WO2024104063A1 - 一种新型聚羧酸减水剂及其制备方法 - Google Patents

一种新型聚羧酸减水剂及其制备方法 Download PDF

Info

Publication number
WO2024104063A1
WO2024104063A1 PCT/CN2023/126337 CN2023126337W WO2024104063A1 WO 2024104063 A1 WO2024104063 A1 WO 2024104063A1 CN 2023126337 W CN2023126337 W CN 2023126337W WO 2024104063 A1 WO2024104063 A1 WO 2024104063A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
water
compound
reducing agent
unsaturated carboxylic
Prior art date
Application number
PCT/CN2023/126337
Other languages
English (en)
French (fr)
Inventor
蒋卓君
林泳珊
熊秋闵
邱年丽
方云辉
陈晓彬
关基灿
黄忠
Original Assignee
科之杰新材料集团有限公司
科之杰新材料集团(广东)有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 科之杰新材料集团有限公司, 科之杰新材料集团(广东)有限公司 filed Critical 科之杰新材料集团有限公司
Publication of WO2024104063A1 publication Critical patent/WO2024104063A1/zh

Links

Classifications

    • 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
    • C04B24/16—Sulfur-containing compounds
    • C04B24/20—Sulfonated aromatic compounds
    • C04B24/22—Condensation or polymerisation products thereof
    • 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
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention relates to the field of admixtures, and in particular to a novel polycarboxylate water reducer and a preparation method thereof.
  • Polycarboxylate water reducer has the characteristics of high water reduction rate, strong performance designability, and convenient production.
  • polycarboxylate water reducer does not produce harmful substances such as formaldehyde and ammonia during the synthesis and production process, and the synthesis temperature is much lower than that of naphthalene water reducer. Due to the energy-saving and environmentally friendly production process of polycarboxylate water reducer, it has been vigorously promoted and applied in the past decade or so, and has become a mainstream product in the water reducer market, widely used in engineering fields such as roads, railways, bridges, nuclear power, dams, tunnels, marine engineering and high-rise buildings.
  • the present invention develops a novel polycarboxylate water reducer and a preparation method thereof, which can use a relatively convenient process method to prepare a high-performance polycarboxylate water reducer with excellent water-reducing effect.
  • the present invention provides a novel polycarboxylic acid water reducer, which is produced by a polymerization reaction of compound A, compound B, unsaturated macromonomer, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride under the action of an initiator and a molecular weight regulator;
  • R 1 is an alkylene group of 0-4 carbon atoms
  • R 2 is COOM or SO 3 M or PO 3 M 2
  • M is H or an alkylene group of 0-4 carbon atoms or Na, K, or NH 4 ;
  • R 3 is H or CH 3
  • R 4 is an alkylene group of 0-4 carbon atoms
  • X is O or S
  • R 5 is an alkylene group of 0-4 carbon atoms
  • R 6 is an alkylene group of 0-4 carbon atoms
  • R 7 is COOM or SO 3 M or PO 3 M 2 or SO 2 NH 2
  • M is H or an alkylene group of 0-4 carbon atoms or Na, K, NH 4 .
  • the mass ratio of the unsaturated macromonomer, compound A, compound B, unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is 180:(1-5):(1-10):(5-30).
  • the compound A is at least one of (4-vinylphenyl)methanesulfonic acid, sodium (4-vinylphenyl)methanesulfonate, 4-vinylphenylacetic acid, 4-vinylbenzoic acid, 2-methyl-2-(4-vinylphenyl)propionic acid, 4-vinyl-benzoic acid methyl ester, 4-vinyl-benzoic acid ethyl ester, 4-vinylphenylethyl ester, and 4-vinylphenyl diethyl phosphate.
  • the compound B is 4-vinyloxybenzenesulfonic acid, 4-vinyloxybenzoic acid, At least one of 4-vinyloxyphenylacetic acid, sodium 4-vinyloxybenzenesulfonate, potassium 4-vinyloxybenzenesulfonate, methyl 4-vinyloxybenzoate, ethyl 4-vinyloxybenzoate, methyl 4-vinyloxyphenylacetate, ethyl 4-vinyloxyphenylacetate, ethyl 4-vinyloxyphenylacetate, ethyl 4-vinyloxyphenylacetate, 4-(allyloxy)benzenesulfonamide, 4-(vinyloxy)benzenesulfonamide, 2-(vinyloxy)benzenesulfonamide and 4-(allyloxy)benzoic acid.
  • the molecular weight of the unsaturated macromonomer is 600-6000, and the unsaturated macromonomer is at least one of 3-methyl-3-butene-1-polyethylene glycol, 2-methylallyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether, 4-hydroxybutyl vinyl polyoxyethylene ether, methoxy polyethylene glycol methacrylate, and methoxy polyethylene glycol acrylate.
  • the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid and maleic anhydride.
  • the amount of the initiator is 0.5-3.0% of the total mass of the reactants; the amount of the molecular weight regulator is 0.2-3.0% of the total mass of the reactants.
  • the initiator includes a water-soluble redox initiator system or a water-soluble peroxide initiator system reagent.
  • the initiator is at least one of hydrogen peroxide-ascorbic acid, hydrogen peroxide-bleaching powder, hydrogen peroxide-ascorbic acid-ferrous sulfate, hydrogen peroxide-bleaching powder-ferrous sulfate, hydrogen peroxide-BRUGGOLITE E51-ferrous sulfate, and ammonium persulfate.
  • the molecular weight regulator includes at least one of thioglycolic acid, mercaptoethanol, mercaptopropionic acid, sulfonated mercaptopropionic acid, and sodium hypophosphite.
  • Another object of the present invention is to provide a method for preparing the novel polycarboxylate water-reducing agent, comprising at least the following steps:
  • the unsaturated macromonomer, compound A, compound B and water are added to the reactor and stirred. After the materials are evenly mixed, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, initiator and molecular weight regulator are added dropwise.
  • the dropping time is 0.5-2h, the initial reaction temperature is 10-25°C, and the material temperature is controlled at 10-30°C during the dropping process; after the dropping is completed, the temperature is kept for 0.5-1h to obtain a copolymer product; in the copolymer product, a base is added to adjust the pH value of the product to 5-7 or no base is added to adjust the pH value, so as to obtain the novel polycarboxylate water reducer.
  • the present invention has the following beneficial effects:
  • the present invention introduces compound A into the molecular structure of the polycarboxylate water-reducing agent through copolymerization, so that the main chain side groups have benzene rings and carboxyl groups or sulfonic acid groups.
  • the carboxyl groups or sulfonic acid groups provide electrostatic repulsion and enhance the water-reducing effect.
  • the benzene ring makes the side chains of the obtained polycarboxylate water-reducing agent molecules more stretched after being adsorbed on the surface of cement particles, and the steric hindrance effect is more obvious, which ultimately makes the water reduction rate of the product higher.
  • This application also uses other different types of macromonomers to match different types of small monomers, which is more conducive to copolymerization and also makes the performance of the final product better.
  • the raw materials used in the present invention are widely available and the preparation process is simple, so that the prepared product is more in line with the application requirements of polycarboxylic acid water reducer.
  • the experimental methods in the following examples are conventional methods unless otherwise specified.
  • the experimental materials and reagents used in the following examples are all commercially available unless otherwise specified.
  • the quantitative tests in the following examples were performed in triplicate, and the data are the average or average ⁇ standard deviation of the triplicate experiments.
  • the "and/or" in the full text includes three solutions. Taking A and/or B as an example, it includes technical solution A, technical solution B, and a technical solution that satisfies both A and B.
  • the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in the field to implement. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.
  • an acrylic acid aqueous solution including 17.00 g of acrylic acid and 20.00 g of water
  • a hydrogen peroxide aqueous solution including 1.50 g of hydrogen peroxide and 20.00 g of water
  • a mercaptopropionic acid aqueous solution including 0.70 g of mercaptopropionic acid and 20.00 g of water
  • a BRUGGOLITE E51 aqueous solution including 0.25 g of BRUGGOLITE E51 and 20.00 g of water
  • an acrylic acid aqueous solution including 18.00 g of acrylic acid and 20.00 g of water
  • a hydrogen peroxide aqueous solution including 1.30 g of hydrogen peroxide and 20.00 g of water
  • a thioglycolic acid aqueous solution including 0.90 g of thioglycolic acid and 20.00 g of water
  • a bleaching powder aqueous solution including 0.30 g of bleaching powder and 20.00 g of water
  • aqueous solution including 14.00 g of acrylic acid, 2.00 g of maleic anhydride and 20.00 g of water
  • aqueous hydrogen peroxide solution including 1.50 g of hydrogen peroxide and 20.00 g of water
  • aqueous ascorbic acid solution including 0.40 g of ascorbic acid and 20.00 g of water
  • acrylic acid mixed aqueous solution including 15.00 g acrylic acid and 20.00 g water
  • hydrogen peroxide aqueous solution including 1.20 g hydrogen peroxide and 20.00 g water
  • BRUGGOLITE E51 aqueous solution including 0.28 g BRUGGOLITE E51 and 20.00 g water
  • an acrylic acid aqueous solution including 20.00 g of acrylic acid and 20.00 g of water
  • a hydrogen peroxide aqueous solution including 1.50 g of hydrogen peroxide and 20.00 g of water
  • a mercaptopropionic acid aqueous solution including 0.70 g of mercaptoethanol and 20.00 g of water
  • an ascorbic acid aqueous solution including 0.40 g of ascorbic acid and 20.00 g of water
  • step (2) Add 11 g of 32% sodium hydroxide aqueous solution to the copolymer product obtained in step (1) to obtain the novel polycarboxylic acid water reducer, which is recorded as KZJ-5.
  • an acrylic acid aqueous solution including 17.00 g of acrylic acid and 20.00 g of water
  • a hydrogen peroxide aqueous solution including 1.50 g of hydrogen peroxide and 20.00 g of water
  • a mercaptopropionic acid aqueous solution including 0.70 g of mercaptopropionic acid and 20.00 g of water
  • a BRUGGOLITE E51 aqueous solution including 0.25 g of BRUGGOLITE E51 and 20.00 g of water
  • an acrylic acid aqueous solution including 17.00 g of acrylic acid and 20.00 g of water
  • a hydrogen peroxide aqueous solution including 1.50 g of hydrogen peroxide and 20.00 g of water
  • a mercaptopropionic acid aqueous solution including 0.70 g of mercaptopropionic acid and 20.00 g of water
  • a BRUGGOLITE E51 aqueous solution including 0.25 g of BRUGGOLITE E51 and 20.00 g of water
  • an acrylic acid aqueous solution including 17.00 g of acrylic acid and 20.00 g of water
  • a hydrogen peroxide aqueous solution including 1.50 g of hydrogen peroxide and 20.00 g of water
  • a mercaptopropionic acid aqueous solution including 0.70 g of mercaptopropionic acid and 20.00 g of water
  • a BRUGGOLITE E51 aqueous solution including 0.25 g of BRUGGOLITE E51 and 20.00 g of water
  • an acrylic acid aqueous solution including 18.00 g of acrylic acid and 20.00 g of water
  • a hydrogen peroxide aqueous solution including 1.30 g of hydrogen peroxide and 20.00 g of water
  • a thioglycolic acid aqueous solution including 0.90 g of thioglycolic acid and 20.00 g of water
  • a bleaching powder aqueous solution including 0.30 bleaching powder and 20.00 g of water
  • the results of the comparison between KZJ-1 and PCE-1 show that after removing the sodium (4-vinylphenyl) methanesulfonate in KZJ-1, the water reduction rate and the 3d, 7d, and 28d compressive strength ratios of the product are slightly reduced;
  • the results of the comparison between KZJ-1 and PCE-2 show that after removing the 4-vinyloxybenzenesulfonic acid in KZJ-1, the water reduction rate and the 3d, 7d, and 28d compressive strength ratios of the product are slightly reduced;
  • the results of the comparison between KZJ-1 and PCE-3 show that after removing the sodium (4-vinylphenyl) methanesulfonate in KZJ-1, the water reduction rate and the 3d, 7d, and 28d compressive strength ratios of the product are slightly reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明涉及一种新型聚羧酸减水剂及其制备方法，由化合物A、化合物B、不饱和大单体、不饱和羧酸和/或不饱和羧酸酐在引发剂和分子量调节剂的作用下发生聚合反应生成的新型聚羧酸减水剂；所述不饱和大单体、化合物A、化合物B、不饱和羧酸和/或不饱和羧酸酐的质量比为180:(1-5):(1-10):(5-30)。本发明将化合物A通过共聚反应引入聚羧酸减水剂分子结构中，使得主链侧基具有苯环和羧基或磺酸基，羧基或磺酸基提供了静电斥力，增强了减水效果；苯环使得得到的聚羧酸减水剂分子在吸附在水泥颗粒表面后，侧链更为舒展，空间位阻效应更为明显，最终也使得产物的减水率更高。

Description

一种新型聚羧酸减水剂及其制备方法 技术领域
本发明涉及外加剂领域，特别涉及一种新型聚羧酸减水剂及其制备方法。
背景技术
聚羧酸减水剂具有减水率高、性能可设计性强、生产方便等特点，且聚羧酸减水剂在合成生产过程中无甲醛、氨等有害物质产生，合成温度相比于萘系减水剂低很多。因聚羧酸减水剂的生产工艺节能环保，近十几年来得到了大力的推广应用，已经成为了减水剂市场上的主流产品，广泛应用于公路、铁路、桥梁、核电、大坝、隧道、海工和高层建筑等工程领域中。
但是，近年来由于我国混凝土用砂石资源供应紧张的局面越来越严峻，全国不少地区的天然砂、石资源日益匮乏，砂石材料供不应求，这导致了砂石材料的供应极不稳定以及砂石含泥量高且不稳定的问题。聚羧酸减水剂应用于混凝土，出现减水率不足的问题日益突出。因此，需要不断改进聚羧酸减水剂的结构，使其具备更高的减水性能是聚羧酸减水剂行业的发展方向。
发明内容
针对现有技术，本发明开发了一种新型聚羧酸减水剂及其制备方法，能够使用比较便利的工艺方法，制备出减水效果优异的高性能聚羧酸减水剂。
基于此，本发明提供了一种新型聚羧酸减水剂，由化合物A、化合物B、不饱和大单体、不饱和羧酸和/或不饱和羧酸酐在引发剂和分子量调节剂的作用下发生聚合反应生成的新型聚羧酸减水剂；
所述化合物A的结构式如下：
其中，R1为0-4个碳的亚烷基，R2为COOM或SO3M或PO3M2，M为H或0-4个碳的亚烷基或Na、K、NH4；
所述化合物B的结构式如下：
其中，R3为H或CH3，R4为0-4个碳的亚烷基，X为O或者S，R5为0-4个碳的亚烷基，R6为0-4个碳的亚烷基，R7为COOM或SO3M或PO3M2或SO2NH2，M为H或0-4个碳的亚烷基或Na、K、NH4。
进一步地，所述不饱和大单体、化合物A、化合物B、不饱和羧酸和/或不饱和羧酸酐的质量比为180:(1-5):(1-10):(5-30)。
进一步地，所述化合物A为(4-乙烯基苯基)甲磺酸、(4-乙烯基苯基)甲磺酸钠、4-乙烯基苯乙酸、4-乙烯基苯甲酸、2-甲基-2-(4-乙烯基苯基)丙酸、4-乙烯基-苯甲酸甲酯、4-乙烯基-苯甲酸乙酯、4-乙烯基苯乙酸乙酯、4-乙烯基苯基磷酸二乙酯中的至少一种。
进一步地，所述化合物B为4-乙烯基氧基苯磺酸、4-乙烯基氧基苯甲酸、 4-乙烯基氧基苯乙酸、4-乙烯基氧基苯磺酸钠、4-乙烯基氧基苯磺酸钾、4-乙烯基氧基苯甲酸甲酯、4-乙烯基氧基苯甲酸乙酯、4-乙烯基氧基苯乙酸甲酯、4-乙烯基氧基苯乙酸乙酯、4-(烯丙氧基)苯磺酰胺、4-(乙烯基氧基)苯磺酰胺、2-(乙烯基氧基)苯磺酰胺、4-(烯丙氧基)苯甲酸中的至少一种。
进一步地，所述不饱和大单体的分子量为600-6000，所述不饱和大单体为3-甲基-3-丁烯-1-聚乙二醇、2-甲基烯丙基聚乙二醇、乙二醇单乙烯基聚乙二醇醚、4-羟丁基乙烯基聚氧乙烯基醚、甲氧基聚乙二醇甲基丙烯酸酯、甲氧基聚乙二醇丙烯酸酯中的至少一种。
进一步地，所述不饱和羧酸和/或不饱和羧酸酐为丙烯酸、甲基丙烯酸、马来酸酐中的至少一种。
进一步地，所述引发剂的用量为反应物总质量的0.5-3.0％；所述分子量调节剂的用量为反应物总质量的0.2-3.0％。
进一步地，所述引发剂包括水溶性氧化还原引发体系或水溶性过氧化物引发体系试剂。
进一步地，所述引发剂为双氧水-抗坏血酸、双氧水-吊白块、双氧水-抗坏血酸-硫酸亚铁、双氧水-吊白块-硫酸亚铁、双氧水-BRUGGOLITE E51-硫酸亚铁、过硫酸铵中的至少一种。
进一步地，所述分子量调节剂包括巯基乙酸、巯基乙醇、巯基丙酸、磺化巯基丙酸、次磷酸钠中的至少一种。
本发明的另一目的是提供一种上述新型聚羧酸减水剂的制备方法，至少包括以下步骤：
将不饱和大单体、化合物A、化合物B和水加入到反应器中搅拌，待物料混合均匀后，滴加不饱和羧酸和/或不饱和羧酸酐、引发剂、分子量调节剂，滴加时间为0.5-2h，起始反应温度为10-25℃，滴加过程控制物料温度10-30℃；滴加完毕后保温0.5-1h，得共聚产物；在共聚产物中，加入碱调节产物pH值至5-7或不加碱调整pH值，即制得所述新型聚羧酸减水剂。
综上所述，本发明具有以下有益效果：
1.本发明将化合物A通过共聚反应引入聚羧酸减水剂分子结构中，使得主链侧基具有苯环和羧基或磺酸基，羧基或磺酸基提供了静电斥力，增强了减水效果；苯环使得得到的聚羧酸减水剂分子在吸附在水泥颗粒表面后，侧链更为舒展，空间位阻效应更为明显，最终也使得产物的减水率更高。
2.本申请还使用了其他不同类型的大单体匹配不同类型的小单体，更有利于共聚反应，也使得最终产物的性能更优异。
3.本发明所用的原材料来源广泛，制备工艺简单，使得制备得到的产品更符合聚羧酸减水剂的应用要求。
具体实施方式
下面将结合本发明实施例，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作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
下述实施例中的实验方法，如无特殊说明，均为常规方法。下述实施例中所用的试验材料和试剂等，如无特殊说明，均可从商业途径获得。以下实施例中的定量试验，均设置三次重复实验，数据为三次重复实验的平均值或平均值±标准差。
另外，全文中的“和/或”包括三个方案，以A和/或B为例，包括A技术方案、B技术方案，以及A和B同时满足的技术方案；另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。
实施例1
(1)将180.00g分子量为3000的乙二醇单乙烯基聚乙二醇醚、2.00g(4-乙烯基苯基)甲磺酸钠、4.00g 4-乙烯基氧基苯磺酸、0.006g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸水溶液(其中，丙烯酸17.00g，水20.00g)、双氧水水溶液(其中，双氧水1.50g，水20.00g)、巯基丙酸水溶液(其中，巯基丙酸0.70g，水20.00g)、BRUGGOLITE E51水溶液(其中，BRUGGOLITE E51 0.25g，水20.00g)，起始反应温度为15℃，滴加时间为1.0h，滴加过程控制物料温度≤30℃，滴加完毕后保温1h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入7g 32％浓度的氢氧化钠水溶液，即得所述新型聚羧酸减水剂KZJ-1。
实施例2
(1)将180.00g分子量为3000的4-羟丁基乙烯基聚氧乙烯基醚、6.00g 4-乙烯基苯甲酸、2.00g 4-(乙烯基氧基)苯磺酰胺、0.005g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸水溶液(其中，丙烯酸18.00g，水20.00g)、双氧水水溶液(其中，双氧水1.30g，水20.00g)、巯基乙酸水溶液(其中，巯基乙酸0.90g，水20.00g)、吊白块水溶液(其中，吊白块0.30，水20.00g)，起始反应温度为13℃，滴加时间为0.75h，滴加过程控制物料温度≤25℃，滴加完毕后保温1h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入9g 32％浓度的氢氧化钠水溶液，即得所述新型聚羧酸减水剂KZJ-2。
实施例3
(1)将180.00g分子量为2400的乙二醇单乙烯基聚乙二醇醚、1.00g 4-乙烯基苯基磷酸二乙酯、1.50g 2-甲基-2-(4-乙烯基苯基)丙酸、4.00g 4-(烯丙氧基)苯甲酸、2.50g次磷酸钠、0.005g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸和马来酸酐混合 水溶液(其中，丙烯酸14.00g，马来酸酐2.00g，水20.00g)、双氧水水溶液(其中，双氧水1.50g，水20.00g)、抗坏血酸水溶液(其中，抗坏血酸0.40，水20.00g)，起始反应温度为12℃，滴加时间为1h，滴加过程控制物料温度≤30℃，滴加完毕后保温1h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入10g 32％浓度的氢氧化钠水溶液，即得所述新型聚羧酸减水剂KZJ-3。
实施例4
(1)将120.00g分子量为3000的乙二醇单乙烯基聚乙二醇醚、60.00g分子量为2400的2-甲基烯丙基聚乙二醇、1.50g(4-乙烯基苯基)甲磺酸、1.50g 4-乙烯基-苯甲酸乙酯、2.00g 4-乙烯基氧基苯磺酸、3.00g 4-(烯丙氧基)苯甲酸、3.00g次磷酸钠、0.004g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸混合水溶液(其中，丙烯酸15.00g，水20.00g)、双氧水溶液(其中，双氧水1.20g，水20.00g)、BRUGGOLITE E51水溶液(其中，BRUGGOLITE E51 0.28g，水20.00g)，起始反应温度为18℃，滴加时间为1.5h，滴加过程控制物料温度≤30℃，滴加完毕后保温0.5h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入6g 32％浓度的氢氧化钠水溶液，即得所述新型聚羧酸减水剂KZJ-4。
实施例5
(1)将140.00g分子量为3000的乙二醇单乙烯基聚乙二醇醚、40.00g分子量为2400的3-甲基-3-丁烯-1-聚乙二醇、2.40g(4-乙烯基苯基)甲磺酸、2.00g4-(烯丙氧基)苯甲酸、2.00g4-(烯丙氧基)苯磺酰胺、0.004g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸水溶液(其中，丙烯酸20.00g，水20.00g)、双氧水水溶液(其中，双氧水1.50g，水20.00g)、巯基丙酸水溶液(其中，巯基乙醇0.70g，水20.00g)、抗坏血酸水溶液(其中，抗坏血酸0.40，水20.00g)，起始反应温 度为15℃，滴加时间为1.0h，滴加过程控制物料温度≤25℃，滴加完毕后保温0.5h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入11g 32％浓度的氢氧化钠水溶液，即得所述新型聚羧酸减水剂，记为KZJ-5。
对比例1
(1)将180.00g分子量为3000的乙二醇单乙烯基聚乙二醇醚、4.00g 4-乙烯基氧基苯磺酸、0.006g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸水溶液(其中，丙烯酸17.00g，水20.00g)、双氧水水溶液(其中，双氧水1.50g，水20.00g)、巯基丙酸水溶液(其中，巯基丙酸0.70g，水20.00g)、BRUGGOLITE E51水溶液(其中，BRUGGOLITE E51 0.25g，水20.00g)，起始反应温度为15℃，滴加时间为1.0h，滴加过程控制物料温度≤30℃，滴加完毕后保温1h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入7g 32％浓度的氢氧化钠水溶液，即得对比样品PCE-1。
对比例2
(1)将180.00g分子量为3000的乙二醇单乙烯基聚乙二醇醚、2.00g(4-乙烯基苯基)甲磺酸钠、0.006g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸水溶液(其中，丙烯酸17.00g，水20.00g)、双氧水水溶液(其中，双氧水1.50g，水20.00g)、巯基丙酸水溶液(其中，巯基丙酸0.70g，水20.00g)、BRUGGOLITE E51水溶液(其中，BRUGGOLITE E51 0.25g，水20.00g)，起始反应温度为15℃，滴加时间为1.0h，滴加过程控制物料温度≤30℃，滴加完毕后保温1h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入7g 32％浓度的氢氧化钠水溶液， 即得比样品PCE-2。
对比例3
(1)将180.00g分子量为3000的乙二醇单乙烯基聚乙二醇醚、0.006g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸水溶液(其中，丙烯酸17.00g，水20.00g)、双氧水水溶液(其中，双氧水1.50g，水20.00g)、巯基丙酸水溶液(其中，巯基丙酸0.70g，水20.00g)、BRUGGOLITE E51水溶液(其中，BRUGGOLITE E510.25g，水20.00g)，起始反应温度为15℃，滴加时间为1.0h，滴加过程控制物料温度≤30℃，滴加完毕后保温1h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入7g 32％浓度的氢氧化钠水溶液，即得比样品PCE-3。
对比例4
(1)将180.00g分子量为3000的4-羟丁基乙烯基聚氧乙烯基醚、6.00g 4-乙烯基苯甲酸、0.005g硫酸亚铁和145.00g水加入到反应器中，开启搅拌器和控温装置，待物料混合均匀，开始滴加丙烯酸水溶液(其中，丙烯酸18.00g，水20.00g)、双氧水水溶液(其中，双氧水1.30g，水20.00g)、巯基乙酸水溶液(其中，巯基乙酸0.90g，水20.00g)、吊白块水溶液(其中，吊白块0.30，水20.00g)，起始反应温度为13℃，滴加时间为0.75h，滴加过程控制物料温度≤25℃，滴加完毕后保温1h，得共聚产物；
(2)在步骤(1)制得的共聚产物中加入9g 32％浓度的氢氧化钠水溶液，即得比样品PCE-4。
混凝土性能测试
按照GB/T8076-2008对实施例1至实施例5所制得的新型聚羧酸减水剂和对比例1至对比例3所制得的对比样品按照折固掺量为0.16％进行性能测试，测试结果如表1所示：
表1混凝土测试结果
如表1所示，KZJ-1与PCE-1对比的结果显示，将KZJ-1中的(4-乙烯基苯基)甲磺酸钠去掉后，产物的减水率和3d、7d、28d抗压强度比略有下降；KZJ-1与PCE-2对比的结果显示，将KZJ-1中的4-乙烯基氧基苯磺酸去掉后，产物的减水率和3d、7d、28d抗压强度比略有下降；KZJ-1与PCE-3对比的结果显示，将KZJ-1中的(4-乙烯基苯基)甲磺酸钠和4-乙烯基氧基苯磺酸去掉后，产物的减水率和3d、7d、28d抗压强度比下降明显；KZJ-2与PCE-4对比的结果显示，将KZJ-2中的4-(乙烯基氧基)苯磺酰胺去掉后，产物的减水率基本不变，但是3d、7d、28d抗压强度比下降明显；按本专利技术方案合成的产品均具有较高的减水率和3d、7d、28d抗压强度比。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干 变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种新型聚羧酸减水剂，其特征在于，由化合物A、化合物B、不饱和大单体、不饱和羧酸和/或不饱和羧酸酐在引发剂和分子量调节剂的作用下发生聚合反应生成的新型聚羧酸减水剂；
    所述化合物A的结构式如下：
    其中，R1为0-4个碳的亚烷基，R2为COOM或SO3M或PO3M2，M为H或0-4个碳的亚烷基或Na、K、NH4；
    所述化合物B的结构式如下：
    其中，R3为H或CH3，R4为0-4个碳的亚烷基，X为O或者S，R5为0-4个碳的亚烷基，R6为0-4个碳的亚烷基，R7为COOM或SO3M或PO3M2或SO2NH2，M为H或0-4个碳的亚烷基或Na、K、NH4。
  2. 根据权利要求1所述的一种新型聚羧酸减水剂，其特征在于：所述不饱和大单体、化合物A、化合物B、不饱和羧酸和/或不饱和羧酸酐的质量比为180:(1-5):(1-10):(5-30)。
  3. 根据权利要求1所述的一种新型聚羧酸减水剂，其特征在于：所述化合物A为(4-乙烯基苯基)甲磺酸、(4-乙烯基苯基)甲磺酸钠、4-乙烯基苯乙酸、4-乙烯基苯甲酸、2-甲基-2-(4-乙烯基苯基)丙酸、4-乙烯基-苯甲酸甲酯、4-乙烯基-苯甲酸乙酯、4-乙烯基苯乙酸乙酯、4-乙烯基苯基磷酸二乙酯中的至少一种。
  4. 根据权利要求1所述的一种新型聚羧酸减水剂，其特征在于：所述化合物B为4-乙烯基氧基苯磺酸、4-乙烯基氧基苯甲酸、4-乙烯基氧基苯乙酸、4-乙烯基氧基苯磺酸钠、4-乙烯基氧基苯磺酸钾、4-乙烯基氧基苯甲酸甲酯、4-乙烯基氧基苯甲酸乙酯、4-乙烯基氧基苯乙酸甲酯、4-乙烯基氧基苯乙酸乙酯、4-(烯丙氧基)苯磺酰胺、4-(乙烯基氧基)苯磺酰胺、2-(乙烯基氧基)苯磺酰胺、4-(烯丙氧基)苯甲酸中的至少一种。
  5. 根据权利要求1所述的一种新型聚羧酸减水剂，其特征在于：所述不饱和大单体的分子量为600-6000，所述不饱和大单体为3-甲基-3-丁烯-1-聚乙二醇、2-甲基烯丙基聚乙二醇、乙二醇单乙烯基聚乙二醇醚、4-羟丁基乙烯基聚氧乙烯基醚、甲氧基聚乙二醇甲基丙烯酸酯、甲氧基聚乙二醇丙烯酸酯中的至少一种。
  6. 根据权利要求1所述的一种新型聚羧酸减水剂，其特征在于：所述不饱和羧酸和/或不饱和羧酸酐为丙烯酸、甲基丙烯酸、马来酸酐中的至少一种。
  7. 根据权利要求1所述的一种新型聚羧酸减水剂，其特征在于：所述引发剂的用量为反应物总质量的0.5-3.0％；所述分子量调节剂的用量为反应物总质量的0.2-3.0％。
  8. 根据权利要求1所述的一种新型聚羧酸减水剂，其特征在于：所述引发剂包括水溶性氧化还原引发体系或水溶性过氧化物引发体系试剂。
  9. 根据权利要求1所述的一种新型聚羧酸减水剂，其特征在于：所述分子量 调节剂包括巯基乙酸、巯基乙醇、巯基丙酸、磺化巯基丙酸、次磷酸钠中的至少一种。
  10. 一种制备如权利要求1-9任一项的新型聚羧酸减水剂的方法，其特征在于：至少包括以下步骤：
    将不饱和大单体、化合物A、化合物B和水加入到反应器中搅拌，待物料混合均匀后，滴加不饱和羧酸和/或不饱和羧酸酐、引发剂、分子量调节剂，滴加时间为0.5-2h，起始反应温度为10-25℃，滴加过程控制物料温度10-30℃；滴加完毕后保温0.5-1h，得共聚产物；在共聚产物中，加入碱调节产物pH值至5-7或不加碱调整pH值，即制得所述新型聚羧酸减水剂。
PCT/CN2023/126337 2022-11-14 2023-10-25 一种新型聚羧酸减水剂及其制备方法 WO2024104063A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211417990.X 2022-11-14
CN202211417990.XA CN115838458A (zh) 2022-11-14 2022-11-14 一种新型聚羧酸减水剂及其制备方法

Publications (1)

Publication Number Publication Date
WO2024104063A1 true WO2024104063A1 (zh) 2024-05-23

Family

ID=85575564

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/126337 WO2024104063A1 (zh) 2022-11-14 2023-10-25 一种新型聚羧酸减水剂及其制备方法

Country Status (2)

Country Link
CN (1) CN115838458A (zh)
WO (1) WO2024104063A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009004348A2 (en) * 2007-07-02 2009-01-08 W.R. Grace & Co. - Conn Slump retention-enhanced cement dispersants
CN108623745A (zh) * 2018-06-08 2018-10-09 科之杰新材料集团有限公司 一种含磷聚羧酸减水剂及其制备方法
CN109970921A (zh) * 2018-06-08 2019-07-05 科之杰新材料集团有限公司 一种高减水低敏感聚羧酸减水剂及其制备方法
CN109970920A (zh) * 2018-06-08 2019-07-05 科之杰新材料集团有限公司 一种磺酸改性聚羧酸减水剂及其制备方法
CN111205412A (zh) * 2020-03-12 2020-05-29 浙江建设职业技术学院 苯基磺酸基嵌段聚合物改性聚羧酸减水剂
CN112708060A (zh) * 2020-11-03 2021-04-27 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
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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110144200B (zh) * 2019-06-14 2020-07-03 黑龙江益瑞化工有限公司 一种油田化学采油用共聚物弹性凝胶类调剖剂
CN111499313B (zh) * 2020-05-28 2024-08-09 贵州航天建设工程有限公司 一种水泥基气凝胶保温隔热板及其制备方法
CN115321873A (zh) * 2022-08-11 2022-11-11 广州奕邦汇科技有限公司 一种无机改性型聚羧酸陶瓷减水剂及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009004348A2 (en) * 2007-07-02 2009-01-08 W.R. Grace & Co. - Conn Slump retention-enhanced cement dispersants
CN108623745A (zh) * 2018-06-08 2018-10-09 科之杰新材料集团有限公司 一种含磷聚羧酸减水剂及其制备方法
CN109970921A (zh) * 2018-06-08 2019-07-05 科之杰新材料集团有限公司 一种高减水低敏感聚羧酸减水剂及其制备方法
CN109970920A (zh) * 2018-06-08 2019-07-05 科之杰新材料集团有限公司 一种磺酸改性聚羧酸减水剂及其制备方法
CN111205412A (zh) * 2020-03-12 2020-05-29 浙江建设职业技术学院 苯基磺酸基嵌段聚合物改性聚羧酸减水剂
CN112708060A (zh) * 2020-11-03 2021-04-27 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
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

Also Published As

Publication number Publication date
CN115838458A (zh) 2023-03-24

Similar Documents

Publication Publication Date Title
CN109970921B (zh) 一种高减水低敏感聚羧酸减水剂及其制备方法
CN109021181A (zh) 一种兼具降粘和保坍功能的聚羧酸系减水剂及其制备方法
WO2021217762A1 (zh) 一种不饱和聚醚单体、聚羧酸减水剂及其制备方法
CN103613306B (zh) 一种含有超支化聚胺-酯结构的聚羧酸系减水剂及其制备方法
CN109627397B (zh) 一种改善水泥浆体流变特性的聚羧酸减水剂及其制备方法
CN105924592B (zh) 一种降粘型聚羧酸系减水剂及其制备方法
CN100381387C (zh) 一种两性羧酸类梳形接枝共聚物混凝土超塑化剂
CN108948288B (zh) 一种采用羧基功能单体的交联型聚羧酸减水剂制备方法
GB2443923A (en) A polymeric set retarder for use in a wellbore cement composition
CN108794700A (zh) 一种羧酸基聚合物及其制备方法和缓释型聚羧酸减水剂
CN103554496B (zh) 一种缓凝保塑型聚羧酸减水剂及其制备方法
CN107325236A (zh) 一种非泥土敏感型聚羧酸减水剂及其制备方法
CN111592272A (zh) 一种机制砂混凝土预应力构件用聚羧酸减水剂及其制备方法
WO2019233085A1 (zh) 一种含磷聚羧酸减水剂及其制备方法
WO2024104063A1 (zh) 一种新型聚羧酸减水剂及其制备方法
CN107652405A (zh) 一种酰胺/酰亚胺结构的聚羧酸减水剂及其制备方法
CN110845672A (zh) 一种聚羧酸系混凝土减胶剂及其制备方法
CN111548459A (zh) 一种高保坍型聚羧酸减水剂的制备方法
CN111349199B (zh) 一种具有核壳结构的稳态聚羧酸超塑化剂及其制备方法
CN109942754B (zh) 原子转移自由基聚合制备缓凝型超塑化剂的方法
CN108530587B (zh) 一种酯类保水触变型聚羧酸减水剂的制备方法
CN110627972A (zh) 新型抗泥聚醚类聚羧酸减水剂及其常温合成工艺
CN114163577A (zh) 一种降粘减水剂及其制备方法与应用
CN114213597A (zh) 一种具有高减水率的缓释型聚羧酸减水剂及其制备方法
JPS62216950A (ja) セメント用分散剤

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23890499

Country of ref document: EP

Kind code of ref document: A1