WO2022095622A1 - Nouveau réducteur d'eau à base d'acide polycarboxylique anticorrosion et procédé de préparation associé - Google Patents

Nouveau réducteur d'eau à base d'acide polycarboxylique anticorrosion et procédé de préparation associé Download PDF

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Publication number
WO2022095622A1
WO2022095622A1 PCT/CN2021/120155 CN2021120155W WO2022095622A1 WO 2022095622 A1 WO2022095622 A1 WO 2022095622A1 CN 2021120155 W CN2021120155 W CN 2021120155W WO 2022095622 A1 WO2022095622 A1 WO 2022095622A1
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WO
WIPO (PCT)
Prior art keywords
corrosion
polycarboxylate water
reducing agent
novel anti
unsaturated carboxylic
Prior art date
Application number
PCT/CN2021/120155
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English (en)
Chinese (zh)
Inventor
蒋卓君
林添兴
朱巧勇
姚晓阳
罗小峰
邓磊
Original Assignee
科之杰新材料集团有限公司
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Publication of WO2022095622A1 publication Critical patent/WO2022095622A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

Definitions

  • the invention relates to the technical field of building materials, in particular to a novel anti-corrosion type polycarboxylate water reducer and a preparation method thereof.
  • the new type of polycarboxylate superplasticizer prepared from vinyl ether macromonomers, as a relatively high-end polycarboxylate superplasticizer, has been used in some key products due to its excellent water-reducing properties and low sensitivity. It has been applied in engineering, and these key projects have strict requirements on its high temperature resistance and anticorrosion stability.
  • the method of compounding and adding preservatives is the most widely used method at present, but the compounded preservatives generally have a small molecular weight. On the one hand, there may be the problem of uneven dispersion of the preservatives in the polycarboxylate At present, the commonly used compound preservatives still have the problem of decomposition and failure in the environment higher than 50 °C, which limits their application to a certain extent.
  • CN110642996A published on January 3, 2020, discloses a self-new anti-corrosion type polycarboxylate water reducer and a preparation method thereof, but the monomer with anti-corrosion properties used in it is polymethacrylate acyloxyethyl Trimethylammonium chloride, poly[2-(acryloyloxy)ethyl]trimethylammonium bromide, polybenzylethyltrimethylammonium chloride, polyallyltrimethylammonium chloride, poly Any one or more of (3-acrylamidopropyl)trimethylammonium bromide.
  • these substances are already polymers and have no polymerization activity, so they cannot be incorporated into the molecular structure of the superplasticizer, so in essence, this method is also a method for compounding preservatives.
  • CN110128048A published on August 16, 2019, discloses a summer antiseptic slump-preserving polycarboxylate water reducer and a preparation method thereof, which is also a method of compounding a fungicide (polyhexamethyleneguanidine phosphate) achieve anti-corrosion properties.
  • CN110015857A published on July 16, 2019, discloses a preparation method and application of a straw-starch-based mixed-modified composite polycarboxylate water-reducing agent, using dimethyl fumarate as a preservative to directly It is compounded into the patented product, but the water solubility of dimethyl fumarate is not very good.
  • polycarboxylate water reducer a large amount of water is generally required to be compounded, and the water content often exceeds 90%. , so the effect of directly compounding and adding dimethyl fumarate is not ideal.
  • CN109796561A published on May 24, 2019, discloses an aromatic ring polycarboxylate water-reducing agent mother liquor and its preparation method and application, using aryl conjugated unsaturated carboxylic acid as an anti-corrosion monomer to prepare a Polycarboxylate water reducing agent with anti-corrosion effect, but there are problems of large steric hindrance and unsatisfactory polymerization effect during the polymerization of aryl conjugated unsaturated carboxylic acid, which will eventually affect the performance of the product.
  • CN109400819A published on March 1, 2019, discloses a viscosity-reducing antibacterial amphoteric polycarboxylate superplasticizer and a preparation method thereof, using guanidine hydrochloride and an alkyl compound with amine groups at both ends to prepare antibacterial The monomer is then used in the synthesis of the polycarboxylate water reducing agent. The synthesis process is complicated and the energy consumption is high.
  • CN108373526A discloses an antifouling and antibacterial polycarboxylate water reducer and a preparation method thereof.
  • (meth)acrylic acid sulfobetaine and methacrylic acid By adding (meth)acrylic acid sulfobetaine and methacrylic acid during polymerization Acyloxyethyltrimethylammonium chloride can achieve antibacterial effect, but the cost of these two monomers is relatively high.
  • CN107698721A published on February 16, 2018, discloses a branched-chain antibacterial polycarboxylate water reducer, its preparation method and application, but the preparation process is too complicated and the production efficiency is low.
  • CN107265907A published on October 20, 2017, discloses an amphoteric antibacterial polycarboxylic acid-based superplasticizer and a preparation method thereof.
  • CN105621927A discloses a preparation method of an antibacterial preservative for polycarboxylate water-reducing agent, and introduces antibacterial and antibacterial preservatives into polyoxyethylene ether with a similar structure to polycarboxylate water-reducing agent.
  • the functional betaine and dimethyl fumarate monomers undergo free radical copolymerization, which makes the molecular structure of the preservative and the polycarboxylic acid water reducer similar and compatible.
  • the product of this patent only has anti-corrosion effect and does not have the effect of water reduction, and the direct polymerization of dimethyl fumarate monomer and unsaturated monomer in the system has poor water solubility and phase separation during the polymerization process. problem, making the polymerization efficiency low.
  • the present invention provides a new type of anti-corrosion polycarboxylate water reducing agent, which is composed of a small anti-corrosion function monomer and an unsaturated large monomer.
  • the polymer, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride are polymerized under the initiator and molecular weight regulator to generate a new type of anti-corrosion polycarboxylate water reducer with anti-corrosion function small monomers linked on the main chain of the molecule;
  • the anti-corrosion functional small monomer is fumarate and/or maleate
  • the unsaturated macromonomer is a vinyl ether macromonomer
  • the vinyl ether macromonomer is at least one of ethylene glycol monovinyl polyglycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether .
  • the mass ratio range of unsaturated macromonomer, anticorrosion functional small monomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is 180:(1 ⁇ 15):(5 ⁇ 30).
  • the dosage of the initiator is 0.5-3.0% of the total mass of the reactant; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of the reactant.
  • the initiator aqueous solution, the molecular weight regulator aqueous solution, the unsaturated carboxylic acid and/or the unsaturated carboxylic acid anhydride aqueous solution are added dropwise within 0.5 to 2 h, and the reaction temperature is 10 ⁇ 40°C, keep the temperature for 0 ⁇ 2h after the dropwise addition is completed, and add alkali to adjust the pH value of the product to 5 ⁇ 7.
  • the initiator includes a water-soluble redox initiation system reagent; specifically, hydrogen peroxide-ascorbic acid-ferrous sulfate, hydrogen peroxide-ascorbic acid-ferrous sulfate can be used;
  • the molecular weight regulator includes at least one of thioglycolic acid, mercaptoethanol, mercaptopropionic acid, sulfonated mercaptopropionic acid, and sodium hypophosphite.
  • the fumaric acid ester includes monomethyl fumarate and monoethyl fumarate.
  • the maleic acid ester includes diethyl maleate, dimethyl maleate and dipropyl maleate.
  • the molecular weight of the unsaturated macromonomer is 600-6000.
  • the unsaturated carboxylic acid and/or the unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid and maleic anhydride.
  • the present invention also provides a preparation method of the novel anti-corrosion type polycarboxylate water reducing agent as described above, comprising the following steps:
  • alkali is added to adjust the pH value of the product to 5-7 to obtain a new type of anti-corrosion polycarboxylate water reducing agent.
  • the novel anti-corrosion polycarboxylate water reducer provided by the present invention introduces fumarate into the molecular structure of the product through the copolymerization of unsaturated macromonomer, anti-corrosion functional small monomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride , at least one monomer unit in maleate, to obtain a new type of anti-corrosion polycarboxylate water reducer with its own anti-corrosion properties, no need to compound small molecule preservatives, no preservatives and polycarboxylate water reducers
  • the problem of uneven distribution caused by poor compatibility, and the final product formed is a stable polymer structure, which can withstand high temperatures above 50 °C, and has better high-temperature anti-corrosion performance.
  • novel anti-corrosion type polycarboxylate water reducer provided by the present invention is suitable for application occasions with high sensitivity to polycarboxylate water reducer and high anti-corrosion requirements.
  • the cost of the product is more in line with the application requirements of the polycarboxylate superplasticizer, and has important practical application value.
  • the present invention also provides the following preparation examples of the novel anti-corrosion type polycarboxylate water reducer:
  • step (2) adding 7g sodium hydroxide aqueous solution of 32% concentration to the copolymerization product obtained in step (1) to obtain the novel anti-corrosion type polycarboxylate water reducer KZJ-1.
  • acrylic acid aqueous solution wherein, acrylic acid 18.00g, water 20.00g
  • hydrogen peroxide solution wherein, hydrogen peroxide 1.80g, water 20.00g
  • thioglycolic acid aqueous solution wherein, thioglycolic acid 0.90g
  • aqueous solution of hanging white block wherein, hanging white block 0.30, water 20.00g
  • the initial reaction temperature is 10 ° C
  • the dropping time is 0.75 h
  • the temperature of the material in the dropping process is controlled ⁇ 30 ° C
  • step (2) adding 6g sodium hydroxide aqueous solution of 32% concentration to the copolymerization product obtained in step (1) to obtain the novel anti-corrosion type polycarboxylate water reducing agent KZJ-3.
  • Aqueous solution (among them, ascorbic acid 0.40, water 20.00g), the initial reaction temperature is 15 °C, the dropwise addition time is 0.5h, the dropwise addition process controls the material temperature ⁇ 30 °C, after the dropwise addition is completed, the temperature is kept for 1h to obtain the copolymerization product;
  • PCE-1 and monomethyl fumarate were compounded according to the mass ratio of 143:1 to obtain the comparative sample PCE-2.
  • the PCE-1 and The K350 preservative is compounded according to the mass ratio of 143:1, that is, the comparative sample PCE-3 is obtained.
  • step (2) adding 7g sodium hydroxide aqueous solution of 32% concentration to the copolymerization product obtained in step (1) to obtain the novel anti-corrosion type polycarboxylate water reducing agent PCE-4.
  • PCE-1 has begun to have odor and mildew at 30 days, and the antiseptic effect of PCE-2 directly compounded with monomethyl fumarate is slightly better than that of PCE-1, but it is also less effective at 60 days. Odor and mildew appear, compound The PCE-3 of K350 preservative and the amount of substances such as monomethyl fumarate in the synthesis are replaced by dimethyl fumarate PCE-4.
  • the antiseptic effect of PCE-4 is equivalent to that of PCE-2, while the embodiment of the present invention 1 to implementation
  • the new type of anti-corrosion polycarboxylate water reducer prepared in Example 4 has a significantly better anti-corrosion effect than the comparative example at 50 ° C.

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  • 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

La présente invention concerne le domaine technique des matériaux de construction et en particulier un nouveau réducteur d'eau à base d'acide polycarboxylique anticorrosion et un procédé de préparation associé, le nouveau réducteur d'eau à base d'acide polycarboxylique anticorrosion étant formé par mise en œuvre d'une réaction de polymérisation sur un petit monomère ayant une fonction anticorrosion avec un gros monomère insaturé, un acide carboxylique insaturé et/ou un anhydride carboxylique insaturé sous l'action d'un amorceur et d'un régulateur de masse moléculaire, en générant ainsi un nouveau réducteur d'eau à base d'acide polycarboxylique anticorrosion ayant un petit monomère présentant une fonction anticorrosion, réuni à la chaîne moléculaire principale. Le gros monomère insaturé est au moins un tel monomère choisi parmi le polyglycoléther monovinylique de l'éthylèneglycol ou le 4-hydroxybutyl-vinyl-éther polyoxyéthyléné. Le nouveau réducteur d'eau à base d'acide polycarboxylique anticorrosion de la présente invention est un réducteur d'eau de type éther ayant son propre effet anticorrosion. Le réducteur présente de bons effets anticorrosion et de réduction de l'eau, et le nouveau produit réducteur d'eau à base d'acide polycarboxylique anticorrosion finalement obtenu présente une structure macromoléculaire stable, capable de supporter des températures de 50 °C et plus. Le réducteur d'eau présente ainsi de meilleures performances anticorrosion à haute température et est caractérisé par un procédé de préparation simple et présente une grande importance pour des applications réelles.
PCT/CN2021/120155 2020-11-03 2021-09-24 Nouveau réducteur d'eau à base d'acide polycarboxylique anticorrosion et procédé de préparation associé WO2022095622A1 (fr)

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CN202011212013.7A CN112708060B (zh) 2020-11-03 2020-11-03 一种新型防腐型聚羧酸减水剂及其制备方法
CN202011212013.7 2020-11-03

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CN112708060B (zh) * 2020-11-03 2022-09-27 科之杰新材料集团有限公司 一种新型防腐型聚羧酸减水剂及其制备方法
CN113698547B (zh) * 2021-08-31 2022-06-03 科之杰新材料集团有限公司 一种高性能聚羧酸减水剂及其制备方法
CN115838458A (zh) * 2022-11-14 2023-03-24 科之杰新材料集团有限公司 一种新型聚羧酸减水剂及其制备方法
CN115850201B (zh) * 2022-12-23 2024-07-30 科之杰新材料集团有限公司 一种杀菌单体、灭藻防腐型聚羧酸减水剂及其制备方法

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