CN114014997A - Method for synthesizing polycarboxylate superplasticizer by taking polyether macromonomer as raw material at normal temperature - Google Patents
Method for synthesizing polycarboxylate superplasticizer by taking polyether macromonomer as raw material at normal temperature Download PDFInfo
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- CN114014997A CN114014997A CN202111440297.XA CN202111440297A CN114014997A CN 114014997 A CN114014997 A CN 114014997A CN 202111440297 A CN202111440297 A CN 202111440297A CN 114014997 A CN114014997 A CN 114014997A
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 86
- 229920000570 polyether Polymers 0.000 title claims abstract description 86
- 239000002994 raw material Substances 0.000 title claims abstract description 21
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 16
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title description 15
- 230000002194 synthesizing effect Effects 0.000 title description 6
- 239000007788 liquid Substances 0.000 claims abstract description 134
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 72
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000007853 buffer solution Substances 0.000 claims abstract description 22
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 238000001308 synthesis method Methods 0.000 claims abstract description 16
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 239000007864 aqueous solution Substances 0.000 claims description 44
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 34
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 230000037452 priming Effects 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 239000002211 L-ascorbic acid Substances 0.000 claims description 6
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007974 sodium acetate buffer Substances 0.000 claims description 6
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008055 phosphate buffer solution Substances 0.000 claims description 5
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 claims description 5
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 claims description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 20
- -1 ethyleneoxy structure Chemical group 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 239000004568 cement Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 101000908015 Homo sapiens Putative inactive carboxylesterase 4 Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 102100023322 Putative inactive carboxylesterase 4 Human genes 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers 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)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a normal-temperature synthesis method of a polycarboxylate superplasticizer by taking a polyether macromonomer as a raw material, which comprises the following steps of preparing an unsaturated carboxylic acid, a neutralizing reagent and water into a dropping liquid A according to a certain mass ratio; preparing a dropping liquid B from a chain transfer agent, a reducing agent and water according to a certain mass ratio; preparing a dripping liquid C from a polyether macromonomer containing a terminal ethyleneoxy structure and water according to a certain mass ratio; preparing a buffer solution, an oxidant and water into a base solution according to a certain proportion; and (3) dropwise adding the dropping liquid A, the dropping liquid B and the dropping liquid C into the base solution, continuing to react for 30-60 min after the dropwise adding is finished, and neutralizing with liquid caustic soda until the pH value is about 7 to obtain a finished product of the polycarboxylic acid water reducing agent. The preparation method of the water reducer is between 20 and 45 ℃, is coincident with the temperature range of the conventional HPEG and IPEG polyether macromonomer for preparing the water reducer, does not need technical modification on water reducer equipment, and can be used for producing and preparing the water reducer containing the polyether macromonomer with the terminal ethyleneoxy structure.
Description
Technical Field
The invention relates to a method for synthesizing a polycarboxylate superplasticizer, in particular to a method for synthesizing the polycarboxylate superplasticizer by taking a polyether macromonomer as a raw material at normal temperature, and belongs to the field of application of concrete admixtures.
Background
The polyether macromonomer commonly used for synthesizing the polycarboxylic acid water reducing agent is a polyether macromonomer such as allyl polyglycol ether (APEG for short), 2-methylpropane-2-alkenyl polyglycol ether (HPEG for short), 3-methylbut-3-alkenyl polyglycol ether (IPEG for short) and the like, and the polyether macromonomer accounts for more than 90 percent of the domestic polyether macromonomer yield. Along with the shortage of natural resources such as concrete, gravel and aggregate in China, the popularization and application of machine-made sand, low-activity bulk industrial solid waste ultrafine powder and the like in the concrete industry put forward higher requirements on the performances such as water reduction, early strength, workability, mud resistance and the like of the water reducer, and the demand of developing a polyether macromonomer with a new structure to be applied to a polycarboxylic acid water reducer is urgent.
The researches of Liu Guanjie and the like show that the polymerization activity of the polyether macromonomer containing the ethyleneoxy structure is higher than that of HPEG and IPEG (Liu Guanjie and the like, the condition and performance research of synthesizing the polycarboxylic acid water reducing agent by vinyl ether macromonomer EPEG [ J ]. concrete, 2021, (5), 61-66). The technical conditions, material ratio and the like of polymerization of the polyether macromonomer EPEG-2400 containing an ethyleneoxy structure and acrylic acid and the like are researched, and research and development find that the water reducing agent has better water reducing and slump retaining performances than water reducing agents prepared from other polyether macromonomers at 15-35 ℃ within 1h of dripping time. The hypotensor and the like are polymerized by using polyether macromonomer EPGG-3000 containing an ethyleneoxy structure and acrylic acid and the like, the dropping temperature is not more than 20 ℃, the dropping time is 45min, and the water reducing performance and 1h slump retaining performance of the water reducing agent are better than those of the water reducing agent prepared by HPEG-3000 and IPEG-3000 polyether macromonomers. According to the method, a polyether macromonomer VPEG-3000 containing an ethyleneoxy structure is polymerized with monomers such as acrylic acid and acrylic ester, the initial dropping temperature is 15 ℃, and the doping amount, temperature and water consumption adaptability and mud resistance of the water reducer are superior to those of a comparative water reducer sample. Patent CN 111808239A reports that polyether macromonomer such as EPEG-4800A and VPEG-4800 and monomers such as acrylic acid are polymerized, the reaction temperature is controlled to be 4-8 ℃, and the early strength performance of the water reducer is excellent.
The research results show that the polymerization activity of the polyether macromonomer containing the terminal ethyleneoxy structure is higher than that of the polyether macromonomer such as HPEG, IPEG and the like, and the prepared water reducing agent has excellent performances in the aspects of water reduction, slump retaining, early strength, mud resistance and the like. However, in the synthesis process of the water reducer, the initial dropping temperature needs to be controlled or the reaction process temperature needs to be controlled at a lower temperature, the existing water reducer synthesis process using the HPEG and IPEG polyether macromonomer as the raw material has the reaction temperature of 30-45 ℃, and the water reducer synthesis equipment cannot be directly used for producing the water reducer using the EPEG or VPEG polyether macromonomer containing the terminal ethyleneoxy group structure as the raw material, so that the popularization and application of the polyether macromonomer containing the terminal ethyleneoxy group structure in the water reducer industry are hindered.
Disclosure of Invention
The invention aims to provide a preparation method of a polycarboxylate superplasticizer, which is simple in synthesis method and can be produced at normal temperature, and particularly relates to a normal-temperature synthesis method of a polycarboxylate superplasticizer taking a polyether macromonomer as a raw material.
The invention achieves the aim through the following technical scheme, and the normal-temperature synthesis method of the polycarboxylic acid water reducing agent by taking the polyether macromonomer as the raw material comprises the following steps,
s1, preparing dropping liquid: mixing unsaturated carboxylic acid and water according to a certain mass ratio, adding a neutralizing agent, adjusting the pH value of an unsaturated carboxylic acid aqueous solution, and preparing a dropping liquid A; preparing a dropping liquid B from a chain transfer agent, a reducing agent and water according to a certain mass ratio; preparing a dripping liquid C from a polyether macromonomer containing a terminal ethyleneoxy structure and water according to a certain mass ratio;
s2, preparing a base solution: preparing an oxidant aqueous solution with a certain concentration by using water, adding the prepared oxidant aqueous solution into a reaction device for priming, and adding a certain amount of buffer solution into the reaction device to prepare a priming solution;
s3, preparing a water reducing agent: and (3) dropwise adding the dropping liquid A, the dropping liquid B and the dropping liquid C into the base solution of the reaction device within a certain time, continuing to react for 30-60 min after dropwise adding is finished, and neutralizing with liquid alkali until the pH value is about 7 to obtain a finished product of the polycarboxylic acid water reducing agent.
Preferably, in step S1, the ratio of the unsaturated carboxylic acid to the water is unsaturated carboxylic acid: water (50-60%): (40% to 50%), mixing unsaturated carboxylic acid and water according to the ratio of unsaturated carboxylic acid: water (50-60%): (40-50%) and adding a neutralizing agent into the mixed solution of the unsaturated carboxylic acid and water to adjust the pH value of the aqueous solution of the unsaturated carboxylic acid to be between 5 and 7.
Preferably, the unsaturated carboxylic acid in step S1 is one or a mixture of acrylic acid, methacrylic acid, maleic acid and itaconic acid, and the neutralizing agent is liquid alkali with a mass concentration of 32%.
Preferably, in step S1, the amount of the chain transfer agent is between 0.3% and 0.8% of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing a terminal ethyleneoxy structure, the amount of the reducing agent is between 0.1% and 0.2% of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing a terminal ethyleneoxy structure, and the dropping solution B is an aqueous solution prepared by using water to prepare a reducing agent and a solute such as a chain transfer agent into a concentration of between 2% and 5%.
Preferably, the chain transfer agent is one of thioglycolic acid, mercaptopropionic acid and mercaptoethanol, and the reducing agent is one of L-ascorbic acid, sodium formaldehyde sulfoxylate and E51.
Preferably, in the step S1, the dropping liquid C is 40% to 60% of an aqueous solution of polyether containing terminal ethyleneoxy group structure, the polyether macromonomer containing terminal ethyleneoxy group structure is commonly commercially available VPEG and EPEG, the polyether weight average molecular weight is 3000-:
wherein X is one of-CH 2-CH2-, -CH2-CH2-CH2-CH 2-CH2-CH 2-O-CH2-CH2-, and y represents the number of structural units of ethylene oxide and is an integer between 70 and 150. The common polyether types are VPEG-3000, VPEG-4000, VPEG-5000, VPEG-6000, EPEG-3000, EPEG-4000, EPEG-5000, and EPEG-6000.
Preferably, in the step S2, the amount of the buffer solution is 10-20% of the mass of the unsaturated carboxylic acid, the amount of the oxidant is 0.3-0.7% of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing a terminal ethyleneoxy structure, and the mass concentration of the aqueous oxidant solution is 5-10%.
Preferably, the buffer solution is one of acetic acid-sodium acetate buffer solution, sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution and citric acid-sodium citrate buffer solution, the concentration of the buffer liquid is 0.1-0.5 mol/L, the pH value range is 5-7, and the oxidant is one of ammonium persulfate, potassium persulfate, sodium persulfate and 30% hydrogen peroxide.
Preferably, in step S3, the mass ratio of the unsaturated carboxylic acid in the dropping liquid a to the polyether macromonomer containing terminal ethyleneoxy structure in the dropping liquid C is 1: (6-11), the dropping time of the dropping liquid A and the dropping time of the dropping liquid C are the same, the dropping time of the dropping liquid B is 10-20 min longer than that of the dropping liquid A or the dropping time of the dropping liquid C within 60-120 min, the temperature is kept for reaction for 30-60 min after the dropping is finished, the whole polymerization reaction is carried out under the conditions of normal pressure and normal temperature in the step S3, and the normal temperature range is 20-45 ℃.
Preferably, in the step S3, the liquid caustic soda is a liquid caustic soda solution with a mass concentration of 32%, and the weight average molecular weight of the polycarboxylate superplasticizer prepared in the step S3 is 20000 to 50000.
The invention has the beneficial effects that: the invention discloses a normal-temperature synthesis method of a polycarboxylic acid water reducing agent by taking a polyether macromonomer as a raw material, which has obvious advantages in the following aspects:
1. the preparation method of the water reducer is between 20 and 45 ℃, is coincident with the temperature range of the conventional HPEG and IPEG polyether macromonomer for preparing the water reducer, does not need technical modification on water reducer equipment, and can be used for producing and preparing the water reducer containing the polyether macromonomer with the terminal ethyleneoxy structure.
2. The polymerization activity of the polyether macromonomer containing the terminal ethyleneoxy structure is higher than that of HPEG and IPEG, and the polymerization activity is close to that of acrylic acid. According to the preparation method of the water reducing agent, acrylic acid is neutralized and then is dripped into the base solution together with the polyether macromonomer, so that the ratio of the polyether macromonomer structural unit in the water reducing agent structure is increased, and the water reducing and slump retaining performances of the water reducing agent are improved.
3. And adding a buffer solution into the primer solution to stabilize the pH value in the polymerization reaction process to be between 5 and 7, so that the influence of the change of the pH value on the polymerization process of the free radicals of the monomers is avoided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art will be able to make variations within the scope of the invention based on the disclosure herein, in reagents, catalysts and reaction process conditions. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
In the examples of the present invention, the molecular weight and molecular weight distribution of the polycarboxylic acid water reducing agent were measured by Wyatt technology corporation gel permeation chromatography.
The gel column comprises Shodex SB806+8032 chromatographic columns which are connected in series; the eluent is tetrahydrofuran; the speed of the mobile phase is 1 ml/min; the sample amount is 20 mul; the sample preparation concentration is 0.5% (sample g/mobile phase g);
detector, Shodex RI-71 type refractive index detector;
polyethylene glycol GPC;
standard sample preparation: Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232.
In the application example of the invention, the cement used is ordinary portland cement (P.O 42.5.5) unless otherwise specified.
The fluidity of the cement paste is measured by referring to the GB/T8077-2000 standard, the water addition amount is 87g, and the fluidity of the cement paste is measured on a flat glass.
The test method of the gas content and the water reducing rate is carried out according to the relevant regulations of GB8076-2008 concrete admixture.
In the embodiment, the parts are referred to as mass parts, and the addition amount of other materials is converted into mass parts.
A normal-temperature synthesis method of a polycarboxylate superplasticizer taking a polyether macromonomer as a raw material comprises the following steps,
s1, preparing dropping liquid: mixing unsaturated carboxylic acid and water according to a certain mass ratio, adding a neutralizing agent, adjusting the pH value of an unsaturated carboxylic acid aqueous solution, and preparing a dropping liquid A; preparing a dropping liquid B from a chain transfer agent, a reducing agent and water according to a certain mass ratio; preparing a dripping liquid C from a polyether macromonomer containing a terminal ethyleneoxy structure and water according to a certain mass ratio;
the literature reports (Jinyong et al, influence of pH on copolymerization of acrylic acid-butenal [ J ], high molecular report, 2003, (1),150-153) show that pH has an important influence on the polymerization conversion rate of acrylic acid and the chain structure of polymer, so that the pH of the aqueous solution of unsaturated carboxylic acid needs to be adjusted by a neutralizing agent in the scheme.
In the preparation process of the dropping liquid A, the dosage proportion of the unsaturated carboxylic acid and the water is (50-60%): (40% -50%), mixing unsaturated carboxylic acid and water according to (50% -60%): (40-50%) and adding a neutralizing agent into the mixed solution of the unsaturated carboxylic acid and water to adjust the pH value of the aqueous solution of the unsaturated carboxylic acid to be between 5 and 7.
In the preparation process of the dropping liquid A, the unsaturated carboxylic acid is one or a mixture of acrylic acid, methacrylic acid, maleic acid and itaconic acid, and the neutralizing agent is liquid alkali with the mass concentration of 32%.
In the preparation process of the dropping liquid B, the dosage of the chain transfer agent is 0.3-0.8% of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing the terminal ethyleneoxy structure, the dosage of the reducing agent is 0.1-0.2% of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing the terminal ethyleneoxy structure, and the dropping liquid B is an aqueous solution prepared from the reducing agent, the chain transfer agent and other solutes into a concentration of 2-5% by using water.
In the preparation process of the dropping liquid B, the chain transfer agent is one of thioglycolic acid, mercaptopropionic acid and mercaptoethanol, and the reducing agent is one of L-ascorbic acid, sodium formaldehyde sulfoxylate and E51.
In the preparation process of the dropping liquid C, the dropping liquid C is 40-60% of polyether aqueous solution containing a terminal ethyleneoxy structure, the polyether macromonomer containing the terminal ethyleneoxy structure is common commercial VPEG and EPEG, the polyether weight average molecular weight is 3000-6000, and the structural formula of the commercial VPEG or EPEG polyether macromonomer is as follows:
wherein X is one of-CH 2-CH2-, -CH2-CH2-CH2-CH 2-CH2-CH 2-O-CH2-CH2-, and y represents the number of structural units of ethylene oxide and is an integer between 70 and 150. The common polyether types are VPEG-3000, VPEG-4000, VPEG-5000, VPEG-6000, EPEG-3000, EPEG-4000, EPEG-5000, and EPEG-6000.
S2, preparing a base solution: preparing an oxidant aqueous solution with a certain concentration by using water, adding the prepared oxidant aqueous solution into a reaction device for priming, and adding a certain amount of buffer solution into the reaction device to prepare a priming solution;
in the step S2, the amount of the buffer solution is 10% to 20% by mass of the unsaturated carboxylic acid, the amount of the oxidant is 0.3% to 0.7% by mass of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing a terminal ethyleneoxy group structure, and the mass concentration of the oxidant aqueous solution is 5% to 10%.
In the step S2, the buffer solution is one of an acetic acid-sodium acetate buffer solution, a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution, and a citric acid-sodium citrate buffer solution, the concentration of the buffer solution is 0.1 to 0.5mol/L, the pH value ranges from 5 to 7, and the oxidant is one of ammonium persulfate, potassium persulfate, sodium persulfate, and 30% hydrogen peroxide.
The buffer solutions used in step S2 are all commercially available products, and the concentration ranges of the buffer solutions are also commercially available common concentration ranges.
S3, preparing a water reducing agent: and (3) dropwise adding the dropping liquid A, the dropping liquid B and the dropping liquid C into the base solution of the reaction device within a certain time, continuing to react for 30-60 min after dropwise adding is finished, and neutralizing with liquid alkali until the pH value is about 7 to obtain a finished product of the polycarboxylic acid water reducing agent.
In the step S3, the mass ratio of the unsaturated carboxylic acid in the dropping liquid a to the polyether macromonomer containing terminal ethyleneoxy structure in the dropping liquid C is 1: (6-11), the dropping time of the dropping liquid A is the same as that of the dropping liquid C, the dropping time of the dropping liquid B is 10-20 min longer than that of the dropping liquid A or the dropping liquid C within 60-120 min, the temperature is kept for reaction for 30-60 min after the dropping is finished, the whole polymerization reaction is carried out under the conditions of normal pressure and normal temperature in the step S3, a jacket or an inner coil pipe is not required to be filled with chilled water, the temperature is reduced to 5-15 ℃ in advance, and the normal temperature range is 20-45 ℃.
In the step S3, the liquid caustic soda is a liquid caustic soda solution with a mass concentration of 32%, and the weight average molecular weight of the polycarboxylic acid water reducer prepared in the step S3 is 20000 to 50000, so that the polycarboxylic acid water reducer has good water reducing and slump retaining effects, and the polyether macromonomer conversion rate or the performance of the prepared water reducer can be adversely affected if the molecular weight is too large or too small.
Example 1
Dropping liquid A: weighing 16.7 parts of acrylic acid, adding 11.1 parts of water, fully and uniformly stirring, neutralizing an acrylic acid aqueous solution by using 32% liquid caustic soda until the pH value is between 5 and 7, and finishing the preparation of a dropping liquid A;
dropping liquid B: weighing 0.35 part of mercaptopropionic acid and 0.12 part of L-ascorbic acid, adding water to dilute the mixture to obtain an aqueous solution with the mass concentration of 2%, and dripping liquid B to prepare the solution B;
dropping liquid C: 100 parts of VPEG-3000 polyether macromonomer is weighed, 66.7 parts of water is added to prepare an aqueous solution with the mass concentration of 60%, and the solution C is dripped to prepare the modified polyether macromonomer.
Weighing 0.35 part of ammonium persulfate in a reaction device, adding water to dilute the ammonium persulfate into a 5% aqueous solution, weighing 1.67 parts of acetic acid-sodium acetate buffer solution with the pH value of 5-7, adding the acetic acid-sodium acetate buffer solution into the reaction device, and finishing the preparation of the primer solution. Starting a mechanical stirring device and circulating water of a reaction device, setting the dropping time of a dropping liquid A and a dropping liquid C to be 60min, setting the dropping time of a dropping liquid B to be 70min, controlling the reaction temperature of the reaction device to be 20 ℃, continuing heat preservation reaction for 30min after the dropping is finished, and after the reaction is finished, adjusting the pH value of a polymerization system to be 7 by using 32% liquid alkali to obtain light yellow viscous liquid, namely a polycarboxylic acid water reducer finished product, which is marked as PCE-1, and through GPC (graphical connectivity analysis) tests, the weight average molecular weight (Mw) is 35420 and the molecular weight distribution (PDI) is 1.79.
Example 2
Dropping liquid A: weighing 12.5 parts of methacrylic acid, adding 12.5 parts of water, fully and uniformly stirring, neutralizing an acrylic acid aqueous solution by using 32% liquid caustic soda until the pH value is between 5 and 7, and dripping liquid A to prepare the acrylic acid aqueous solution;
dropping liquid B: weighing 0.56 part of thioglycolic acid and 0.23 part of sodium formaldehyde sulfoxylate, adding water to dilute the mixture to obtain an aqueous solution with the mass concentration of 5%, and dripping liquid B to prepare the solution;
dropping liquid C: 100 parts of EPEG-3000 polyether macromonomer is weighed, 100 parts of water is added to prepare an aqueous solution with the mass concentration of 50%, and the solution C is dripped to prepare the polyether macromonomer.
Weighing 0.56 part of potassium persulfate in a reaction device, adding water to dilute the potassium persulfate into a 10% aqueous solution, weighing 2.25 parts of sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH value of 5-7, adding the sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution into the reaction device, and finishing the preparation of the primer solution. Starting a mechanical stirring device and circulating water of a reaction device, setting the dropping time of a dropping liquid A and a dropping liquid C to be 120min, setting the dropping time of a dropping liquid B to be 140min, controlling the reaction temperature of the reaction device to be 45 ℃, continuing to perform heat preservation reaction for 60min after the dropping is finished, and after the reaction is finished, adjusting the pH value of a polymerization system to be 7 by using 32% liquid alkali to obtain light yellow viscous liquid, namely a polycarboxylic acid water reducer finished product, which is marked as PCE-2, and performing GPC (graphical user connectivity analysis) test to obtain a weight average molecular weight (Mw) of 48170 and a molecular weight distribution (PDI) of 1.91.
Example 3
Dropping liquid A: weighing 9.1 parts of itaconic acid, adding 9.1 parts of water, fully and uniformly stirring, neutralizing an acrylic acid aqueous solution by using 32% liquid alkali until the pH value is between 5 and 7, and dropwise adding liquid A to prepare the acrylic acid aqueous solution;
dropping liquid B: weighing 0.87 part of mercaptoethanol and 510.16 parts of E, adding water to dilute the mercaptoethanol and the E to obtain an aqueous solution with the mass concentration of 3%, and dripping liquid B to prepare the solution;
dropping liquid C: weighing 100 parts of EPEG-6000 polyether macromonomer, adding 150 parts of water to prepare an aqueous solution with the mass concentration of 40%, and dripping liquid C to prepare the polyether macromonomer.
Weighing 0.76 part of potassium persulfate in a reaction device, adding water to dilute the potassium persulfate into an aqueous solution with the mass concentration of 8%, weighing 1.37 parts of citric acid-sodium citrate buffer solution with the pH value of 5-7, adding the citric acid-sodium citrate buffer solution into the reaction device, and finishing the preparation of the primer solution. Starting a mechanical stirring device and circulating water of a reaction device, setting the dropping time of a dropping liquid A and a dropping liquid C to be 80min, setting the dropping time of a dropping liquid B to be 90min, controlling the reaction temperature of the reaction device to be 30 ℃, continuing to perform heat preservation reaction for 40min after the dropping is finished, and after the reaction is finished, adjusting the pH value of a polymerization system to be 7 by using 32% liquid alkali to obtain light yellow viscous liquid, namely a polycarboxylic acid water reducer finished product, which is marked as PCE-3, and through GPC (polymer permeation chromatography) test, the weight average molecular weight (Mw) is 39930 and the molecular weight distribution (PDI) is 1.87.
Example 4
Dropping liquid A: weighing 15.0 parts of maleic acid, adding 10.0 parts of water, fully and uniformly stirring, neutralizing an acrylic acid aqueous solution by using 32% liquid alkali until the pH value is between 5 and 7, and dropwise adding a liquid A to prepare the acrylic acid aqueous solution;
dropping liquid B: weighing 0.72 part of mercaptopropionic acid and E510.18 parts, adding water to dilute the mercaptopropionic acid and E510.18 parts to obtain an aqueous solution with the mass concentration of 4%, and dripping liquid B to prepare the solution B;
dropping liquid C: weighing 100 parts of VPEG-4000 polyether macromonomer, adding 100 parts of water to prepare an aqueous solution with the mass concentration of 50%, and dripping liquid C to prepare the polyether macromonomer.
Weighing 0.69 part of 30% solid hydrogen peroxide in a reaction device, adding water to dilute the mixture to form an aqueous solution with the mass concentration of 6%, weighing 2.7 parts of acetic acid-sodium acetate buffer solution with the pH value of 5-7, adding the solution into the reaction device, and finishing the preparation of the primer solution. Starting a mechanical stirring device and circulating water of a reaction device, setting the dropping time of a dropping liquid A and a dropping liquid C to be 70min, setting the dropping time of a dropping liquid B to be 80min, controlling the reaction temperature of the reaction device to be 35 ℃, continuing heat preservation reaction for 50min after the dropping is finished, and after the reaction is finished, adjusting the pH value of a polymerization system to be 7 by using 32% liquid alkali to obtain light yellow viscous liquid, namely a polycarboxylic acid water reducer finished product, which is marked as PCE-4, and through GPC (polymer permeation chromatography) test, the weight average molecular weight (Mw) is 32060 and the molecular weight distribution (PDI) is 1.69.
Comparative example 1
Dropping liquid A: weighing 12.5 parts of acrylic acid, adding 12.5 parts of water, fully and uniformly stirring, and completing the preparation of the dropping liquid A;
dropping liquid B: weighing 0.68 part of mercaptopropionic acid and 0.11 part of L-ascorbic acid, adding water to dilute the mixture to obtain an aqueous solution with the mass concentration of 5%, and dripping liquid B to prepare the solution B;
100 parts of EPEG-4000 polyether macromonomer is weighed and put into a reaction device, 100 parts of water is added to prepare aqueous solution with the mass concentration of 50%. And (3) weighing 0.69 part of 30% solid hydrogen peroxide, adding into a reaction device, and finishing the preparation of the primer solution. Starting a mechanical stirring device of the reaction device and chilled water, setting the dropping time of the dropping liquid A to be 60min, setting the dropping time of the dropping liquid B to be 80min, controlling the reaction temperature of the reaction device to be 15 ℃, continuing heat preservation reaction for 30min after the dropping is finished, and after the reaction is finished, adjusting the pH value of a polymerization system to be 7 by using 32% liquid caustic soda to obtain light yellow viscous liquid, namely a polycarboxylic acid water reducer finished product, namely PCE-5, and performing GPC (GPC) test to obtain a weight average molecular weight (Mw) of 35840 and a molecular weight distribution (PDI) of 1.87.
Remarking: comparative example Using a conventional Low temperature polymerization Process, polyether priming, acrylic acid was added dropwise without neutralization
Comparative example 2
Dropping liquid A: weighing 12.0 parts of acrylic acid, adding 8.0 parts of water, fully and uniformly stirring, and completing the preparation of the dropping liquid A;
dropping liquid B: weighing 0.72 part of thioglycolic acid and 0.18 part of L-ascorbic acid, adding water to dilute the mixture to obtain an aqueous solution with the mass concentration of 3%, and dripping liquid B to prepare the solution;
100 parts of EPEG-5000 polyether macromonomer is weighed and put into a reaction device, 150 parts of water is added to prepare aqueous solution with the mass concentration of 40 percent. And 0.45 part of sodium persulfate is weighed and added into the reaction device, and the preparation of the primer solution is finished. Starting a mechanical stirring device and circulating water of a reaction device, setting the dripping time of dripping liquid A to be 120min, setting the dripping time of dripping liquid B to be 130min, controlling the reaction temperature of the reaction device to be 30 ℃, continuing heat preservation reaction for 30min after the dripping is finished, and adjusting the pH value of a polymerization system to be 7 by using 32% liquid caustic soda after the reaction is finished to obtain light yellow viscous liquid, namely a polycarboxylic acid water reducer finished product, namely PCE-6, and performing GPC (GPC) test to obtain a weight average molecular weight (Mw) of 69170 and a molecular weight distribution (PDI) of 2.83.
Remarking: the comparative example uses a normal temperature polymerization process, polyether priming, no buffer solution, and no acrylic acid neutralization.
The application example is as follows:
in the application examples, the cement used was ordinary portland cement (p.o42.5) unless otherwise specified. The test temperature is controlled to be 25 +/-5 ℃, and the test of the fluidity of the cement paste refers to the method specified in GB/T8077-2000 'test method for the homogeneity of concrete additives'. And (3) testing the cement paste: the cement flow rate was measured on a flat glass plate at 300g of cement and 87g of added water, and the test results are shown in Table 1 for the net flow rate over time at 60min and 120 min.
TABLE 1 Cement paste fluidity test results
The results in table 1 show that the polycarboxylic acid water reducer prepared by the normal temperature synthesis process of the invention has better initial flow property and slump retaining property, the initial water reducing property of the water reducer is similar to that of the water reducer prepared by the low temperature process in comparative example 1, and the slump retaining property of the water reducer is slightly better than that of the water reducer prepared by the low temperature process. In comparative example 2, the unsaturated carboxylic acid does not neutralize and buffer solution is not used to stabilize the pH value of the reaction system, and the initial fluidity and slump retention performance of the prepared water reducing agent are significantly inferior to those of the water reducing agent prepared by the low temperature process in comparative example 1 and the water reducing agent prepared by the normal temperature synthesis process of the present invention.
Based on the above, the normal-temperature synthesis process of the polyether macromonomer containing the terminal ethyleneoxy structure as the raw material has obvious innovation and performance advantages.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A normal-temperature synthesis method of a polycarboxylate superplasticizer by taking a polyether macromonomer as a raw material is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, preparing dropping liquid: mixing unsaturated carboxylic acid and water according to a certain mass ratio, adding a neutralizing agent, adjusting the pH value of an unsaturated carboxylic acid aqueous solution, and preparing a dropping liquid A; preparing a dropping liquid B from a chain transfer agent, a reducing agent and water according to a certain mass ratio; preparing a dripping liquid C from a polyether macromonomer containing a terminal ethyleneoxy structure and water according to a certain mass ratio;
s2, preparing a base solution: preparing an oxidant aqueous solution with a certain concentration by using water, adding the prepared oxidant aqueous solution into a reaction device for priming, and adding a certain amount of buffer solution into the reaction device to prepare a priming solution;
s3, preparing a water reducing agent: and (3) dropwise adding the dropping liquid A, the dropping liquid B and the dropping liquid C into the base solution of the reaction device within a certain time, continuing to react for 30-60 min after dropwise adding is finished, and neutralizing with liquid alkali until the pH value is about 7 to obtain a finished product of the polycarboxylic acid water reducing agent.
2. The normal-temperature synthesis method of the polycarboxylate superplasticizer taking the polyether macromonomer as the raw material according to claim 1, characterized by comprising the following steps: in the step S1, the ratio of the unsaturated carboxylic acid to the water is unsaturated carboxylic acid: water (50-60%): (40% to 50%), mixing unsaturated carboxylic acid and water according to the ratio of unsaturated carboxylic acid: water (50-60%): (40-50%) and adding a neutralizing agent into the mixed solution of the unsaturated carboxylic acid and water to adjust the pH value of the aqueous solution of the unsaturated carboxylic acid to be between 5 and 7.
3. The normal-temperature synthesis method of the polycarboxylic acid water reducer by taking the polyether macromonomer as the raw material according to claim 1 or claim 2, characterized in that: the unsaturated carboxylic acid in the step S1 is one or a mixture of several of acrylic acid, methacrylic acid, maleic acid and itaconic acid, and the neutralizing agent is liquid alkali with a mass concentration of 32%.
4. The normal-temperature synthesis method of the polycarboxylate superplasticizer taking the polyether macromonomer as the raw material according to claim 1, characterized by comprising the following steps: in the step S1, the amount of the chain transfer agent is 0.3% to 0.8% of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing a terminal ethyleneoxy structure, the amount of the reducing agent is 0.1% to 0.2% of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing a terminal ethyleneoxy structure, and the dropping liquid B is an aqueous solution prepared from a reducing agent, a chain transfer agent and other solutes with water to a concentration of 2% to 5%.
5. The normal-temperature synthesis method of the polycarboxylic acid water reducer by taking the polyether macromonomer as the raw material according to claim 1 or claim 4, characterized in that: the chain transfer agent is one of thioglycolic acid, mercaptopropionic acid and mercaptoethanol, and the reducing agent is one of L-ascorbic acid, rongalite and E51.
6. The normal-temperature synthesis method of the polycarboxylate superplasticizer taking the polyether macromonomer as the raw material according to claim 1, characterized by comprising the following steps: in the step S1, the dropping liquid C is 40% to 60% of an aqueous solution of a polyether containing a terminal ethyleneoxy group structure, the polyether macromonomer containing a terminal ethyleneoxy group structure is commonly commercially available VPEG and EPEG, the polyether weight average molecular weight is 3000-6000, and the commercially available VPEG or EPEG polyether macromonomer has the following structural formula:
wherein X is one of-CH 2-CH2-, -CH2-CH2-CH2-CH 2-CH2-CH 2-O-CH2-CH2-, and y represents the number of structural units of ethylene oxide and is an integer between 70 and 150. The common polyether types are VPEG-3000, VPEG-4000, VPEG-5000, VPEG-6000, EPEG-3000, EPEG-4000, EPEG-5000, and EPEG-6000.
7. The normal-temperature synthesis method of the polycarboxylate superplasticizer taking the polyether macromonomer as the raw material according to claim 1, characterized by comprising the following steps: in the step S2, the amount of the buffer solution is 10% to 20% of the mass of the unsaturated carboxylic acid, the amount of the oxidant is 0.3% to 0.7% of the total mass of the unsaturated carboxylic acid and the polyether macromonomer containing a terminal ethyleneoxy group structure, and the mass concentration of the oxidant aqueous solution is 5% to 10%.
8. The normal-temperature synthesis method of the polycarboxylic acid water reducer by taking the polyether macromonomer as the raw material according to claim 1 or claim 7, characterized in that: the buffer solution is one of acetic acid-sodium acetate buffer solution, sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution and citric acid-sodium citrate buffer solution, the concentration of the buffer solution is 0.1-0.5 mol/L, the pH value range is 5-7, and the oxidant is one of ammonium persulfate, potassium persulfate, sodium persulfate and 30% hydrogen peroxide.
9. The normal-temperature synthesis method of the polycarboxylate superplasticizer taking the polyether macromonomer as the raw material according to claim 1, characterized by comprising the following steps: in the step S3, the mass ratio of the unsaturated carboxylic acid in the dropping liquid a to the polyether macromonomer containing terminal ethyleneoxy structure in the dropping liquid C is 1: (6-11), the dropping time of the dropping liquid A and the dropping time of the dropping liquid C are the same, the dropping time of the dropping liquid B is 10-20 min longer than that of the dropping liquid A or the dropping time of the dropping liquid C within 60-120 min, the temperature is kept for reaction for 30-60 min after the dropping is finished, the whole polymerization reaction is carried out under the conditions of normal pressure and normal temperature in the step S3, and the normal temperature range is 20-45 ℃.
10. The normal-temperature synthesis method of the polycarboxylate superplasticizer taking the polyether macromonomer as the raw material according to claim 1, characterized by comprising the following steps: in the step S3, the liquid caustic soda is a liquid caustic soda solution with a mass concentration of 32%, and the weight average molecular weight of the polycarboxylic acid water reducing agent prepared in the step S3 is 20000-50000.
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| US20150291716A1 (en) * | 2012-12-05 | 2015-10-15 | Sobute New Materials Co., Ltd. | Slump retaining polycarboxylic acid superplasticizer |
| WO2016026346A1 (en) * | 2014-08-22 | 2016-02-25 | 科之杰新材料集团有限公司 | Low-temperature method for preparing high-adaptability ether polycarboxylic acid water reducer |
| CN112979214A (en) * | 2021-02-23 | 2021-06-18 | 厦门路桥翔通建材科技有限公司 | Polyether water-retaining agent, preparation method thereof and cement-based building material |
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| US20150291716A1 (en) * | 2012-12-05 | 2015-10-15 | Sobute New Materials Co., Ltd. | Slump retaining polycarboxylic acid superplasticizer |
| WO2016026346A1 (en) * | 2014-08-22 | 2016-02-25 | 科之杰新材料集团有限公司 | Low-temperature method for preparing high-adaptability ether polycarboxylic acid water reducer |
| CN112979214A (en) * | 2021-02-23 | 2021-06-18 | 厦门路桥翔通建材科技有限公司 | Polyether water-retaining agent, preparation method thereof and cement-based building material |
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