CN110938183A - ATRP (atom transfer radical polymerization) preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization - Google Patents
ATRP (atom transfer radical polymerization) preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- 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
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- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- 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
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- 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
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- C08F4/00—Polymerisation catalysts
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- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals
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- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
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- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Abstract
The invention discloses an ATRP (atom transfer radical polymerization) preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization, wherein the polycarboxylic acid water reducing agent is prepared from the following materials: 345 parts of polyether macromonomer, 20-28 parts of alkyl acrylate, 5-10 parts of phenyl monomer, 12-18 parts of hydroxyl monomer, 0.8-1.5 parts of initiator, 0.6-0.9 part of chain transfer agent, 0.8-1.5 parts of ligand, 0.02-0.1 part of catalyst and the balance of water, wherein the phenyl monomer, the hydroxyl monomer, the initiator and the chain transfer agent are subjected to free radical polymerization at the temperature of 60-70 ℃, the temperature is kept for 1h after the reaction is finished, and chlorine is introduced for halogenation under the illumination condition after nitrogen is introduced for 5min to obtain halogenated polymer I. And then placing the polyether macromonomer, alkyl acrylate, 0.8-1.5 ligand and 0.02-0.1 catalyst at the bottom of a second reaction kettle, dropwise adding the halogenated polymer I into the second reaction kettle, controlling the temperature at 40-50 ℃, preserving heat for 1h after dropwise adding is finished, and completely reacting to obtain the polycarboxylic acid slump retaining agent. The polycarboxylic acid slump retaining agent prepared by the method disclosed by the invention is narrow in molecular mass distribution, high in effective component and strong in slump retaining capability.
Description
Technical Field
The invention belongs to the technical field of building materials, and relates to a preparation method of a polycarboxylic acid slump retaining agent, in particular to an ATRP (atom transfer radical polymerization) preparation method of a polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization.
Background
The concrete admixture is a substance which is added for improving and adjusting the performance of concrete, can regulate and control the rheological property of the concrete, improve the mechanical property and improve the durability, and provides powerful guarantee for the quality of large-scale engineering, so that the concrete admixture is widely applied as the 3 rd major breakthrough of the concrete technology after reinforced concrete and prestressed concrete. Concrete is a building material with the widest application and the largest dosage in civil engineering application at present. With the wide application of commercial concrete, the centralized stirring and commercial supply become the main characteristics of the commercial concrete, which requires that the concrete still has larger slump after being transported and parked for a longer time.
With the vigorous development of commercial concrete industry for construction, the concrete admixture in China is widely applied in recent years, and the polycarboxylic acid water reducing agent gradually becomes a non-replaceable component in the concrete admixture. The water reducing agents endow fresh concrete with better fluidity and strength, can basically meet construction requirements for on-site stirring, but generally have the problems of larger slump and too fast loss for commercial concrete. At present, there are many methods for solving the slump loss of concrete, and the methods are common in construction: (1) adding a retarder; (2) adding for multiple times; (3) post-doping method; (4) is used by being compounded with slump retaining agent.
Patent CN201711310750.9 discloses a concrete slump retaining agent and a preparation method thereof, belonging to the field of concrete admixtures. The main raw materials comprise a macromonomer, unsaturated acid, unsaturated ester, unsaturated amide, an initiator and a chain transfer agent, wherein the molar ratio of the macromonomer to the unsaturated acid to the unsaturated ester to the unsaturated amide is 1: 1-3.5: 1-3: 1-3, the initiator accounts for 0.5-1.8% of the total mass of the macromonomer, the unsaturated acid, the unsaturated ester and the unsaturated amide, and the chain transfer agent accounts for 0.1-0.5% of the total mass of the macromonomer, the unsaturated acid, the unsaturated ester and the unsaturated amide, wherein the macromonomer is ammonium allyl polyoxyethylene ether sulfonate. The slump retaining agent synthesized by the invention has good slump retaining performance and is convenient to produce.
Patent CN201710400769.6 discloses a concrete slump retaining agent. The material is prepared from the following components in percentage by weight: HPEG: 30-35%, acrylic acid: 0.1-0.5%, hydrogen peroxide: 0.05-0.1%, mercaptopropionic acid: 0.01-0.03%, ascorbic acid: 0.006-0.008%, hydroxy acrylate: 2-3%, sodium hydroxide: 0.1-0.2%, water: 62 to 67 percent. The invention not only improves the durability of the concrete and the slump retaining capacity of the concrete, but also is environment-friendly.
Patent CN201510930837.0 discloses a concrete slump retaining agent with super-long slump retaining function, which is a polycarboxylic acid slump retaining agent simultaneously having hydroxyl and phenyl, and the weight-average molecular weight is 20000-. The polycarboxylic slump retaining agent is prepared by carrying out free radical copolymerization on a monomer a, a monomer b, a monomer c and a monomer d, wherein the molar ratio of the monomer a to the monomer b to the monomer c to the monomer d is 1: 1-10: 2-8: 2-10; dropwise adding monomers at different time periods, wherein the monomers b only participate in the reaction within the initial dropwise adding time, and a uniform dropwise adding mode is adopted; and the monomer c and the monomer d all participate in the reaction in a variable-speed dripping mode. The concrete slump retaining agent disclosed by the invention can meet the requirement of long-time slump retaining (more than 4 h) of concrete under the conditions of high temperature and long-distance transportation.
Different from the patents, the invention uses ATRP method to prepare the polycarboxylic slump retaining agent, compared with the traditional free radical polymerization, avoids the polymer dead chain formed by chain transfer and chain termination, and realizes the living free radical polymerization. The method has the advantages that a halide initiator is not required to be added, the phenyl monomer and the hydroxyl monomer are used for preparing the hydrophilic polymer and carrying out halogenation treatment, so that the low-molecular-weight halogenated polymer is obtained, and a strong initiating effect is provided; the conversion of free radicals between active species and dormant species is controlled by the electrovalence change of transition metal and the gain and loss of halogen atoms in a polymer chain, so that the polymerization rate in the reaction process is controlled, the generation of closed chains is reduced, the reaction conditions are mild, and the polymer with single molecular weight distribution is prepared.
Disclosure of Invention
The invention aims to solve the technical problem of providing an ATRP (atom transfer radical polymerization) preparation method of polycarboxylic slump retaining agent based on phenyl hydroxyl halogenated polymerization.
The preparation method comprises the steps of taking a phenyl monomer and a hydroxyl monomer as raw materials, preparing a phenyl hydroxyl polymer through free radical polymerization, introducing chlorine for halogenation under the protection of inert gas to obtain a small-molecule halogenated initiator, and preparing the polycarboxylic acid slump retaining agent through an ATRP method under the combined action of a ligand and a catalyst. The preparation method ensures that the polymerization speed of the reaction is still higher under the condition of lower free radical concentration by controlling the activity of the free radicals and taking the transition metal as the catalyst. The transition between active species and dormant species is controlled by the electrovalence change of transition metal and the gain and loss of halogen atoms in the polymer, so that the polymerization rate in the reaction process is controlled, the generation of closed chains is reduced, the reaction conditions are mild, and the polymer with single molecular weight distribution is prepared
The technical scheme of the invention is as follows:
a preparation method of ATRP of polycarboxylic acid slump retaining agent based on halogenated polymerization of phenyl hydroxyl is characterized by comprising the following steps:
the method comprises the following steps: placing 5-10 parts of phenyl monomer, 12-18 parts of hydroxyl monomer and 100 parts of deionized water in a first reaction kettle, and dripping A, B materials for 1-2.5 hours, wherein the material A is a mixed solution of 0.8-1.5 parts of initiator and 50 parts of deionized water; the material B is a mixed solution of 0.6-0.9 part of chain transfer agent and 50 parts of deionized water; free radical polymerization is carried out at the temperature of 60-70 ℃, heat preservation is carried out for 1-2h after the reaction is finished, nitrogen is introduced for 5min, and then chlorine is introduced for halogenation for 0.5-1h under the illumination condition, thus obtaining halogenated polymer I;
step two: 345 portions of polyether macromonomer, 20 to 28 portions of alkyl acrylate, 0.8 to 1.5 portions of ATRP ligand, 0.02 to 0.1 portion of ATRP catalyst and 400 portions of water are placed at the bottom of a second reaction kettle, the temperature is raised to 40 to 50 ℃ under the protection of inert gas atmosphere, halogenated polymer I is dripped into the second reaction kettle for 2 to 3 hours, the temperature is kept for 1 to 3 hours after the dripping is finished, and the polycarboxylic acid slump retaining agent is obtained after the reaction is completed.
Preferably, the polyether macromonomer is vinyl butyl ether polyoxyethylene ether.
Preferably, the phenyl monomer is any one or more of 1-allyl-2-fluorobenzene, 1-allyl-4-fluorobenzene, styrene, 1-phenyl vinyl boric acid and 4-methoxy-2-vinyl aniline.
Preferably, the hydroxyl monomer is any one or more of propylene hydroxyl, 4- (propylene hydroxyl) benzoic acid, 2-propylene hydroxyl benzene boric acid, 4-ethylene benzene methyl hydroxyl, cinnamyl hydroxyl, (4-vinyl benzene) sulfo hydroxyl, N-dimethyl propylene hydroxyl and N, N-dimethyl methyl propylene hydroxyl.
Preferably, the ATRP ligand is one or more of N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N', N '-pentamethyl methacrylate divinyl triamine, N, N, N', N ', N' -N-butyl hexamethylacrylate trivinyl tetramine, 2-bipyridine, N, N, N ', N', N '-pentamethyl divinyl triamine, N, N, N', N ', N' -hexamethyl methacrylate trivinyl tetramine.
Preferably, the catalyst for the ATRP method is any one or more of cuprous bromide, cuprous chloride, ferrous bromide and ferrous chloride.
Preferably, the initiator is any one or more of ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile and dibenzoyl peroxide.
Preferably, the alkyl acrylate is hydroxyethyl acrylate and/or hydroxypropyl acrylate.
Preferably, the chain transfer agent is mercaptoethanol and/or mercaptopropanol.
A polycarboxylic acid slump retaining agent based on halogenated polymerization of phenyl hydroxyl, which is characterized in that: prepared by any one of the methods.
In the process of preparing the polycarboxylic acid slump retaining agent of the phenyl hydroxyl halogenation polymerization by adopting ATRP, the raw materials are mainly prepared from the following components:
polyether macromonomer: 345 and 350 parts
Alkyl acrylate: 20-28 parts of
Phenyl monomer: 5-10 parts of
Hydroxyl monomer: 12 to 18 portions of
Initiator: 0.8 to 1.5 portions of
Chain transfer agent: 0.6 to 0.9 portion
Ligand: 0.8 to 1.5 portions of
Catalyst: 0.02-0.1 portion
The balance of water, the total mass is 1000 parts, and the solid content is about 40%.
The invention has the advantages of
1. The invention synthesizes polymer blocks in an atom transfer radical polymerization mode, prepares a final polymer through continuous chain growth, takes polyether as a side chain, takes functional groups such as phenyl, hydroxyl and the like as polycarboxylic slump retaining agents of short side chain functional groups, is different from comb slump retaining agents of the traditional radical polymerization, and has a hydrophilic block polymerization structure in the slump retaining agents, and the block structure is the short side chain group. Compared with a comb-type slump retaining agent, the slump retaining agent has the advantages that the main chain is strong in flexibility, the polyether side chain is radial, larger steric hindrance is formed, ester groups are hydrolyzed into carboxyl groups in cement alkaline slurry and are adsorbed on the surfaces of cement particles, the dispersing ability is enhanced, and the slump retaining agent has stronger water reducing ability and lasting slump retaining performance.
2. Preparing a hydrophilic block polymer by free radical polymerization, preparing a 2000 molecular weight polymer by using a phenyl monomer and a hydroxyl monomer under the condition of high chain transfer agent dosage, increasing the proportion of hydrophilic groups and hydrophobic groups to obtain a hydrophilic block with proper HLB, introducing bromine gas for halogenation after the reaction is finished to obtain a halogenated polymer, initiating polymerization of a polyether macromonomer and unsaturated monomers such as alkyl acrylate and the like under the combined action of a halogenated initiator, a ligand, a catalyst and the like, and copolymerizing at 50-60 ℃ to prepare the polycarboxylic acid slump retaining agent.
3. The invention uses atom transfer radical polymerization, which is more controllable compared with the traditional radical polymerization reaction, and uses transition metal as a catalyst to ensure higher reaction polymerization speed under lower radical concentration. The transition between active species and dormant species is controlled by the electrovalence change of transition metal and the gain and loss of halogen atoms, so that the polymerization rate in the reaction process is controlled, the generation of closed chains is reduced, the reaction conditions are mild, and the polymer with single molecular weight distribution is prepared.
Detailed Description
It should be noted that, in step two of all the following examples of the present invention, the reaction is not limited to be performed under the protection of nitrogen atmosphere, and may be performed under the protection of other inert gas atmosphere, such as argon, etc.
Example 1
An ATRP preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization comprises the following steps of raw materials, wherein the total mass of the raw materials is 1000 parts, the mass fraction is about 40%, and the ATRP is mainly prepared from the following components:
vinyl butyl ether polyoxyethylene ether: 345 parts by weight of
Hydroxyethyl acrylate: 28 portions of
1-allyl-2-fluorobenzene: 5 portions of
An allyl hydroxyl group: 18 portions of
Ammonium persulfate: 1.2 parts of
Mercaptopropanol: 0.9 portion
N, N' -tetramethylethylenediamine: 0.8 portion of
Cuprous bromide: 0.1 part
The balance of water.
The method comprises the following steps: placing 5 parts of 1-allyl-2-fluorobenzene, 18 parts of propylene hydroxyl and 100 parts of deionized water in a first reaction kettle, and dropwise adding A, B materials for 2 hours, wherein the material A is a mixed solution of 1.2 parts of ammonium persulfate and 50 parts of deionized water; the material B is a mixed solution of 0.9 part of mercaptopropanol and 50 parts of deionized water; free radical polymerization is carried out at the temperature of 60 ℃, heat preservation is carried out for 1h after the reaction is finished, nitrogen is introduced for 5min, and then chlorine is introduced for halogenation for 0.5h under the illumination condition, thus obtaining halogenated polymer I;
step two: putting 345 parts of vinyl butyl ether polyoxyethylene ether, 28 parts of hydroxyethyl acrylate, 0.8 part of N, N, N ', N' -tetramethylethylenediamine, 0.1 part of cuprous bromide and 400 parts of water at the bottom of a second reaction kettle, flushing nitrogen, repeatedly removing oxygen for 3-5 times, heating to 50 ℃ under the protection of nitrogen, dropwise adding the halogenated polymer I into the second reaction kettle for 2.5 hours, preserving heat for 1 hour after dropwise adding is finished, and completely reacting to obtain the polycarboxylic acid slump retaining agent.
Example 2
An ATRP preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization comprises the following steps of raw materials, wherein the total mass of the raw materials is 1000 parts, the mass fraction is about 40%, and the ATRP is mainly prepared from the following components:
vinyl butyl ether polyoxyethylene ether: 347 parts by weight
Hydroxypropyl acrylate: 27 portions of
1-allyl-4-fluorobenzene: 10 portions of
4- (allyloxy) benzoic acid: 12 portions of
Azobisisobutyronitrile: 1.5 parts of
Mercaptoethanol: 0.6 part
N, N ', N ", N' -pentamethylmethacrylate divinyltriamine: 1.1 parts of
Cuprous chloride: 0.05 part
The balance of water.
The method comprises the following steps: placing 10 parts of 1-allyl-4-fluorobenzene, 12 parts of 4- (allyloxy) benzoic acid and 100 parts of deionized water in a first reaction kettle, and dropwise adding A, B materials for 1.5 hours, wherein the material A is a mixed solution of 1.5 parts of azobisisobutyronitrile and 50 parts of deionized water; the material B is a mixed solution of 0.6 part of mercaptoethanol and 50 parts of deionized water; free radical polymerization is carried out at 70 ℃, heat preservation is carried out for 1h after the reaction is finished, nitrogen is introduced for 5min, and then chlorine is introduced to carry out halogenation for 0.5h under the illumination condition, thus obtaining halogenated polymer I;
step two: putting 347 parts of vinyl butyl ether polyoxyethylene ether, 27 parts of hydroxypropyl acrylate, 1.1 parts of N, N, N ', N' -pentamethyl methyl methacrylate divinyl triamine, 0.05 part of cuprous chloride and 400 parts of water at the bottom of a second reaction kettle, flushing nitrogen, repeatedly removing oxygen for 3-5 times, heating to 45 ℃ under the protection of nitrogen, dropwise adding a halogenated polymer I into the second reaction kettle for 3 hours, preserving heat for 1 hour after dropwise adding is finished, and completely reacting to obtain the polycarboxylic acid slump retaining agent.
Example 3
An ATRP preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization comprises the following steps of raw materials, wherein the total mass of the raw materials is 1000 parts, the mass fraction is about 40%, and the ATRP is mainly prepared from the following components:
vinyl butyl ether polyoxyethylene ether: 349 parts of
Hydroxyethyl acrylate: 26 portions of
Styrene: 7 portions of
2-Propenyloxybenzoic acid: 13 portions of
Azobisisoheptonitrile: 1.3 parts of
Mercaptopropanol: 0.8 portion of
N, N, N ', N ', N ' -N-butylhexamethylacrylate triethylenetetramine: 1.5 parts of
Cuprous bromide: 0.02 portion
The balance of water.
The method comprises the following steps: placing 7 parts of styrene, 13 parts of 2-propylene oxybenzene boric acid and 100 parts of deionized water in a first reaction kettle, and dripping A, B materials for 1 hour, wherein the material A is a mixed solution of 1.3 parts of azodiisoheptanonitrile and 50 parts of deionized water; the material B is a mixed solution of 0.8 part of mercaptopropanol and 50 parts of deionized water; free radical polymerization is carried out at 70 ℃, heat preservation is carried out for 1h after the reaction is finished, nitrogen is introduced for 5min, and then chlorine is introduced to carry out halogenation for 0.5h under the illumination condition, thus obtaining halogenated polymer I;
step two: 349 parts of vinyl butyl ether polyoxyethylene ether, 26 parts of hydroxyethyl acrylate, 1.5 parts of N, N, N ', N ', N ' -N-butyl methacrylate trivinyl tetramine, 0.02 part of cuprous bromide and 400 parts of water are placed at the bottom of a second reaction kettle, nitrogen is injected into the reaction kettle for 3-5 times to remove oxygen, the temperature is raised to 60 ℃ under the protection of the nitrogen, a halogenated polymer I is dropwise added into the second reaction kettle for 2 hours, heat preservation is carried out for 1 hour after dropwise addition is finished, and the polycarboxylic acid slump retaining agent is completely obtained after reaction.
Example 4
An ATRP preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization comprises the following steps of raw materials, wherein the total mass of the raw materials is 1000 parts, the mass fraction is about 40%, and the ATRP is mainly prepared from the following components:
vinyl butyl ether polyoxyethylene ether: 351 parts by weight of
Hydroxypropyl acrylate: 24 portions of
1-phenyl vinyl boronic acid: 6 portions of
4-vinylbenzyl hydroxide: 16 portions of
Azobisisovaleronitrile: 1.0 part
Mercaptoethanol: 0.7 portion of
2, 2-bipyridine: 1.2 parts of
Ferrous bromide: 0.08 portion of
The balance of water.
The method comprises the following steps: placing 6 parts of 1-phenyl vinyl boric acid, 16 parts of 4-vinyl benzene formoxyl and 100 parts of deionized water in a first reaction kettle, and dropwise adding A, B materials for 2 hours, wherein the material A is a mixed solution of 1.0 part of azobisisovaleronitrile and 50 parts of deionized water; the material B is a mixed solution of 0.7 part of mercaptoethanol and 50 parts of deionized water; free radical polymerization is carried out at the temperature of 65 ℃, heat preservation is carried out for 1h after the reaction is finished, nitrogen is introduced for 5min, and then chlorine is introduced for halogenation for 0.5h under the illumination condition, thus obtaining halogenated polymer I;
step two: putting 351 parts of vinyl butyl ether polyoxyethylene ether, 24 parts of hydroxypropyl acrylate, 1.2 parts of 2, 2-bipyridine, 0.08 part of ferrous bromide and 400 parts of water at the bottom of a second reaction kettle, flushing nitrogen gas, repeatedly removing oxygen for 3-5 times, heating to 50 ℃ under the protection of the nitrogen gas, dropwise adding a halogenated polymer I into the second reaction kettle for 3 hours, preserving heat for 1 hour after dropwise adding is finished, and completely reacting to obtain the polycarboxylic acid slump retaining agent.
Example 5
An ATRP preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization comprises the following steps of raw materials, wherein the total mass of the raw materials is 1000 parts, the mass fraction is about 40%, and the ATRP is mainly prepared from the following components:
vinyl butyl ether polyoxyethylene ether: 353 parts of
Hydroxyethyl acrylate: 22 portions of
4-methoxy-2-vinylaniline: 8 portions of
Cinnamon hydroxyl: 15 portions of
Dibenzoyl peroxide: 0.8 portion of
Mercaptopropanol: 0.8 portion of
N, N', N "-pentamethyldivinyltriamine: 0.9 portion
Cuprous chloride: 0.06 part
The balance of water.
The method comprises the following steps: placing 8 parts of 4-methoxy-2-vinylaniline, 15 parts of cinnamon hydroxyl and 100 parts of deionized water in a first reaction kettle, and dropwise adding A, B materials for 1.5 hours, wherein the material A is a mixed solution of 0.8 part of dibenzoyl peroxide and 50 parts of deionized water; the material B is a mixed solution of 0.8 part of mercaptopropanol and 50 parts of deionized water; free radical polymerization is carried out at 70 ℃, heat preservation is carried out for 1h after the reaction is finished, nitrogen is introduced for 5min, and then chlorine is introduced to carry out halogenation for 0.5h under the illumination condition, thus obtaining halogenated polymer I;
step two: placing 353 parts of vinyl butyl ether polyoxyethylene ether, 22 parts of hydroxyethyl acrylate, 0.9 part of N, N, N ', N ', N ' -pentamethyl divinyl triamine, 0.06 part of cuprous chloride and 400 parts of water at the bottom of a second reaction kettle, flushing nitrogen, repeatedly removing oxygen for 3-5 times, heating to 45 ℃ under the protection of nitrogen, dropwise adding the halogenated polymer I into the second reaction kettle for 2.5 hours, and preserving heat for 1 hour after dropwise adding is finished, thus obtaining the polycarboxylic acid slump retaining agent after complete reaction.
Example 6
An ATRP preparation method of polycarboxylic acid slump retaining agent based on phenyl hydroxyl halogenation polymerization comprises the following steps of raw materials, wherein the total mass of the raw materials is 1000 parts, the mass fraction is about 40%, and the ATRP is mainly prepared from the following components:
vinyl butyl ether polyoxyethylene ether: 355 parts of
Hydroxypropyl acrylate: 20 portions of
4-methoxy-2-vinylaniline: 9 portions of
(4-vinylbenzene) sulfonic acid: 13 portions of
Dibenzoyl peroxide: 0.9 portion
Mercaptoethanol: 0.7 portion of
N, N, N ', N ', N ' -hexamethyl methacrylate triethylenetetramine: 1.4 parts of
Ferrous chloride: 0.07 part of
The balance of water.
The method comprises the following steps: placing 9 parts of 4-methoxy-2-vinylaniline, 13 parts of (4-vinylbenzene) sulfonyl hydroxide and 100 parts of deionized water in a first reaction kettle, and dropwise adding A, B materials for 1.5 hours, wherein the material A is a mixed solution of 0.9 part of dibenzoyl peroxide and 50 parts of deionized water; the material B is a mixed solution of 0.7 part of mercaptoethanol and 50 parts of deionized water; free radical polymerization is carried out at the temperature of 60 ℃, heat preservation is carried out for 1h after the reaction is finished, nitrogen is introduced for 5min, and then chlorine is introduced for halogenation for 0.5h under the illumination condition, thus obtaining halogenated polymer I;
step two: 355 parts of vinyl butyl ether polyoxyethylene ether, 20 parts of hydroxypropyl acrylate, 1.4 parts of N, N, N ', N ', N ' -hexamethyl methyl acrylate trivinyl tetramine, 0.07 part of ferrous chloride and 400 parts of water are placed at the bottom of a second reaction kettle, nitrogen is filled in the reaction kettle for repeatedly removing oxygen for 3-5 times, the temperature is raised to 50 ℃ under the protection of the nitrogen, a halogenated polymer I is dropwise added into the second reaction kettle for 2 hours, the temperature is kept for 1 hour after the dropwise addition is finished, and the polycarboxylic acid slump retaining agent is completely obtained after the reaction.
The polycarboxylic acid slump retaining agent prepared by the above example and the common polycarboxylic acid slump retaining agent are prepared into slump retaining agents with the same concentration, and the influence of different slump retaining agents with the same concentration and different formulas on the performance of concrete under the same condition is tested respectively. The cement used in the experiment is Huaxin 42.5 ordinary silica cement, and the test standard GB/8076-.
Effect of different slump-retaining agents on concrete Performance
According to the influence table of different slump retaining agents on the performance of concrete, the compression strength and the slump/expansion degree of different slump retaining agents are obviously reflected, the 3d strength and the 7d strength of the polycarboxylic acid slump retaining agent in the example 2 are both greater than the corresponding age strength of a common polycarboxylic acid slump retaining agent, and the 28d strength is relatively slowly improved; where example 4 is best in strength and slump/spread and strength has an early strength effect, the formulation and preparation process of example 4 is most preferred. The polycarboxylic acid slump retaining agent prepared by the ATRP method has better performance, has great significance to concrete engineering, and enriches the preparation and application of concrete additives.
Claims (10)
1. A preparation method of ATRP of polycarboxylic acid slump retaining agent based on halogenated polymerization of phenyl hydroxyl is characterized by comprising the following steps:
the method comprises the following steps: placing 5-10 parts of phenyl monomer, 12-18 parts of hydroxyl monomer and 100 parts of deionized water in a first reaction kettle, and dripping A, B materials for 1-2.5 hours, wherein the material A is a mixed solution of 0.8-1.5 parts of initiator and 50 parts of deionized water; the material B is a mixed solution of 0.6-0.9 part of chain transfer agent and 50 parts of deionized water; free radical polymerization is carried out at the temperature of 60-70 ℃, heat preservation is carried out for 1-2h after the reaction is finished, nitrogen is introduced for 5min, and then chlorine is introduced for halogenation for 0.5-1h under the illumination condition, thus obtaining halogenated polymer I;
step two: 345 portions of polyether macromonomer, 20 to 28 portions of alkyl acrylate, 0.8 to 1.5 portions of ATRP ligand, 0.02 to 0.1 portion of ATRP catalyst and 400 portions of water are placed at the bottom of a second reaction kettle, the temperature is raised to 40 to 50 ℃ under the protection of inert gas atmosphere, halogenated polymer I is dripped into the second reaction kettle for 2 to 3 hours, the temperature is kept for 1 to 3 hours after the dripping is finished, and the polycarboxylic acid slump retaining agent is obtained after the reaction is completed.
2. The method for preparing ATRP of polycarboxylic acid slump retaining agent according to claim 1, wherein: the polyether macromonomer is vinyl butyl ether polyoxyethylene ether.
3. The method for preparing ATRP of polycarboxylic acid slump retaining agent according to claim 1, wherein: the phenyl monomer is any one or more of 1-allyl-2-fluorobenzene, 1-allyl-4-fluorobenzene, styrene, 1-phenyl vinyl boric acid and 4-methoxy-2-vinyl aniline.
4. The method for preparing ATRP of polycarboxylic acid slump retaining agent according to claim 1, wherein: the hydroxyl monomer is any one or more of propylene hydroxyl, 4- (propylene hydroxyl) benzoic acid, 2-propylene hydroxyl benzene boric acid, 4-ethylene benzene methyl hydroxyl, cinnamon hydroxyl, (4-vinyl benzene) sulfo hydroxyl, N-dimethyl propylene hydroxyl and N, N-dimethyl methyl propylene hydroxyl.
5. The method for preparing ATRP of polycarboxylic acid slump retaining agent according to claim 1, wherein: the ligand of the ATRP method is any one or more of N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N', N '-pentamethyl methacrylate divinyl triamine, N, N, N', N ', N' -N-butyl hexamethylacrylate trivinyl tetramine, 2-bipyridine, N, N, N ', N', N '-pentamethyl divinyl triamine, N, N, N', N ', N' -methyl hexamethylacrylate trivinyl tetramine.
6. The method for preparing ATRP of polycarboxylic acid slump retaining agent according to claim 1, wherein: the catalyst of the ATRP method is any one or more of cuprous bromide, cuprous chloride, ferrous bromide and ferrous chloride.
7. The method for preparing ATRP of polycarboxylic acid slump retaining agent according to claim 1, wherein: the initiator is any one or more of ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile and dibenzoyl peroxide.
8. The method for preparing ATRP of polycarboxylic acid slump retaining agent according to claim 1, wherein: the alkyl acrylate is hydroxyethyl acrylate and/or hydroxypropyl acrylate.
9. The method for preparing ATRP of polycarboxylic acid slump retaining agent according to claim 1, wherein: the chain transfer agent is mercaptoethanol and/or mercaptopropanol.
10. A polycarboxylic acid slump retaining agent based on halogenated polymerization of phenyl hydroxyl, which is characterized in that: prepared by the process of any one of claims 1 to 9.
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| CN110922546A (en) * | 2019-11-21 | 2020-03-27 | 湖北工业大学 | Phenyl hydroxyl compound ATRP method modified polycarboxylic acid slump retaining agent and preparation method thereof |
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