid reagents are dissolved, heating to 85 ℃, stirring at constant temperature for reaction for 24 hours, washing the product with diethyl ether, and distilling under reduced pressure to obtain the G4-substituted hydroxyl-terminated hyperbranched polymer. Dissolving 61.15g of 61.15g G4-substituted hydroxyl-terminated hyperbranched monomer and 40.03g of succinic anhydride in 100mL and 300mL of tetrahydrofuran respectively, mixing the two after dissolving, dissolving 0.61g of DMAP in 20mL of tetrahydrofuran, then slowly dropwise adding the DMAP into a mixed system, carrying out reflux reaction until the acid value of the system is 1/2 of the initial value, and removing the solvent through reduced pressure distillation to obtain the hyperbranched monomer D5.
(2) 0.59g of sodium methallyl sulfonate is prepared into an aqueous solution with the mass fraction of 25%; 2.16g of acrylic acid, 18g of TPEG-2400 and 10.12g of hyperbranched monomer D5 are respectively prepared into 25 mass percent aqueous solutions and then mixed; 0.93g of ammonium persulfate was prepared as a 25% aqueous solution. Placing a sodium methallylsulfonate aqueous solution into a three-neck flask, stirring and heating to 60 ℃, then respectively dropwise adding 1/4 initiator and monomer mixed solution, then heating to 80 ℃, dropwise adding the initiator and monomer mixed solution once every half hour, after the three times of dropwise adding are finished, heating to 85-90 ℃ after the dropwise adding is finished, continuing stirring and reacting for 4 hours, then adjusting the pH to = 7-7.5 by using a NaOH solution with the mass fraction of 40%, and obtaining a novel polycarboxylate-based water reducing agent containing a hyperbranched structure, which is recorded as G4-PC 2.
The cement paste test and the concrete performance test were performed on the novel polycarboxylic acid water reducing agents prepared in the above 6 examples, respectively. Note: all tests refer to national standard GB/T8077-; the cement used was portland cement 42.5.
A hyperbranched polymer and a hyperbranched polycarboxylic acid water reducer disclosed in CN102002134A mentioned in the background art are taken as a comparison 1, and a water reducer disclosed in CN101580353A is taken as a comparison 2 to carry out a cement paste test and a concrete performance test experiment.
TABLE 1 Cement paste fluidity test results
TABLE 2 concrete test results
Therefore, the novel polycarboxylic acid water reducing agent synthesized by the invention has high water reducing rate, good dispersibility and fluidity and strong pressure resistance, and can be widely used in various concretes.
Claims (10)
1. A polycarboxylic acid water reducing agent containing a hyperbranched polyurethane structure is characterized by having a structural formula as follows:
wherein a, b, c and d are natural numbers,
n is a natural number from 8 to 100;
R1、R2、R3are each a hydrogen atom or a methyl group,
m is a hydrogen atom or an alkali metal cation,
x=
；y=2gwherein g is a natural number from 1 to 4, representing the generation number of the hyperbranched polymer.
2. The polycarboxylic acid-based water reducing agent according to claim 1, characterized in that a: b: c: d = 3.0 to 7.0: 0.5-1.5: 1.0-2.0: 0.5 to 1.0.
3. A preparation method of a polycarboxylic acid water reducer containing a hyperbranched polyurethane structure is characterized in that unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated polyether and a hyperbranched monomer are copolymerized to obtain the polycarboxylic acid water reducer containing the hyperbranched polyurethane structure;
the hyperbranched monomer has a general structural formula of
Wherein, x =
；y=2g ；
g is a natural number from 1 to 4, representing the generation number of the hyperbranched polymer.
4. The process according to claim 3, wherein the unsaturated carboxylic acid has the formula
Wherein R is1Is H atom or methyl, M is H atom orAn alkali metal cation.
5. The process according to claim 3 or 4, wherein the unsaturated sulfonic acid has the formula
Wherein R is2Is H atom or methyl, M is H atom or alkali metal cation.
6. The process according to claim 3 or 4, wherein the unsaturated polyether has the formula
Wherein R is2Is H atom or methyl, and has molecular weight of 400-3000.
7. The method according to claim 3, wherein the hyperbranched monomer is obtained by: diethanolamine and methyl acrylate react to generate AB2Monomer, AB2The monomer reacts with propylene alcohol to obtain a hydroxyl-terminated hyperbranched polymer, and succinic anhydride is used for carrying out end group modification to obtain a hyperbranched monomer.
8. The process of claim 7, wherein the allylic alcohol is reacted with AB2The molar ratio of the monomers is 1:1 to 15.
9. The method of claim 3, comprising the steps of:
(1) preparing a novel hyperbranched monomer: diethanolamine and propylene under the protection of nitrogenMethyl ester reacts to generate AB2A monomer; AB under the catalysis of p-toluenesulfonic acid2Reacting the monomer with allyl alcohol to obtain a hydroxyl-terminated hyperbranched polymer; performing end group modification on the prepared hydroxyl-terminated hyperbranched monomer by succinic anhydride to obtain a hyperbranched monomer;
(2) respectively preparing monomer unsaturated carboxylic acid, unsaturated sulfonic acid, unsaturated polyether and hyperbranched monomer into aqueous solution, dropwise adding mixed solution of initiator, unsaturated sulfonic acid, unsaturated polyether and hyperbranched monomer into the aqueous solution of unsaturated carboxylic acid in batches at 60-80 ℃, stirring for reaction, keeping the temperature at 85-90 ℃ for 4 hours after dropwise adding, and adjusting the pH to 7-7.5 to obtain the polycarboxylate-type water reducer containing a hyperbranched polyurethane structure;
the mixed solution of the initiator, the unsaturated sulfonic acid, the unsaturated polyether and the hyperbranched monomer is dripped once every half hour for three times;
the initiator is ammonium persulfate, potassium persulfate or sodium persulfate, and the dosage of the initiator is 2.0-3.0% of the total mass of the monomers.
10. The polycarboxylic acid-based water-reducing agent according to claim 1 or 2 or the polycarboxylic acid-based water-reducing agent obtained by the production method according to any one of claims 3 to 9, characterized in that the amount of the broken solid incorporated in concrete is 0.2 to 1.0%.
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