WO2023213064A1 - 一种抗絮凝型聚羧酸减水剂及其制备方法 - Google Patents
一种抗絮凝型聚羧酸减水剂及其制备方法 Download PDFInfo
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- WO2023213064A1 WO2023213064A1 PCT/CN2022/129699 CN2022129699W WO2023213064A1 WO 2023213064 A1 WO2023213064 A1 WO 2023213064A1 CN 2022129699 W CN2022129699 W CN 2022129699W WO 2023213064 A1 WO2023213064 A1 WO 2023213064A1
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- parts
- water
- flocculation
- reducing agent
- ammonium persulfate
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 38
- 238000005189 flocculation Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000008030 superplasticizer Substances 0.000 title abstract 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001868 water Inorganic materials 0.000 claims abstract description 32
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 8
- -1 alcohol compound Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000003638 chemical reducing agent Substances 0.000 claims description 36
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 claims 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims 1
- YFDKVXNMRLLVSL-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O YFDKVXNMRLLVSL-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000004576 sand Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000002411 adverse Effects 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 3
- 230000008719 thickening Effects 0.000 abstract description 3
- QAVGKCMDOKZSBK-UHFFFAOYSA-N 1-morpholin-4-ylbut-2-en-1-one Chemical compound CC=CC(=O)N1CCOCC1 QAVGKCMDOKZSBK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 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 4
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NSXOFALHYZPMNH-UHFFFAOYSA-N 1-(3-methylmorpholin-4-yl)prop-2-en-1-one Chemical compound CC1COCCN1C(=O)C=C NSXOFALHYZPMNH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
Definitions
- the invention relates to an anti-flocculation polycarboxylate water-reducing agent and a preparation method thereof.
- the residual flocculant has a very strong adsorption effect on the water-reducing agent molecules, which greatly reduces the effectiveness of the water-reducing agent and seriously affects the quality of concrete. For example, the fluidity of fresh concrete is short-lived and becomes sticky and difficult to construct. Research on polycarboxylate superplasticizers with anti-flocculation properties is rare.
- the main technical problem solved by the present invention is to provide an anti-flocculation polycarboxylate water-reducing agent and a preparation method thereof. From the level of the water-reducing agent, the cations in the residual flocculant in machine-made sand can be reduced.
- the polycarboxylate water-reducing agent The adsorption effect of the polycarboxylate water-reducing agent thereby improves the utilization efficiency of the polycarboxylate water-reducing agent and improves the anti-flocculation property of the polycarboxylate water-reducing agent; from the concrete level, it can greatly reduce the viscosity increase of the concrete caused by the residue of the machine-made sand and gravel flocculant. It has adverse performance effects such as thickening, increased dosage and water demand, serious fluidity loss, and reduced concrete strength.
- one technical solution adopted by the present invention is to provide an anti-flocculation polycarboxylate water-reducing agent, including polyester macromonomer, acrylic acid, acrylammonium, methacryloyl morpholine, alkyl Acrylate phosphate, sodium dodecyl benzene sulfonate, alcohol compounds, ammonium persulfate, sodium hydroxide and water, each component is calculated by weight: 300-360 parts of polyester macromonomer, 20-35 parts of acrylic acid parts, 50-70 parts of acrylammonium, 30-40 parts of methacryloyl morpholine, 20-35 parts of alkyl acrylate phosphate, 20-35 parts of sodium dodecyl benzene sulfonate, 20-35 parts of chain transfer agent 40 parts, 10-20 parts of initiator, 15-35 parts of neutralizer, 460-455 parts of water.
- polyester macromonomer acrylic acid, acrylammonium, methacryloyl morpholine, alky
- the polyester macromonomer is polyethylene glycol dimethacrylate.
- the chain transfer agent is an alcohol compound
- the alcohol compound is one or more complex mixtures of thiol ethanol, isopropyl alcohol or dodecyl mercaptan. .
- the initiator is ammonium persulfate.
- the neutralizing agent is sodium hydroxide solution.
- a method for preparing an anti-flocculation polycarboxylate water-reducing agent includes the following steps:
- S1 Combine 300-360 parts of polyester macromonomer, 20-45 parts of acrylic acid, 50-70 parts of acrylammonium, 30-40 parts of methacryloyl morpholine, 20-50 parts of alkyl acrylate phosphate, 20 -Put 50 parts of sodium dodecylbenzene sulfonate and 260-355 parts of water into the reaction kettle, heat and stir until they dissolve;
- the specific steps are: first add 260-355 parts of water to the reaction kettle, and then add 300-360 parts of polyester macromonomer and 30-40 parts of methyl Acryloyl morpholine, 20-50 parts alkyl acrylate phosphate, 20-50 parts sodium dodecyl benzene sulfonate, 20-45 parts acrylic acid, 50-70 parts acrylammonium.
- steps S3 and S4 ammonium persulfate solution and sodium hydroxide are added dropwise.
- the anti-flocculation polycarboxylate water-reducing agent and its preparation method pointed out in the present invention have the following advantages:
- the same gel material When used on the ground after leveling with gypsum-based leveling mortar, the same gel material has better adaptability, which can avoid the different expansion and shrinkage rates of the material when the ambient temperature and humidity change, which may cause bonding problems. Risk of peeling or cracking of material layers;
- the dry shrinkage rate is extremely low or even non-shrinking.
- the bonding mortar can be directly used for leveling and tiling in one go, simplifying the construction process.
- ammonium persulfate solution After the dropwise addition of the ammonium persulfate solution is completed, add the ammonium persulfate solution to the reaction kettle. The temperature was raised to 80°C and kept at a constant temperature for 3 hours. After the reaction, it was lowered to room temperature. The room temperature was kept for 1 hour. Add 15 parts of sodium hydroxide solution drop by drop to adjust the pH to 7; adjust the obtained polycarboxylate water-reducing agent by adding water. mass fraction to 40%.
- ammonium persulfate solution After the ammonium persulfate solution is added dropwise, raise the temperature in the reaction kettle to 75°C and maintain it at a constant temperature for 4 hours. After the reaction, it is lowered to room temperature and maintained at room temperature for 1 hour. Add 15 parts of sodium hydroxide solution drop by drop to adjust the pH to 6.5; Adjust the mass fraction of the obtained polycarboxylate water-reducing agent to 40% by adding water.
- a mixture of mercaptans with a molar ratio of 1:1 put 20 parts of ammonium persulfate into 100 parts of water, wait until it is completely dissolved to form an ammonium persulfate solution, then add it drop by drop into the reaction kettle, and complete the dripping operation in 2 hours; persulfate After the ammonium solution is added dropwise, raise the temperature in the reaction kettle to 75°C and maintain it at a constant temperature for 4 hours. After the reaction, it is lowered to room temperature and maintained at room temperature for 1 hour. Add 35 parts of sodium hydroxide solution drop by drop to adjust the pH to 7.5; by adding water Adjust the mass fraction of the obtained polycarboxylate water-reducing agent to 40%.
- the chain transfer agent causes free radical transfer of chain growth free radicals to adjust the relative molecular weight of the polymer
- the initiator is used to form active species to initiate chain polymerization reactions
- the neutralizer is used to adjust the pH to 7 ⁇ 0.5.
- the selected flocculant is the most widely used cationic polyacrylamide in the current sand making industry, with a molecular weight of 12 million;
- the polycarboxylate water-reducing agent used in the blank sample is a commercially available conventional polycarboxylate water-reducing agent product with a concentration of 40%.
- the dosage added to the blank sample was 0.5% of the gelling material.
- the anti-flocculation polycarboxylate water-reducing agent obtained in Examples 1 to 4 was tested for comparative performance with the blank sample at the same dosage.
- the specific testing methods are as follows: Initial concrete slump expansion, 60 Min. Concrete slump expansion, 28d concrete Standard curing strength; refer to the standard "GBT50082-2019 Test Method for Long-term Performance and Durability of Ordinary Concrete".
- the invention points out an anti-flocculation polycarboxylate water-reducing agent and its preparation method. From the level of water-reducing agent, it can reduce the cations in the residual flocculant in machine-made sand.
- the adsorption effect of the polycarboxylate water-reducing agent thereby improves the utilization efficiency of the polycarboxylate water-reducing agent and improves the anti-flocculation property of the polycarboxylate water-reducing agent; from the concrete level, it can greatly reduce the viscosity increase of the concrete caused by the residue of the machine-made sand and gravel flocculant. It has adverse performance effects such as thickening, increased dosage and water demand, serious fluidity loss, and reduced concrete strength.
Abstract
本发明公开了一种抗絮凝型聚羧酸减水剂及其制备方法，包括聚酯大单体、丙烯酸、丙烯酰铵、甲基丙烯酰吗啉、烷基丙烯酸酯磷酸酯、十二烷基苯磺酸钠、醇类化合物、过硫酸铵、氢氧化钠和水。本发明从减水剂的层面，可以降低机制砂中残留絮凝剂中的阳离子对聚羧酸减水剂的吸附作用，从而提高聚羧酸减水剂的利用效率，提升聚羧酸减水剂的抗絮凝性；从混凝土的层面，可以大幅减轻因机制砂石絮凝剂残留对混凝土造成的增粘增稠、掺量及需水量变大、流动性损失严重、混凝土强度降低等不良性能影响。
Description
本发明涉及一种抗絮凝型聚羧酸减水剂及其制备方法。
混凝土作为最主要的一类土木工程材料具有原料丰富、价格低廉、生产工艺简单、抗压强度高、耐久性好、强度等级范围宽等特点，被广泛用于各种结构工程。混凝土的巨大使用量导致天然沙石逐渐枯竭而不得不使用机制砂石。机制砂石生产过程中必须进行水洗，以控制杂质及泥含量。砂石企业为了使机制砂石中的含泥量、含粉量达标，同时控制污水排放量，在清洗过程中都会加入絮凝剂以提高去除泥粉的效果，清洗后的机制砂石会含有一定量的残留絮凝剂。
残留的絮凝剂对减水剂分子有着非常强力的吸附作用，大幅降低减水剂的使用效果，严重影响混凝土质量，如新拌混凝土的流动性保持时间短，继而变得粘稠难以施工。而具有抗絮凝的聚羧酸减水剂研究很少见。
发明内容
本发明主要解决的技术问题是提供一种抗絮凝型聚羧酸减水剂及其制备方法，从减水剂的层面，可以降低机制砂中残留絮凝剂中的阳离子对聚羧酸减水剂的吸附作用，从而提高聚羧酸减水剂的利用效率，提升聚羧酸减水剂的抗絮凝性；从混凝土的层面，可以大幅减轻因机制砂石絮凝剂残留对混凝土造成的增粘增稠、掺量及需水量变大、流动性损失严重、混凝土强度降低等不良性能影响。
为解决上述技术问题，本发明采用的一个技术方案是：提供一种抗絮凝型 聚羧酸减水剂，包括聚酯大单体、丙烯酸、丙烯酰铵、甲基丙烯酰吗啉、烷基丙烯酸酯磷酸酯、十二烷基苯磺酸钠、醇类化合物、过硫酸铵、氢氧化钠和水，各成分按重量份计为：聚酯大单体300-360份，丙烯酸20-35份，丙烯酰铵50-70份，甲基丙烯酰吗啉30-40份，烷基丙烯酸酯磷酸酯20-35份，十二烷基苯磺酸钠20-35份，链转移剂20-40份，引发剂10-20份，中和剂15-35份，水460-455份。
在本发明一个较佳实施例中，所述聚酯大单体为聚乙二醇二甲基丙烯酸酯。
在本发明一个较佳实施例中，所述链转移剂为醇类化合物，所述醇类化合物为疏基乙醇、异丙醇或十二烷基硫醇中的一种或几种复合的混合物。
在本发明一个较佳实施例中，所述引发剂为过硫酸铵。
在本发明一个较佳实施例中，所述中和剂为氢氧化钠溶液。
提供一种抗絮凝型聚羧酸减水剂的制备方法，包括如下步骤：
S1：将300-360份聚酯大单体、20-45份丙烯酸、50-70份丙烯酰铵、30-40份甲基丙烯酰吗啉、20-50份烷基丙烯酸酯磷酸酯、20-50份十二烷基苯磺酸钠和260-355份水投入反应釜中，加热搅拌，至其溶解；
S2：测定釜内反应温度，当釜内温度为60-65℃时，向反应釜内投入20-40份链转移剂；
S3：将10-20份过硫酸铵投入100份水中，待完全溶解形成过硫酸铵溶液，再加入反应釜中，在1.5-2h间完成滴加操作；
S4：过硫酸铵溶液滴加完成后，将反应釜内温度升至80±5℃，恒温保持3-4h，待其反应后降至室温，室温保持1h，加入15-35份氢氧化钠溶液，调节pH至7±0.5；
S5：通过加水的方式调节所得聚羧酸减水剂的质量分数至40％。
在本发明一个较佳实施例中，所述S1步骤中，具体为：先在反应釜中加入260-355份水，再依次加入300-360份聚酯大单体、30-40份甲基丙烯酰吗啉、20-50份烷基丙烯酸酯磷酸酯、20-50份十二烷基苯磺酸钠、20-45份丙烯酸、50-70份丙烯酰铵。
在本发明一个较佳实施例中，所述S3和S4步骤中，过硫酸铵溶液和氢氧化钠采用滴加方式逐滴加入。
本发明的有益效果是：本发明指出的一种抗絮凝型聚羧酸减水剂及其制备方法，具备如下优点：
1)在石膏基找平砂浆找平后的地面使用时，相同凝胶材料的适应性更优，可避免在环境温度和湿度变化时，材料的膨胀率和收缩率不一样，粘结处可能会出现剥离或材料层开裂的风险；
2)具有操作时间可调整，强度发展快，无需养护，工期短等特点；
3)针对石膏基找平砂浆找平后的地面使用，其适用环境为室内干区地面，材料的绝干粘结强度可达0.7-1.0MPa；
4)干缩率极低、甚至无收缩，可以直接使用该粘结砂浆进行找平及贴砖一次完成，简化施工过程。
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例一
先在反应釜中加入270份水，再依次加入360份聚乙二醇二甲基丙烯酸酯、30份甲基丙烯酰吗啉、20份烷基丙烯酸酯磷酸酯、20份十二烷基苯磺酸钠、45份丙烯酸、70份丙烯酰铵，加热搅拌，至其溶解；测定釜内反应温度，当釜内温度为60-65℃时，向反应釜内投入40份异丙醇；将20份过硫酸铵投入100份水中，待完全溶解形成过硫酸铵溶液，再逐滴加入加入反应釜中，在1.5h完成滴加操作；过硫酸铵溶液滴加完成后，将反应釜内温度升至85℃，恒温保持4h，待其反应后降至室温，室温保持1h，逐滴加入25份氢氧化钠溶液，调节pH至7；通过加水的方式调节所得聚羧酸减水剂的质量分数至40％。
实施例二
先在反应釜中加入325份水，再依次加入330份聚乙二醇二甲基丙烯酸酯、40份甲基丙烯酰吗啉、30份烷基丙烯酸酯磷酸酯、30份十二烷基苯磺酸钠、20份丙烯酸、60份丙烯酰铵，加热搅拌，至其溶解；测定釜内反应温度，当釜内温度为65℃时，向反应釜内投入30份十二烷基硫醇；将20份过硫酸铵投入100份水中，待完全溶解形成过硫酸铵溶液，再逐滴加入加入反应釜中，在1.5h完成滴加操作；过硫酸铵溶液滴加完成后，将反应釜内温度升至80℃，恒温保持3h，待其反应后降至室温，室温保持1h，逐滴加入15份氢氧化钠溶液，调节pH至7；通过加水的方式调节所得聚羧酸减水剂的质量分数至40％。
实施例三
先在反应釜中加入355份水，再依次加入300份聚乙二醇二甲基丙烯酸酯、40份甲基丙烯酰吗啉、40份烷基丙烯酸酯磷酸酯、40份十二烷基苯磺酸钠、20份丙烯酸、50份丙烯酰铵，加热搅拌，至其溶解；测定釜内反应温度，当釜内温度为65℃时，向反应釜内投入20份疏基乙醇；将20份过硫酸铵投入100份 水中，待完全溶解形成过硫酸铵溶液，再逐滴加入加入反应釜中，在1.5h完成滴加操作；
过硫酸铵溶液滴加完成后，将反应釜内温度升至75℃，恒温保持4h，待其反应后降至室温，室温保持1h，逐滴加入15份氢氧化钠溶液，调节pH至6.5；通过加水的方式调节所得聚羧酸减水剂的质量分数至40％。
实施例四
先在反应釜中加入260份水，再依次加入300份聚乙二醇二甲基丙烯酸酯、40份甲基丙烯酰吗啉、50份烷基丙烯酸酯磷酸酯、50份十二烷基苯磺酸钠、45份丙烯酸、70份丙烯酰铵，加热搅拌，至其溶解；测定釜内反应温度，当釜内温度为60℃时，向反应釜内投入40份异丙醇与十二烷基硫醇按摩尔比1:1的混合物；将20份过硫酸铵投入100份水中，待完全溶解形成过硫酸铵溶液，再逐滴加入加入反应釜中，在2h完成滴加操作；过硫酸铵溶液滴加完成后，将反应釜内温度升至75℃，恒温保持4h，待其反应后降至室温，室温保持1h，逐滴加入35份氢氧化钠溶液，调节pH至7.5；通过加水的方式调节所得聚羧酸减水剂的质量分数至40％。
其中，链转移剂使链增长自由基发生自由基转移，用以调节聚合物的相对分子质量，引发剂用以形成活性种引发连锁聚合反应，中和剂用以调节pH至7±0.5。
对比例(C30泵送混凝土)：
| 除减水剂外的混凝土配比 | kg/m 3 |
| 铜陵海螺P.O42.5水泥 | 280 |
| 望亭电厂II级粉煤灰 | 110 |
| 无絮凝剂机制砂 | 780 |
| 5-31.5mm碎石 | 1035 |
| 水 | 175 |
| 5‰浓度絮凝剂溶液 | 1.5‰拌合用水 |
其中，所选絮凝剂为当前制砂行业应用最广泛的阳离子聚丙烯酰胺，分子量为1200万；空白样中所用聚羧酸减水剂为40％浓度市售常规聚羧酸减水剂产品，空白样中添加掺量为0.5％胶凝材料用量。
将实例一至实例四所得抗絮凝型聚羧酸减水剂与空白样按照相同添加掺量进行对比性能测试，具体检测方法如下：初始混凝土坍落扩展度，60Min.混凝土坍落扩展度，28d混凝土标准养护强度；参考标准《GBT50082-2019普通混凝土长期性能和耐久性能试验方法》。
具体检测结果如下表所示：
综上所述，本发明指出的一种抗絮凝型聚羧酸减水剂及其制备方法，从减水剂的层面，可以降低机制砂中残留絮凝剂中的阳离子对聚羧酸减水剂的吸附作用，从而提高聚羧酸减水剂的利用效率，提升聚羧酸减水剂的抗絮凝性；从混凝土的层面，可以大幅减轻因机制砂石絮凝剂残留对混凝土造成的增粘增稠、 掺量及需水量变大、流动性损失严重、混凝土强度降低等不良性能影响。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其它相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (8)
- 一种抗絮凝型聚羧酸减水剂，其特征在于，包括聚酯大单体、丙烯酸、丙烯酰铵、甲基丙烯酰吗啉、烷基丙烯酸酯磷酸酯、十二烷基苯磺酸钠、醇类化合物、过硫酸铵、氢氧化钠和水，各成分按重量份计为：聚酯大单体300-360份，丙烯酸20-35份，丙烯酰铵50-70份，甲基丙烯酰吗啉30-40份，烷基丙烯酸酯磷酸酯20-35份，十二烷基苯磺酸钠20-35份，链转移剂20-40份，引发剂10-20份，中和剂15-35份，水460-455份。
- 根据权利要求1所述的抗絮凝型聚羧酸减水剂，其特征在于，所述聚酯大单体为聚乙二醇二甲基丙烯酸酯。
- 根据权利要求1所述的抗絮凝型聚羧酸减水剂，其特征在于，所述链转移剂为醇类化合物，所述醇类化合物为疏基乙醇、异丙醇或十二烷基硫醇中的一种或几种复合的混合物。
- 根据权利要求1所述的抗絮凝型聚羧酸减水剂，其特征在于，所述引发剂为过硫酸铵。
- 根据权利要求1所述的抗絮凝型聚羧酸减水剂，其特征在于，所述中和剂为氢氧化钠溶液。
- 一种应用权利要求1-5所述的抗絮凝型聚羧酸减水剂的制备方法，其特征在于，包括如下步骤：S1：将300-360份聚酯大单体、20-45份丙烯酸、50-70份丙烯酰铵、30-40份甲基丙烯酰吗啉、20-50份烷基丙烯酸酯磷酸酯、20-50份十二烷基苯磺酸钠和260-355份水投入反应釜中，加热搅拌，至其溶解；S2：测定釜内反应温度，当釜内温度为60-65℃时，向反应釜内投入20-40份链转移剂；S3：将10-20份过硫酸铵投入100份水中，待完全溶解形成过硫酸铵溶液，再加入反应釜中，在1.5-2h间完成滴加操作；S4：过硫酸铵溶液滴加完成后，将反应釜内温度升至80±5℃，恒温保持3-4h，待其反应后降至室温，室温保持1h，加入15-35份氢氧化钠溶液，调节pH至7±0.5；S5：通过加水的方式调节所得聚羧酸减水剂的质量分数至40％。
- 根据权利要求6所述的抗絮凝型聚羧酸减水剂，其特征在于，所述S1步骤中，具体为：先在反应釜中加入260-355份水，再依次加入300-360份聚酯大单体、30-40份甲基丙烯酰吗啉、20-50份烷基丙烯酸酯磷酸酯、20-50份十二烷基苯磺酸钠、20-45份丙烯酸、50-70份丙烯酰铵。
- 根据权利要求6所述的抗絮凝型聚羧酸减水剂，其特征在于，所述S3和S4步骤中，过硫酸铵溶液和氢氧化钠采用滴加方式逐滴加入。
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| CN110317304A (zh) * | 2019-07-22 | 2019-10-11 | 北京慕湖房地产开发股份有限公司 | 一种抗泥型聚羧酸减水剂及其制备方法 |
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| CN110317304A (zh) * | 2019-07-22 | 2019-10-11 | 北京慕湖房地产开发股份有限公司 | 一种抗泥型聚羧酸减水剂及其制备方法 |
| CN115010880A (zh) * | 2022-05-06 | 2022-09-06 | 苏州市兴邦化学建材有限公司 | 一种抗絮凝型聚羧酸减水剂及其制备方法 |
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