CN107987230B - Star-shaped polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Star-shaped polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 30
- 239000002253 acid Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- -1 isoamylene alcohol Chemical compound 0.000 claims abstract description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 238000003756 stirring Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 3
- 229920005646 polycarboxylate Polymers 0.000 description 14
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 12
- 102100026735 Coagulation factor VIII Human genes 0.000 description 10
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 10
- 239000008030 superplasticizer Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 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 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A star-shaped polycarboxylic acid water reducing agent and a preparation method thereof comprise the following steps: (1) a macroinitiator POSS-Cl; (2) Adding a macroinitiator POSS-Cl into a reaction bottle, dissolving in DMSO, adding a mixed solution of isoamylene alcohol polyoxyethylene ether (TPEG), an unsaturated carboxylic acid monomer and a hydroxyl-containing acrylic monomer, and reacting to obtain a star polycarboxylic acid water reducing agent; the prepared star-shaped polycarboxylic acid water reducing agent is added into concrete, and the net slurry fluidity and the concrete strength are obviously improved at the same time.
Description
Technical Field
The invention relates to a preparation method of a star-shaped polycarboxylic acid water reducing agent.
Background
Patent CN102887979B relates to a preparation method of a star-shaped polycarboxylic acid high-performance water reducing agent. The star-shaped polycarboxylic acid high-performance water reducing agent material is prepared by taking polyalcohol and (methyl) acrylic acid as main esterification raw materials and adopting a method of esterification and polymerization, namely (methyl) acrylic acid and polyalcohol are taken as reactants, a star-shaped polymerizable active end is prepared through esterification reaction under the action of a catalyst, and then the star-shaped polymerizable active end is subjected to free radical polymerization with unsaturated polyoxyethylene ether, a molecular weight regulator and an unsaturated carboxylic acid monomer under the action of an initiator. The method has the advantages that the method is simple and easy to control, high in polymerization degree, low in cost and free of pollution, an active core is formed through esterification reaction, and then a chain-shaped arm is generated through free radical polymerization, so that the polycarboxylic acid high-performance water reducing agent with a star-shaped molecular structure is realized, the polycarboxylic acid high-performance water reducing agent has more excellent cement paste fluidity and retention capacity than the traditional linear and comb-shaped polycarboxylic acid water reducing agents under common doping amount and low doping amount, and the cement adaptability and the concrete application performance are good.
The patent CN105271897B protects a star-shaped polycarboxylate superplasticizer with high water reducing rate and a preparation method thereof, and is characterized in that: firstly, carrying out acyl bromination reaction on triethanolamine to obtain a star-shaped initiator with a bromine end group; and then, the hydroxyethyl methacrylate is connected to the star initiator to obtain the star polycarboxylic acid water reducer with high water reducing rate. The star polycarboxylate water reducing agent designed by the patent has the advantages of high water reducing rate, and can improve the compressive strength of concrete and meet higher construction requirements.
The patent application CN106750046A discloses a star-shaped amphoteric polycarboxylate water reducer and a preparation method thereof, which is to esterify cyclodextrin to obtain a star-shaped initiator, initiate the atom transfer radical polymerization of polyethylene glycol (meth) acrylate, sodium (meth) acrylate, methyl (meth) acryloyloxyethyl trimethyl ammonium chloride and hydroxyethyl (meth) acrylate to obtain a star-shaped copolymer of the four monomers, and further process to obtain the star-shaped amphoteric polycarboxylate water reducer with the solid content of 20%. The polycarboxylate superplasticizer prepared by the method has the advantages of high water reducing rate, good mud resistance, capability of meeting higher construction requirements and good application prospect.
Patent application CN106084157A discloses a three-arm high-efficiency water reducing agent and a preparation method thereof, belonging to the technical field of building concrete admixtures. The preparation of the high-efficiency water reducing agent is to obtain the AB type diblock copolymer with a three-arm structure by adopting three steps of atom transfer radical polymerization step-by-step polymerization. The water reducing agent designed by the application has the characteristics of controllable chemical structure, controllable molecular weight, narrow molecular weight distribution and simple process, has high water reducing rate and good slump retention property, can obviously improve the fluidity of concrete, and has low sensitivity to mud. The comb-shaped polycarboxylate superplasticizer has the advantages that compared with the traditional comb-shaped polycarboxylate superplasticizer, the comb-shaped polycarboxylate superplasticizer can solve the problems that the polycarboxylate superplasticizer is sensitive to soil in concrete and has performance reduction due to the existence of the soil to a certain extent, and is particularly suitable for concrete with high mud content.
Patent application CN106519142A discloses a preparation method of a star-shaped polycarboxylate water reducer, which belongs to the technical field of polycarboxylate water reducers for concrete, and the star-shaped polycarboxylate water reducer is prepared by taking a monomer containing double bonds, a multi-group nucleating agent, an initiator and double-bond-terminated polyoxyethylene ether as raw materials through a polymerization reaction.
Therefore, the water reducing rate of the star polycarboxylic acid water reducing agent is generally improved, but the structure obtained by preparing the water reducing agent by adopting ATRP or RAFT is clear from the structure, and experimental basis is provided for further analyzing the relation between the performance and the structure, so that compared with other free radical polymerization methods, the ATRP or RAFT reaction is more suitable for preparing the star polycarboxylic acid water reducing agent.
Disclosure of Invention
The invention adopts specific type of initiator and specific type of monomer, adjusts the reaction steps, and obtains the star-shaped polycarboxylate superplasticizer which is used in concrete, and the net slurry fluidity and the concrete strength are obviously improved at the same time.
The invention firstly provides a star-shaped polycarboxylic acid water reducing agent which is prepared from a multi-arm initiator, isopentenol polyoxyethylene ether (TPEG) and a reactive monomer.
The invention provides a preparation method of a star-shaped polycarboxylic acid water reducing agent, which comprises the following steps:
(1) Dissolving hydroxyl octa-polyhedral oligomeric silsesquioxane (POSS-OH) in dimethyl sulfoxide (DMSO) to form a solution with the concentration of 20-25%, stirring for 4-6h, cooling to 0-5 ℃, adding triethylamine, dropwise adding 2-chloroacetyl chloride under the stirring state, reacting at room temperature for 15-24h after dropwise adding, sequentially cleaning with alkali liquor, acid liquor and deionized water, adding the lower layer liquor into methanol for precipitation, and performing vacuum drying on the obtained precipitate to obtain a macromolecular initiator POSS-Cl;
(2) Adding a macroinitiator POSS-Cl into a reaction bottle, dissolving in DMSO, adding a mixed solution of isoamylene alcohol polyoxyethylene ether (TPEG), unsaturated carboxylic acid monomer and hydroxyl-containing acrylic monomer, performing vacuum pumping and filling nitrogen N 2 Circulating for more than 3 times, dissolving cuprous chloride serving as a catalyst and pentamethyldiethylenetriamine serving as a ligand in DMSO, adding the solution into a reaction bottle by using an injector, reacting for 8-12 hours at 30-60 ℃ under magnetic stirring, and dialyzing to remove residual monomers and other impurities after the reaction is finished to obtain the star-shaped polycarboxylic acid water reducer;
wherein the macroinitiator POSS-Cl, TPEG, unsaturated carboxylic acid monomer, acrylic monomer containing hydroxyl, catalyst, and ligand in the following molar ratio: 1: 30-40: 10-20: 5-10: 3-5: 8-10.
Preferably, the macroinitiator POSS-Cl, TPEG, unsaturated carboxylic acid monomer, hydroxyl-containing acrylic monomer, catalyst and ligand are in a molar ratio of: 1: 30: 10: 5: 3: 9.
Preferably, the base in step (1) is NaOH, KOH, or Ca (O)H) 2 。
Preferably, the acid in step (1) is hydrochloric acid or sulfuric acid or phosphoric acid.
Preferably, the molecular weight of TPEG is 1000-3000.
Preferably, the reaction temperature in step (2) is 40-45 ℃.
Preferably, the unsaturated carboxylic acid monomer is at least one of acrylic acid AA, methacrylic acid MA, maleic anhydride and itaconic acid.
Preferably, the hydroxyl group-containing acrylic monomer is hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, such as hydroxyethyl methacrylate HEMA, and the like.
The star-shaped polycarboxylate superplasticizer prepared by the invention has excellent net slurry fluidity, and can obviously improve the concrete strength while resisting mud.
Detailed Description
Preparation example 1
(1) Dissolving hydroxyl octa-polyhedral oligomeric silsesquioxane (POSS-OH) in dimethyl sulfoxide (DMSO) to form a solution with a concentration of 20%, stirring for 5 hours, cooling to O ℃, adding triethylamine, dropwise adding 2-chloroacetyl chloride under a stirring state, reacting at room temperature for 24 hours after dropwise adding, sequentially cleaning with NaOH solution, hydrochloric acid solution and deionized water, adding the lower layer solution into methanol for precipitation, and performing vacuum drying on the obtained precipitate to obtain a macromolecular initiator POSS-Cl;
(2) Adding a macroinitiator POSS-Cl into a reaction bottle, dissolving in DMSO, adding a mixed solution of TPEG, AA and HEMA, performing vacuum pumping, and filling nitrogen N 2 Circulating for 3 times, dissolving cuprous chloride serving as a catalyst and pentamethyldiethylenetriamine serving as a ligand in DMSO, adding the solution into a reaction bottle by using a syringe, reacting for 10 hours at 40 ℃ under magnetic stirring, and dialyzing to remove residual monomers and other impurities after the reaction is finished to obtain the star-shaped polycarboxylic acid water reducer;
wherein the macromolecular initiators POSS-Cl, TPEG, AA and HEMA, the catalysts and the ligands have the molar ratios as follows: 1: 30: 10: 5: 3: 9.
Preparation example 2
Wherein the macromolecular initiators are POSS-Cl, TPEG, AA and HEMA, and the molar ratios of the catalyst and the ligand are as follows: 1: 40: 10: 5: 3: 9. The rest was the same as in preparation example 1.
Preparation example 3
Wherein the macromolecular initiators POSS-Cl, TPEG, AA and HEMA, the catalysts and the ligands have the molar ratios as follows: 1: 30: 20: 5: 3: 9. The rest is the same as in preparation example 1.
Preparation example 4
Wherein the macromolecular initiators POSS-Cl, TPEG, AA and HEMA, the catalysts and the ligands have the molar ratios as follows: 1: 20: 10: 3: 5. The rest is the same as in preparation example 1.
Comparative example 1:
otherwise as in preparation example 1, AA and HEMA were exchanged for equimolar TPEG, i.e., only the TPEG macromonomer was used.
Comparative example 2
Otherwise as in preparation 1, AA was replaced by equimolar HEMA, i.e., TPEG and AA were used.
Comparative example 3
Otherwise as in preparation example 1, HEMA was replaced with equimolar AA, i.e., TPEG and HEMA were used.
Testing the performance of the concrete;
the net pulp fluidity of the sample is tested by referring to GB8077-2000, and 0h and 1h of the preparation examples 1-4 are both more than 260mm and 230mm respectively. Concrete strength tests were carried out on the samples obtained in the preparation examples with reference to GB8076-2008< concrete admixture >, the flexural anchoring amount of the admixture was 0.1wt% (relative to the amount of cement), the compressive strength of the obtained samples 3d,7d and 28d were as shown in Table 1 below, and the net paste fluidity properties were as shown in Table 2 below.
TABLE 1 mechanical Properties of the concrete for the different samples
TABLE 2 mechanical Properties of concrete of different samples
Claims (6)
1. A preparation method of a star-shaped polycarboxylic acid water reducing agent comprises the following steps:
(1) Dissolving hydroxyl octamer polyhedral oligomeric silsesquioxane in dimethyl sulfoxide (DMSO) to form a solution with the concentration of 20-25%, stirring for 4-6h, cooling to 0-5 ℃, adding triethylamine, dropwise adding 2-chloroacetyl chloride under stirring, reacting at room temperature for 15-24h after dropwise adding, sequentially cleaning with alkali liquor, acid liquor and deionized water, adding lower-layer liquor into methanol for precipitation, and performing vacuum drying on the obtained precipitate to obtain a macroinitiator POSS-Cl;
(2) Adding a macroinitiator POSS-Cl into a reaction bottle, dissolving in DMSO, adding a mixed solution of isoamylene alcohol polyoxyethylene ether (TPEG), unsaturated carboxylic acid monomer and hydroxyl-containing acrylic monomer, performing vacuum pumping and filling nitrogen N 2 Circulating for more than 3 times, dissolving cuprous chloride serving as a catalyst and pentamethyldiethylenetriamine serving as a ligand in DMSO, adding the solution into a reaction bottle by using an injector, reacting for 8-12 hours at 30-60 ℃ under magnetic stirring, and dialyzing to remove residual monomers and other impurities after the reaction is finished to obtain the star-shaped polycarboxylic acid water reducer;
the molar ratio of the macromolecular initiator POSS-Cl, TPEG, unsaturated carboxylic acid monomer, hydroxyl-containing acrylic monomer, catalyst and ligand is as follows: 1: 30-40: 10-20: 5-10: 3-5: 8-10.
2. The method of claim 1, wherein: the alkali in the step (1) is NaOH, KOH or Ca (OH) 2 (ii) a The acid in the step (1) is hydrochloric acid, sulfuric acid or phosphoric acid.
3. The method of claim 1, wherein: TPEG has a molecular weight of 1000-3000.
4. The method of claim 1, wherein: the reaction temperature in step (2) was 40 ℃.
5. The method of claim 1, wherein: the unsaturated carboxylic acid monomer is at least one of acrylic acid AA, methacrylic acid MA, maleic anhydride and itaconic acid.
6. The method of claim 1, wherein: the acrylic monomer containing hydroxyl is hydroxyethyl (methyl) acrylate or hydroxypropyl (methyl) acrylate.
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| CN110721632B (en) * | 2019-10-13 | 2021-12-21 | 武汉善达化工有限公司 | Water-based inorganic filler dispersant and preparation method thereof |
| CN112724412A (en) * | 2021-01-21 | 2021-04-30 | 江苏奥莱特新材料股份有限公司 | POSS structure-terminated polycarboxylate superplasticizer and preparation method thereof |
| CN116178617A (en) * | 2022-10-25 | 2023-05-30 | 江苏超力建材科技有限公司 | Star-shaped high-performance polycarboxylate superplasticizer and preparation method thereof |
| CN117303779B (en) * | 2023-09-27 | 2024-06-07 | 长沙千巽新材料科技有限公司 | Bi-component concrete additive, preparation method and application |
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| CN102910855A (en) * | 2012-10-18 | 2013-02-06 | 江苏博特新材料有限公司 | Super plasticizer for precast concrete component |
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| CN105669913A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Preparation method of star polycarboxylate water reducing agent with controllable molecular structure |
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| CN102910855A (en) * | 2012-10-18 | 2013-02-06 | 江苏博特新材料有限公司 | Super plasticizer for precast concrete component |
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