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Preparing method for polycarboxylate-type anti-mud water reducer with modified side chain terminal group

A technology of polycarboxylate and terminal group modification, which is applied in the field of polycarboxylate water reducer for cement concrete, can solve the problems of increasing uncertainty, complicated process, and affecting copolymerization reaction, so as to reduce the difficulty of reaction and improve The effect of reaction efficiency and simple operation

Active Publication Date: 2016-02-17
JIANGSU CHINA RAILWAY ARIT NEW MATEIRALS CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, the main way to deal with concrete mud is to modify the traditional polycarboxylate superplasticizer. The main methods are divided into three types: the first is to esterify first, that is, to modify the polyether unsaturated macromonomer by esterification first. properties, and then copolymerized with other small molecule monomers, this method is prone to side reactions, and the obtained macromolecular polyether double bond retention value is not high, which will affect the subsequent copolymerization reaction, resulting in a decline in product quality and instability; the second The first method is the post-esterification method. Although the disadvantages of the pre-esterification method can be avoided, the polycarboxylate water reducer is first synthesized by free radical polymerization, and then esterified and grafted. Although this method does not affect the subsequent copolymerization reaction, However, the process is very complicated, and the efficiency of re-esterification of macromolecules of water reducing agent is difficult to improve, and side reactions are prone to occur
The third is to add a third monomer, such as styrene, quaternary ammonium salt and other unsaturated small monomers directly into the main chain, which turns the simple direct free radical polymerization of two monomers into three One kind of monomer, or even four or five kinds, increases a lot of uncertainty, seriously affects the water reducing ability of traditional water reducing agents, and the anti-mud effect is not very obvious

Method used

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  • Preparing method for polycarboxylate-type anti-mud water reducer with modified side chain terminal group
  • Preparing method for polycarboxylate-type anti-mud water reducer with modified side chain terminal group

Examples

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Embodiment 1

[0022] 1) Preparation of azido-terminated polycarboxylate water reducer: dissolve 1 mol of dry solid polycarboxylate water reducer (the side chain polyether is TPEG with a molecular weight of 2400) in tetrahydrofuran (THF), add 10.1 mol thionyl chloride, add 20mol sodium azide after reacting for 30min, react under reduced pressure after reacting for 2h to obtain azide-terminated polycarboxylate water reducer;

[0023] 2) Preparation of phenyl-terminated / pyridyl-based polycarboxylic acid-based mud-resistance superplasticizer: 1 mol of azido-terminated polycarboxylic acid-based water-reducer obtained in step 1) was dissolved in 10 mol of alkyne phenyl / pyridylbenzenesulfonic acid. In tetrahydrofuran (THF), react under the catalysis of 0.001molCuBr / pentamethyldiethylenetriamine (PMDETA) for 10min and then desalt through neutral alumina to obtain the phenyl-terminated / pyridyl polycarboxylate anti-sludge Water reducing agent.

Embodiment 2

[0025] 1) Preparation of azido-terminated polycarboxylate water-reducer: dissolve 1 mol of dry solid polycarboxylate water-reducer (its side chain polyether is HPEG with a molecular weight of 2400) in dimethyl sulfoxide (DMSO) In, add 10.2 thionyl chloride, add 21mol sodium azide after reacting for 35 minutes, react under reduced pressure after reacting for 2.5 hours to obtain azido-terminated polycarboxylate water reducer;

[0026] 2) Preparation of phenyl-terminated / pyridine-based polycarboxylic acid-based anti-sludge water-reducer: 1 mol of azido-terminated polycarboxylic acid-based water-reducer obtained in step 1) was dissolved in dimethyl by adding 10 mol of phenol-4-ethynyl In base sulfoxide (DMSO), react for 15 minutes under the catalysis of 0.002molCuCl / HMTETA, and then desalinate through neutral alumina to obtain phenyl-terminated / pyridyl-based polycarboxylic acid-based mud-resistance and water-reducer.

Embodiment 3

[0028] 1) Preparation of azido-terminated polycarboxylate water reducer: dissolve 1 mol of dry solid polycarboxylate water reducer (the side chain polyether is TPEG with a molecular weight of 1200) in N,N-dimethyl formaldehyde Add 10.3 mol of thionyl chloride to amide (DMF), add 22 mol of sodium azide after reacting for 40 minutes, react for 3 hours and then distill under reduced pressure to obtain azide-terminated polycarboxylate water reducer;

[0029] 2) Preparation of phenyl-terminated / pyridine-based polycarboxylic acid-based anti-sludge water-reducer: add 20 mol of p-methylphenylacetylene N,N-Di In methylformamide (DMF), react under the catalysis of 0.03molCuBr / tetra[(2-pyridyl)methyl]ethylenediamine (TPEN) for 50min and then desalt through neutral alumina to obtain terminal phenyl / Pyridyl polycarboxylate anti-mud superplasticizer.

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Abstract

The invention discloses a preparing method for polycarboxylate-type anti-mud water reducer with a modified side chain terminal group. The preparing method includes the steps that azido-terminated polycarboxylate-type water reducer is prepared first, and then the azido-terminated polycarboxylate-type water reducer and an alkyne-terminated benzene-pyridine derivative are subjected to a click chemical reaction to prepare the polycarboxylate-type anti-mud water reducer with the side chain terminal group being the alkyne-terminated benzene-pyridine derivative. As the terminal hydroxyl group of the polycarboxylate-type water reducer is modified into a five-membered ring and a benzene / pyridine ring, the physical size of the side chain terminal of the polycarboxylate-type water reducer is greatly increased, and the polycarboxylate-type water reducer is not prone to be inserted into a layered structure of clay to achieve the anti-mud effect without affecting the inherent functions. The technical problems that as a side chain of existing polycarboxylate-type water reducer is prone to be inserted into the layered structure of the clay, the polycarboxylate-type water reducer is lost fast, and then the work performance of concrete is lowered are solved.

Description

technical field [0001] The present invention relates to the technical field of a polycarboxylate water-reducer for cement concrete, in particular to a side-chain end-group modified polycarboxylate mud-resistance water-reducer modified by a click chemical method method of preparation. Background technique [0002] Polycarboxylate superplasticizer is widely used because of its low dosage, high water reducing rate, low concrete shrinkage, and environmental protection. However, in the actual production and application of concrete, it is found that the mud in the aggregate will absorb the polycarboxylate superplasticizer. The traditional polycarboxylate superplasticizer is very sensitive to the mud content in the aggregate. As the mud content increases, the polycarboxylate superplasticizer The dispersibility and slump retention performance of the carboxylic acid superplasticizer are significantly reduced, resulting in a significant decrease in the workability of fresh concrete. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G65/333C04B24/32C04B103/30
Inventor 钱珊珊张岭尤迁丁蓓王毅姜海东郑春扬
Owner JIANGSU CHINA RAILWAY ARIT NEW MATEIRALS CO LTD
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