CN111560104B - Star polycarboxylic acid water reducing agent prepared by using tannic acid azo compound as initiator - Google Patents
Star polycarboxylic acid water reducing agent prepared by using tannic acid azo compound as initiator Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 33
- 239000003999 initiator Substances 0.000 title claims abstract description 26
- -1 tannic acid azo compound Chemical class 0.000 title claims abstract description 24
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000001263 FEMA 3042 Substances 0.000 title claims abstract description 21
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 title claims abstract description 21
- 229940033123 tannic acid Drugs 0.000 title claims abstract description 21
- 235000015523 tannic acid Nutrition 0.000 title claims abstract description 21
- 229920002258 tannic acid Polymers 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 48
- 239000002253 acid Substances 0.000 title 1
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 43
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 10
- 239000008030 superplasticizer Substances 0.000 claims abstract description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims abstract description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229960003151 mercaptamine Drugs 0.000 claims abstract description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 11
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims 2
- 229940035429 isobutyl alcohol Drugs 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract description 3
- 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 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 239000004567 concrete Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 239000012895 dilution Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010998 test method Methods 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
- 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)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (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
本发明公开了一种用单宁酸偶氮化合物作引发剂制备的星形聚羧酸减水剂，所述星形聚羧酸减水剂是以不饱和聚醚大单体、丙烯酸为原料，在引发剂和链转移剂存在下通过自由基共聚反应聚合而成的共聚物；所述的不饱和聚醚大单体选自APEG、HPEG或TPEG中的任意一种或两种；所述的链转移剂选自巯基丙酸、巯基乙酸、巯基乙醇、次磷酸钠、巯基乙胺、甲基丙烯磺酸钠或丙烯磺酸钠中的至少一种。本发明设计合成的星形聚羧酸减水剂分子支链多、粘度低、流体力学体积小、表面官能团丰富，单宁酸分子上有大量的羟基，从而使水泥颗粒得到充分分散和润湿性；同时星形聚羧酸减水剂臂上含有的长疏水链及大量疏水芳香环核为水泥颗粒提供较大空间位阻，从而使水泥颗粒均匀分散。The invention discloses a star-shaped polycarboxylate water-reducer prepared by using tannic acid azo compound as an initiator. The star-shaped polycarboxylate water-reducer is made of unsaturated polyether macromonomer and acrylic acid as raw materials , a copolymer formed by radical copolymerization in the presence of an initiator and a chain transfer agent; the unsaturated polyether macromonomer is selected from any one or both of APEG, HPEG or TPEG; the The chain transfer agent is selected from at least one of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite, mercaptoethylamine, sodium methacrylene sulfonate or sodium propylene sulfonate. The star-shaped polycarboxylate superplasticizer designed and synthesized by the present invention has many molecular branches, low viscosity, small hydrodynamic volume, rich surface functional groups, and a large number of hydroxyl groups on the tannic acid molecules, so that the cement particles can be fully dispersed and wetted. At the same time, the long hydrophobic chain and a large number of hydrophobic aromatic ring nuclei contained in the arms of the star-shaped polycarboxylate superplasticizer provide a large steric hindrance for the cement particles, so that the cement particles are evenly dispersed.
Description
技术领域technical field
本发明属于建筑材料外加剂技术领域，具体涉及一种利用单宁酸偶氮化合物作引发剂制备星形聚羧酸减水剂的方法。The invention belongs to the technical field of building material admixtures, and in particular relates to a method for preparing star-shaped polycarboxylate water reducers by using tannic acid azo compounds as initiators.
背景技术Background technique
近年来，建筑施工技术发展迅速，对作为主要建筑材料的混凝土的性能提出了更高的标准。高性能混凝土不仅要求新拌混凝土具有优异的流动性，而且还需其流动性经时保持能力较好。因此，减水剂成为配置高性能、高流动性和高流动性经时保持能力及绿色混凝土不可或缺的重要组分之一，减水剂可以使混凝土在使用过程中减少其用水量，并提高其使用耐久性，提高保坍性，改变混凝土性质，提高强度。聚羧酸系高性能减水剂具有掺量低、减水率高、保塌性能好、分子结构可调性强等优点，成为国内外混凝土减水剂研究开发重点和市场的热点，具有广阔的应用前景，已广泛应用于大坝、桥梁、隧道、高铁等重点工程。聚羧酸系高性能减水剂只有几十年的发展历史，无论分子结构、产品种类都不足够丰富完善，不能完全满足当前混凝土的理论和应用的需求。目前研究者主要集中于通过分子结构设计，制备梳型聚羧酸减水剂解决混凝土分散性和分散保持性等问题，但往往存在分子结构单、制备工艺复杂、生产成本高等问题。因此研究开发新型分子结构的聚羧酸减水剂势在必行，并对混凝土外加剂和混凝土行业的发展都具有重要的意义。In recent years, the rapid development of building construction technology has put forward higher standards for the performance of concrete as the main building material. High-performance concrete not only requires fresh concrete to have excellent fluidity, but also requires a good ability to maintain its fluidity over time. Therefore, the water reducing agent has become one of the indispensable important components for the configuration of high performance, high fluidity, high fluidity and long-term retention ability and green concrete. The water reducing agent can reduce the water consumption of concrete during use, and Improve its durability, improve slump retention, change the properties of concrete, and increase strength. Polycarboxylate-based high-performance water-reducing agent has the advantages of low dosage, high water-reducing rate, good slump-retaining performance, and strong molecular structure adjustability. It has been widely used in key projects such as dams, bridges, tunnels, and high-speed rail. The polycarboxylate high-performance water reducer has only a few decades of development history, and its molecular structure and product types are not rich enough to fully meet the current theoretical and application needs of concrete. At present, researchers mainly focus on preparing comb-type polycarboxylate superplasticizers to solve the problems of concrete dispersion and dispersion retention through molecular structure design, but there are often problems such as single molecular structure, complicated preparation process, and high production cost. Therefore, it is imperative to research and develop polycarboxylate superplasticizers with new molecular structures, and it is of great significance to the development of concrete admixtures and the concrete industry.
发明内容Contents of the invention
本发明要解决的第一个技术问题是提供一种支链多、粘度低、流体力学体积小、表面官能团丰富、适应性好的新型星形聚羧酸减水剂。The first technical problem to be solved by the present invention is to provide a new type of star-shaped polycarboxylate superplasticizer with many branches, low viscosity, small hydrodynamic volume, rich surface functional groups and good adaptability.
本发明要解决的第二个技术问题是提供一种制备工艺简单、易操作、成本低、利用单宁酸偶氮化合物作引发剂，制备过程无污染的星形聚羧酸减水剂的制备方法。The second technical problem to be solved by the present invention is to provide a star-shaped polycarboxylate water reducer with simple preparation process, easy operation, low cost, using tannic acid azo compound as initiator, and no pollution in the preparation process. method.
本发明的技术方案：一种用单宁酸偶氮化合物作引发剂制备的星形聚羧酸减水剂，其化学结构通式如下式(I)所示：Technical scheme of the present invention: a kind of star-shaped polycarboxylate superplasticizer prepared with tannic acid azo compound as initiator, its general chemical structure is as shown in formula (I):
其中R1为-H或-CH3；R2为-CH2-或-CH2CH2-；y、x、n均为非0整数。Wherein R 1 is -H or -CH 3 ; R 2 is -CH 2 - or -CH 2 CH 2 -; y, x, n are non-zero integers.
本发明优选的星形聚羧酸减水剂，其结构如上述式(I)所示，所述的不饱和聚醚大分子单体的分子量为1000～3000；最优选2400。The preferred star-shaped polycarboxylate water-reducer of the present invention has a structure as shown in the above formula (I), and the molecular weight of the unsaturated polyether macromonomer is 1000-3000; most preferably 2400.
本发明优选的星形聚羧酸减水剂，其结构如上述式(I)所示，所述的R1为 -CH3且R2为-CH2CH2-。The structure of the preferred star polycarboxylate water reducer of the present invention is shown in the above formula (I), wherein R 1 is -CH 3 and R 2 is -CH 2 CH 2 -.
本发明优选的所述星形聚羧酸减水剂是以不饱和聚醚大单体、丙烯酸为原料，在引发剂和链转移剂存在下通过自由基共聚反应聚合而成的共聚物；所述的不饱和聚醚大单体选自烯丙基聚氧乙烯醚(APEG)、异丁烯醇聚氧乙烯醚(HPEG) 或异戊烯聚氧乙烯醚(TPEG)中的任意一种或两种；所述的链转移剂选自巯基丙酸、巯基乙酸、巯基乙醇、次磷酸钠、巯基乙胺、甲基丙烯磺酸钠或丙烯磺酸钠中的至少一种。所述的引发剂单宁酸偶氮化合物的结构如下式(II)所示。The preferred star-shaped polycarboxylate water-reducer of the present invention is a copolymer made of unsaturated polyether macromonomer and acrylic acid as raw materials and polymerized by free radical copolymerization in the presence of an initiator and a chain transfer agent; The unsaturated polyether macromonomer is selected from any one or both of allyl polyoxyethylene ether (APEG), isobutylene alcohol polyoxyethylene ether (HPEG) or isopentyl polyoxyethylene ether (TPEG) The chain transfer agent is selected from at least one of mercaptopropionic acid, thioglycolic acid, mercaptoethanol, sodium hypophosphite, mercaptoethylamine, sodium methacrylene sulfonate or sodium propylene sulfonate. The structure of the initiator tannic acid azo compound is shown in the following formula (II).
本发明优选的制备所述星形聚羧酸减水剂的方法，包括以下步骤：The preferred method of preparing the star polycarboxylate water reducer of the present invention comprises the following steps:
1)取所述的不饱和聚醚大单体、丙烯酸、引发剂和链转移剂与水在50-80℃共聚反应3-5小时，得到共聚物溶液；其中，各原料占总反应体系的摩尔百分比分别为：不饱和聚醚大单体10-35％，丙烯酸60-80％，引发剂0.5-5％，链转移剂 0.1-3％，余量为水；1) Copolymerize the unsaturated polyether macromonomer, acrylic acid, initiator and chain transfer agent with water at 50-80°C for 3-5 hours to obtain a copolymer solution; wherein, each raw material accounts for 1% of the total reaction system The molar percentages are: 10-35% of unsaturated polyether macromonomer, 60-80% of acrylic acid, 0.5-5% of initiator, 0.1-3% of chain transfer agent, and the balance is water;
2)将1)所得共聚物溶液降温至40℃以下，然后用碱性物质调整pH值在 5.0-7.0的范围内，得到红棕色溶液即为所述星形聚羧酸减水剂。2) Cool the copolymer solution obtained in 1) to below 40°C, and then use alkaline substances to adjust the pH value in the range of 5.0-7.0 to obtain a reddish-brown solution, which is the star polycarboxylate superplasticizer.
本发明优选的方案中，所述的烯丙基聚氧乙烯醚(APEG)、异丁烯醇聚氧乙烯醚(HPEG)或异戊烯聚氧乙烯醚(TPEG)的分子量在1000-3000。In a preferred solution of the present invention, the molecular weight of the allyl polyoxyethylene ether (APEG), isobutylene alcohol polyoxyethylene ether (HPEG) or isopentyl polyoxyethylene ether (TPEG) is 1000-3000.
本发明进一步优选的方案中，1)所述的共聚反应温度为63～65℃。In a further preferred solution of the present invention, the temperature of the copolymerization reaction described in 1) is 63-65°C.
本发明所述与现有聚羧酸减水剂相比，具有以下优点：结构新颖，设计合理，设计合成的星形聚羧酸减水剂分子支链多、粘度低、流体力学体积小、表面官能团丰富，单宁酸分子上有大量的羟基，这些丰富的极性基团与水泥颗粒的极性表面具有较强的亲水作用，可使水泥颗粒表面生成水化膜，从而使水泥颗粒得到充分分散和润湿性；同时，星形聚羧酸减水剂臂上含有的长疏水链及大量疏水芳香环核可以为水泥颗粒提供较大的空间位阻，从而使水泥颗粒均匀分散。Compared with the existing polycarboxylate superplasticizer, the present invention has the following advantages: novel structure, reasonable design, and the designed and synthesized star-shaped polycarboxylate superplasticizer has many molecular branches, low viscosity, small hydrodynamic volume, The surface functional groups are rich, and there are a large number of hydroxyl groups on the tannic acid molecule. These rich polar groups have a strong hydrophilic interaction with the polar surface of the cement particles, which can make the surface of the cement particles form a hydration film, so that the cement particles To obtain sufficient dispersion and wettability; at the same time, the long hydrophobic chains and a large number of hydrophobic aromatic ring cores contained in the arms of the star-shaped polycarboxylate superplasticizer can provide larger steric hindrance for the cement particles, so that the cement particles can be evenly dispersed.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步详述。The present invention will be described in further detail below in conjunction with specific examples.
实施例1Example 1
一种星形聚羧酸减水剂的制备方法，包括以下步骤：A preparation method of star-shaped polycarboxylate water reducer, comprising the following steps:
在装有温度计、电动搅拌器、恒温电热套、蠕动泵的1000mL的四口圆底烧瓶中加入水250g、聚醚大单体APEG 300g，所用APEG的分子量为2400，搅拌升温至58℃，溶解均匀后直接加入12g单宁酸偶氮化合物引发剂和20g水的混合溶液搅拌10分钟使其充分溶解。在3小时内分别滴加由丙烯酸45g、水76g 组成的混合水溶液和巯基丙酸1.8g、水90g组成的混合溶液，温度保持在63-65℃之间；滴加完成后继续反应2小时，然后降温至30-35℃，加入30％氢氧化钠溶液及稀释水，得到pH为5-7浓度为40％左右的星形聚羧酸减水剂，其结构式如下式所示：Add 250g of water and 300g of polyether macromonomer APEG to a 1000mL four-neck round bottom flask equipped with a thermometer, an electric stirrer, a constant temperature electric heating mantle, and a peristaltic pump. After uniformity, directly add the mixed solution of 12g tannic acid azo compound initiator and 20g water and stir for 10 minutes to fully dissolve it. Within 3 hours, add dropwise the mixed aqueous solution composed of 45g of acrylic acid and 76g of water and the mixed solution of 1.8g of mercaptopropionic acid and 90g of water, and keep the temperature between 63-65°C; Then cool down to 30-35°C, add 30% sodium hydroxide solution and dilution water to obtain a star-shaped polycarboxylate water reducer with a pH of 5-7 and a concentration of about 40%. Its structural formula is as follows:
实施例2Example 2
一种星形聚羧酸减水剂的制备方法，包括以下步骤：A preparation method of star-shaped polycarboxylate water reducer, comprising the following steps:
在装有温度计、电动搅拌器、恒温电热套、蠕动泵的1000mL的四口圆底烧瓶中加入水250g、聚醚大单体HPEG 300g，所用HPEG的分子量为2400，搅拌升温至58℃，溶解均匀后直接加入12g单宁酸偶氮化合物引发剂和20g水的混合溶液搅拌10分钟使其充分溶解。在3小时内分别滴加由丙烯酸45g、水76g 组成的混合水溶液和巯基丙酸1.8g、水90g组成的混合溶液，温度保持在63-65℃之间；滴加完成后继续反应2小时，然后降温至30-35℃，加入30％氢氧化钠溶液及稀释水，得到pH为5-7浓度为40％左右的星形聚羧酸减水剂，其结构式如下式所示：Add 250g of water and 300g of polyether macromonomer HPEG into a 1000mL four-necked round-bottom flask equipped with a thermometer, an electric stirrer, a constant temperature electric heating mantle, and a peristaltic pump. After uniformity, directly add the mixed solution of 12g tannic acid azo compound initiator and 20g water and stir for 10 minutes to fully dissolve it. Within 3 hours, add dropwise the mixed aqueous solution composed of 45g of acrylic acid and 76g of water and the mixed solution of 1.8g of mercaptopropionic acid and 90g of water, and keep the temperature between 63-65°C; Then cool down to 30-35°C, add 30% sodium hydroxide solution and dilution water to obtain a star-shaped polycarboxylate water reducer with a pH of 5-7 and a concentration of about 40%. Its structural formula is as follows:
实施例3Example 3
一种星形聚羧酸减水剂的制备方法，包括以下步骤：A preparation method of star-shaped polycarboxylate water reducer, comprising the following steps:
在装有温度计、电动搅拌器、恒温电热套、蠕动泵的1000mL的四口圆底烧瓶中加入水250g、聚醚大单体TPEG 300g，所用TPEG的分子量为2400，搅拌升温至58℃，溶解均匀后直接加入12g单宁酸偶氮化合物引发剂和20g水的混合溶液搅拌10分钟使其充分溶解。在3小时内分别滴加由丙烯酸45g、水76g 组成的混合水溶液和巯基丙酸1.8g、水90g组成的混合溶液，温度保持在63-65℃之间；滴加完成后继续反应2小时，然后降温至30-35℃，加入30％氢氧化钠溶液及稀释水，得到pH为5-7浓度为40％左右的星形聚羧酸减水剂，其结构式如下式所示：Add 250g of water and 300g of polyether macromonomer TPEG to a 1000mL four-necked round-bottomed flask equipped with a thermometer, an electric stirrer, a constant temperature electric heating mantle, and a peristaltic pump. After uniformity, directly add the mixed solution of 12g tannic acid azo compound initiator and 20g water and stir for 10 minutes to fully dissolve it. Within 3 hours, add dropwise the mixed aqueous solution composed of 45g of acrylic acid and 76g of water and the mixed solution of 1.8g of mercaptopropionic acid and 90g of water, and keep the temperature between 63-65°C; Then cool down to 30-35°C, add 30% sodium hydroxide solution and dilution water to obtain a star-shaped polycarboxylate water reducer with a pH of 5-7 and a concentration of about 40%. Its structural formula is as follows:
实施例4Example 4
一种星形聚羧酸减水剂的制备方法，包括以下步骤：A preparation method of star-shaped polycarboxylate water reducer, comprising the following steps:
在装有温度计、电动搅拌器、恒温电热套、蠕动泵的1000mL的四口圆底烧瓶中加入水250g、聚醚大单体TPEG 300g，所用TPEG的分子量为2400，搅拌升温至58℃，溶解均匀后直接加入12g单宁酸偶氮化合物引发剂和20g水的混合溶液搅拌10分钟使其充分溶解。在3小时内分别滴加由丙烯酸45g、水76g 组成的混合水溶液和次磷酸钠2.8g、水90g组成的混合溶液，温度保持在63-65℃之间；滴加完成后继续反应2小时，然后降温至30-35℃，加入30％氢氧化钠溶液及稀释水，得到pH为5-7浓度为40％左右的星形聚羧酸减水剂，其结构式如下式所示：Add 250g of water and 300g of polyether macromonomer TPEG to a 1000mL four-necked round-bottomed flask equipped with a thermometer, an electric stirrer, a constant temperature electric heating mantle, and a peristaltic pump. After uniformity, directly add the mixed solution of 12g tannic acid azo compound initiator and 20g water and stir for 10 minutes to fully dissolve it. Within 3 hours, add dropwise the mixed aqueous solution consisting of 45g of acrylic acid, 76g of water, 2.8g of sodium hypophosphite, and 90g of water, and keep the temperature between 63-65°C; continue the reaction for 2 hours after the addition is completed, Then cool down to 30-35°C, add 30% sodium hydroxide solution and dilution water to obtain a star-shaped polycarboxylate water reducer with a pH of 5-7 and a concentration of about 40%. Its structural formula is as follows:
对比例comparative example
常规聚羧酸减水剂的制备方法，包括以下步骤：The preparation method of conventional polycarboxylate water reducer comprises the following steps:
在装有温度计、电动搅拌器、电热套、蠕动泵的1000mL的四口圆底烧瓶中加入水250g、聚醚大单体HPEG 300g，所用HPEG的分子量为2400，搅拌溶解均匀后直接加入3.9g双氧水溶液搅拌10分钟使其充分溶解。在3小时内和3.5 小时内分别滴加由丙烯酸45g、水60g组成的混合水溶液和抗坏血酸1.6g、巯基丙酸2.0g、水60g组成的混合溶液，常温滴加；滴加完成后继续反应1小时，加入30％氢氧化钠溶液及稀释水，得到pH为6-7浓度为40％左右的常规聚羧酸减水剂，其结构式如下式所示：Add 250g of water and 300g of polyether macromonomer HPEG to a 1000mL four-necked round-bottomed flask equipped with a thermometer, an electric stirrer, an electric heating mantle, and a peristaltic pump. The hydrogen peroxide solution was stirred for 10 minutes to fully dissolve it. Within 3 hours and within 3.5 hours, add dropwise the mixed aqueous solution composed of 45g of acrylic acid, 60g of water and 1.6g of ascorbic acid, 2.0g of mercaptopropionic acid, and 60g of water, dropwise at room temperature; after the dropwise addition, continue the reaction 1 Hours, add 30% sodium hydroxide solution and diluting water to obtain a conventional polycarboxylate water reducer with a pH of 6-7 and a concentration of about 40%. Its structural formula is as follows:
应用实施例Application example
本发明星形聚羧酸减水剂按照GB/T8000-2000《混凝土外加剂均质性试验方法》对净浆流动进行测定，水泥为基准水泥。试验结果如表1。According to GB/T8000-2000 "Concrete Admixture Homogeneity Test Method", the star-shaped polycarboxylate water reducer of the present invention is used to measure the flow of the clean slurry, and the cement is the reference cement. The test results are shown in Table 1.
表1水泥净浆流动度测试结果Table 1 Cement paste fluidity test results
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，任何未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Any simple modification, Equivalent changes and modifications still fall within the scope of the technical solution of the present invention.
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| CN106750076A (en) * | 2017-01-24 | 2017-05-31 | 福州大学 | A kind of preparation method and applications of cement water reducing agent |
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