CN109369858B - Super-strong adsorption type concrete rheological agent and preparation method thereof - Google Patents

Super-strong adsorption type concrete rheological agent and preparation method thereof Download PDF

Info

Publication number
CN109369858B
CN109369858B CN201810851245.3A CN201810851245A CN109369858B CN 109369858 B CN109369858 B CN 109369858B CN 201810851245 A CN201810851245 A CN 201810851245A CN 109369858 B CN109369858 B CN 109369858B
Authority
CN
China
Prior art keywords
methyl
amine
terminated polyether
super
rheological agent
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN201810851245.3A
Other languages
Chinese (zh)
Other versions
CN109369858A (en
Inventor
王子明
钱珊珊
崔素萍
王亚丽
毛倩瑾
刘晓
姚燕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
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 Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN201810851245.3A priority Critical patent/CN109369858B/en
Publication of CN109369858A publication Critical patent/CN109369858A/en
Application granted granted Critical
Publication of CN109369858B publication Critical patent/CN109369858B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Abstract

The invention discloses a super-strong adsorption type concrete rheological agent and a preparation method thereof, wherein the weight average molecular weight of the rheological agent is 20000-80000. The rheological agent is prepared by the following method: firstly, carrying out amino-epoxy ring-opening polymerization reaction on amine-terminated polyether and diepoxy oxide to obtain a polymer with a side chain grafted by the amine-terminated polyether, then carrying out esterification reaction modification on hydroxyl generated by the amino-epoxy ring-opening polymerization reaction by using halogenated alkyl acyl halide to obtain halogen-terminated polyether, and finally carrying out Atom Transfer Radical Polymerization (ATRP) to obtain the super-strong adsorption type concrete rheological agent. The super-strong adsorptive concrete rheological agent prepared by the method improves the dispersion performance by utilizing a large number of adsorption groups to enhance electrostatic repulsion, and improves the dispersion retention capacity by utilizing strong steric hindrance. The method has the advantages of good controllability of the production process, less side reaction, strong adaptability to different cement varieties, high water reducing rate, high cost performance, obvious competitive advantage and the like.

Description

Super-strong adsorption type concrete rheological agent and preparation method thereof
Technical Field
The invention relates to the technical field of water reducing agents for cement concrete, in particular to a method for preparing a water reducing agent by combining amino-epoxy ring-opening polymerization reaction and Atom Transfer Radical Polymerization (ATRP).
Background
For the dispersibility, slump retaining capacity and action mechanism of the polycarboxylic acid water reducing agent, scientific researchers at home and abroad carry out extensive research on the polycarboxylic acid water reducing agent, and a plurality of research achievements are obtained, and the relatively consistent view is as follows: the polycarboxylic acid water reducing agent mainly plays a role in dispersing cement particles through steric hindrance, but the electrostatic repulsion function is not negligible and is related to the molecular structure of the water reducing agent. The premise that the polycarboxylate superplasticizer has dispersibility is that the polycarboxylate superplasticizer is adsorbed on the surfaces of cement particles, which inevitably influences the contact state of the cement particles and water, thereby influencing the hydration process of cement and directly relating to the compatibility of the polycarboxylate superplasticizer and the cement.
CN105504175A reports a preparation method of polycarboxylic acid water reducer with polyacrylic acid as side chain: the polyacrylic acid is obtained by taking polyacrylic acid in methallyl polyacrylic acid as a side chain and hydroxyethyl acrylate as a main chain through polymerization reaction, wherein the preparation process of the methallyl polyacrylic acid is as follows: (1) adding tert-butyl acrylate, ethyl dibromoisobutyrate and PMDETA into a reactor by using 1, 4-dioxane as a solvent, freezing the solution into liquid nitrogen to form a solid, adding refined cuprous bromide into the reactor, vacuumizing the reactor by using a vacuum pump, and finally reacting for 12 hours at 100 ℃; after the reaction is finished, pouring the product into a beaker, fully oxidizing the product in the air until the color of the product is changed into dark green, then pouring the product into a column filled with neutral alumina, and collecting yellow liquid at the bottom of the column to obtain a crude product; precipitating the crude product in ice water to obtain a light yellow solid, namely the product poly (tert-butyl acrylate); wherein the molar ratio of tert-butyl acrylate, ethyl dibromoisobutyrate, PMDETA and cuprous bromide is (50-150) to 1:3: 3; (2) adding isobutene alcohol and sodium hydride into a reactor to react by taking DMF as a solvent until no bubbles appear in the reactor to generate sodium alkoxide; slowly dripping tert-butyl polyacrylate into sodium alkoxide, and reacting for 6 hours at 40 ℃; then filtering the obtained product to remove unreacted sodium hydride, precipitating the filtered solution in ice water to obtain light yellow solid powder, namely the methyl allyl poly-tert-butyl acrylate product; wherein the molar ratio of poly (tert-butyl acrylate), isobutene alcohol and sodium hydride is 1:1: 1; (3) and (3) taking dichloromethane as a solvent, adding tert-butyl methallyl polyacrylate and trifluoroacetic acid into a reactor for reaction for 2 hours, and removing the solvent and the trifluoroacetic acid after the reaction is finished to obtain a white solid, namely the product methallyl polyacrylic acid. The whole preparation engineering process is complex, the operation is complex, a large amount of organic solvents are used, the preparation cost is high, the reaction conditions are harsh, the product yield is low, and the industrial production is difficult.
Aiming at the defects and problems in the prior art, the invention utilizes the amino-epoxy ring-opening polymerization reaction and adjusts the structure and the spatial arrangement of the molecular side chain of the water reducing agent effectively by adjusting the amine-terminated polyether with different structures/weight average molecular weights, changes the performance of the polycarboxylic acid water reducing agent and increases the super-strong adsorption and dispersion functions of the polycarboxylic acid water reducing agent under the condition of not influencing the inherent performance of the polycarboxylic acid water reducing agent. The main chain of the water reducing agent obtained by the method of the invention is provided with a large number of adsorption groups, so that not only is strong adsorption dispersion ensured, but also the steric effect is ensured. The water reducing agent prepared by the method is easier to adsorb on the surface of cement particles, and can improve the dispersion and dispersion stability of the cement particles.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a super-adsorption type concrete rheological agent and a preparation method thereof, and the method can be used for endowing a water reducing agent with new functions.
The method for synthesizing amine-terminated polyether by using amino-epoxy ring-opening polymerization reaction and the application thereof in the synthesis of the water reducing agent comprise the following steps:
1. a molecular structure of amine-terminated polyether is shown as a structural formula 1:
Figure BDA0001747568460000021
wherein R is1The polyether monomer is H or methyl, m, n and p are integers which are more than or equal to zero, m + n + p is more than or equal to 6 and less than or equal to 68, m, n and p are not 0 at the same time, and the weight average molecular weight of the polyether monomer is 500-3000.
2. A super-strong adsorption type concrete rheological agent has a molecular structure shown as a structural formula 2:
Figure BDA0001747568460000022
wherein R is1Is H or methyl; r2Is aliphatic, alicyclic or aromatic; r4Is H, methyl or aromatic; r5、R6Is H, aliphatic, alicyclic or aromatic; x is Cl, Br, or I; z is O or N, m, N and p are integers which are more than or equal to zero, m + N + p is more than or equal to 6 and less than or equal to 68, and m, N and p are not 0 at the same time; q is 1-30; k is 5-110, and the weight average molecular weight of the super-adsorption type concrete rheological agent is 20000-80000.
3. The preparation method of the super-strong concrete rheological agent comprises the following steps:
1) preparation of halogen-terminated polyether (ATRP initiator):
stirring the amine-terminated polyether and the diepoxy oxide at normal temperature and pressure for 1-5 h to perform an amine-epoxy ring-opening polymerization reaction, grafting the amine-terminated polyether on a main chain to form a polymer of a side chain, dehydrating and drying the amine-terminated polyether after the reaction is finished, and adding halogenated alkyl acyl halide to perform an esterification reaction for 0.5-1 h to obtain an end halogen-based polyether (ATRP initiator), wherein the molar ratio of the amine-terminated polyether to the diepoxy oxide to the halogenated alkyl acyl halide is 1: (1.01-1.1): (2.01-2.2).
2) Preparing a super-strong adsorption concrete rheological agent:
reacting the halogen-terminated polyether (ATRP initiator) obtained in the step 2), the carbonyl-containing unsaturated monomer and the transition metal complex at 50-80 ℃ for 30-240 min, and adding alkali to adjust the pH value to 6-7 to obtain the super-strong adsorption type concrete rheological agent; wherein the mol ratio of the halogen-terminated polyether (ATRP initiator), the carbonyl-containing unsaturated monomer and the transition metal complex is 1: (2-60): (0.01-0.1).
4. In the method of the present invention, the diepoxide in the step 1) is 1, 3-butadiene diepoxide, 1, 5-hexadiene diepoxide, bis (2, 3-epoxycyclopentyl) ether, vinylcyclohexene oxide, diisopropadiene diepoxide, one or more of dicyclopentadiene diepoxide, 3, 4-epoxy-6-methyl cyclohexyl formic acid-3 ', 4' -epoxy-6 '-methyl cyclohexyl methyl ester, 3, 4-epoxy-6-cyclohexyl formic acid-3', 4 '-epoxy-6' -methyl cyclohexyl methyl ester, adipic acid di (3, 4-epoxy-6-methyl cyclohexyl methyl ester) and phthalic acid diglycidyl ester.
5. In the method, the halogenated alkyl acyl halide in the step 1) is one or the combination of more than two of 2-bromo isobutyryl bromide, 2-bromo isobutyryl chloride, 2-chloro propionyl chloride and 2-bromo propionyl chloride.
6. In the method of the present invention, the unsaturated monomer containing carbonyl group in step 2) is acrylic acid, sodium acrylate, methacrylic acid, sodium methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, propyl methacrylate, ethyl methacrylate, methyl methacrylate, hydroxy-N-butyl methacrylate, acrylamide, N-methacrylamide, N-ethylacrylamide, N-dimethylacrylamide, N-diethyl 2-acrylamide, 2-vinylbenzoic acid, 2-vinylphenylacetic acid, 4-vinylbenzoic acid, or, One or more than two of 4-vinyl methyl benzoate and 4-vinyl ethyl benzoate;
7. in the method of the present invention, the transition metal complex described in step 2); is CuBr/Pentamethyldiethylenetriamine (PMDETA), CuCl/HMTETA, CuBr/tetra [ (2-pyridyl) methyl group]Ethylenediamine (TPEN), CuBr/tris [2- (dimethylamino) ethyl group]Amine (Me)6TREN), CuCl/Pentamethyldiethylenetriamine (PMDETA), CuBr/HMTETA, CuCl/tetrakis [ (2-pyridyl) methyl group]Ethylenediamine (TPEN), CuCl/tris [2- (dimethylamino) ethyl ] methyl]Amine (Me)6TREN) or a combination of several kinds.
8. In the method, the alkali in the step 2) is one or the combination of more than two of sodium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium tert-butoxide and potassium tert-butoxide.
The preparation process of the super-strong adsorption type concrete rheological agent comprises the steps of firstly carrying out amino-epoxy ring-opening polymerization reaction on amine-terminated polyether and diepoxide, effectively reducing the reaction difficulty, having rapid and efficient reaction, no toxicity or pollution and simple operation, modifying hydroxyl generated by the amino-epoxy ring-opening polymerization reaction into halogen, and carrying out Atom Transfer Radical Polymerization (ATRP) reaction with carbonyl-containing unsaturated monomers to obtain the strong adsorption type concrete rheological agent with controllable weight average molecular weight and weight average molecular weight distribution coefficient. The strong adsorption type concrete rheological agent prepared by the method is a functional polycarboxylic acid high-efficiency water reducing agent, and has high conversion rate and more excellent performance.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the water reducing agent prepared by the method disclosed by the invention keeps the advantages of the existing water reducing agent, and has the advantages of simple production process, safety, good controllability, good cost performance and competitive advantage.
2. The water reducing agent prepared by the method can reduce the production of byproducts and obviously improve the purity of products due to the amino-epoxy ring-opening polymerization reaction.
3. The amine-terminated polyether prepared by the method can have different block structures, and the water reducing agent product with corresponding performance can be obtained by adjusting the position of the block structure and the change of the block number.
4. The concrete prepared by the invention has a novel structure and excellent concrete rheological property.
5. The unsaturated polyether prepared by the invention has a multi-component system of ethylene oxide-propylene oxide-butylene oxide, and oxygen atoms on a polyoxyethylene molecular chain and hydrogen atoms of water molecules form hydrogen bonds in an aqueous medium to extend the molecular chain, so that the reaction activity of double bonds in a branched chain is ensured. Molecular chains of polyoxypropylene and polyoxybutylene are easy to curl and fold, and hydrophobic methyl is far away from water molecules, so that the steric effect is increased, and the dispersibility and slump retaining property of the concrete rheological agent are improved.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
1) Preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1And m and n are zero, p is 10, the weight-average molecular weight is 500), 11mol of 1, 3-butadiene diepoxide is stirred for 5 hours at normal temperature and normal pressure to carry out amino-epoxy ring-opening polymerization reaction, the end amino polyether is grafted into a polymer of a side chain on a main chain, and after the reaction is finished, 22mol of 2-bromoisobutyryl chloride is added for esterification reaction for 0.5 hour after dehydration and drying, so that the end bromo polyether (ATRP initiator) is obtained.
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of bromine-terminated polyether (ATRP initiator), 20mol of acrylic acid and 0.1mol of CuBr/Pentamethyldiethylenetriamine (PMDETA) are reacted for 120min at 50 ℃, and sodium hydroxide is added to adjust the pH value to be 6, thus obtaining the super-strong adsorption type concrete rheological agent (R of the super-strong adsorption type concrete rheological agent1Is methyl, R2Is ethylene, R3Is isobutyl, R4、R5、R6Is H; x is Br, Z is O, m, n are all zero, p is 10, q is 10, k is 9, weight average molecular weight 20000).
Example 2
1) Preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1M and n are zero, p is 17, the weight-average molecular weight is 800), 10.1mol of 1, 5-hexadiene diepoxide is stirred for 1h at normal temperature and normal pressure to carry out amino-epoxy ring-opening polymerization reaction, the end amino polyether is grafted into a polymer of a side chain on a main chain, and after the reaction is finished, 20.1mol of 2-bromo isobutyryl bromide is added to carry out esterification reaction for 0.1h to obtain the end bromo polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
reacting 10mol of bromine-terminated polyether (ATRP initiator), 26mol of methacrylic acid and 0.2mol of CuCl/HMTETA at 55 ℃ for 240min, and adding sodium methoxide to adjust the pH value to 7 to obtain the productSuper-strong adsorption type concrete rheological agent (R thereof)1Is methyl, R2Is butylene, R3Is isobutyl, R4Is methyl, R5Is H, no R6X is Br, Z is O, m, n are all zero, p is 10, q is 13, k is 10, and weight average molecular weight is 40000).
Example 3:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1The method comprises the steps of stirring for 5 hours at normal temperature and pressure to carry out amino-epoxy ring opening polymerization reaction on methyl, m is 0, n is 7, p is 10, the weight average molecular weight is 1000 and 10.2mol of bis (2, 3-epoxy cyclopentyl) ether to realize that amine-terminated polyether is grafted to a polymer of a side chain on a main chain, and after the reaction is finished, adding 21.1mol of 2-bromoisobutyryl chloride to carry out esterification reaction for 0.9 hour to obtain the bromine-terminated polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of bromine-terminated polyether (ATRP initiator), 30mol of hydroxymethyl acrylate and 0.3mol of CuBr/tetra [ (2-pyridyl) methyl]Reacting ethylenediamine (TPEN) at 60 deg.C for 90min, adding sodium ethoxide to adjust pH to 7 to obtain super-strong adsorption type concrete rheological agent (R of the agent)1Is methyl, R2Is (2, 3-epoxycyclopentyl) ether group, R3Is isobutyl, R4Is H, R5Is methyl, no R6X is Br, Z is O, m is 0, n is 7, p is 10, q is 15, k is 9, and the weight average molecular weight is 50000).
Example 4:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1Stirring H, n is 0, m is 6, p is 20, the weight average molecular weight is 1200) and 10.3mol of vinylcyclohexene oxide at normal temperature and normal pressure for 4.5H to carry out amino-epoxy ring opening polymerization reaction, grafting amine-terminated polyether on a main chain to form a polymer of a side chain, dehydrating and drying the polymer after the reaction is finished, and adding 21mol of 2-chloroisobutyryl chloride to carry out esterification reaction for 0.7H to obtain chlorine-terminated polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of chlorine-terminated polyether (ATRP initiator), 44mol of hydroxyethyl acrylate and 0.4mol of CuBr/tris [2- (dimethylamino) ethyl ester]Amine (Me)6TREN) reacting at 65 deg.C for 60min, adding potassium methoxide to adjust pH to 6 to obtain super-strong adsorption type concrete rheological agent (R of the agent1Is H, R2Is vinylcyclohexyl, R3Is isobutyl, R4Is H, R5Is ethyl, free of R6X is Cl, Z is O, n is 0, m is 6, p is 20, q is 22, k is 11, and the weight average molecular weight is 60000).
Example 5:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1The method is characterized in that m is 0, n is 4, p is 40, the weight average molecular weight is 2000), 10.4mol of diisopropadiene diepoxide is stirred for 2.5h at normal temperature and normal pressure to carry out amino-epoxy ring-opening polymerization reaction, the end amino polyether is grafted into a polymer of a side chain on a main chain, and after the reaction is finished, 20.9mol of 2-bromopropionyl chloride is added for esterification reaction for 0.6h after dehydration and drying, so that the end bromo polyether (ATRP initiator) is obtained.
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of bromine-terminated polyether (ATRP initiator), 50mol of acrylamide and 0.5mol of CuCl/pentamethyl diethylenetriamine (PMDETA) are reacted for 30min at 70 ℃, potassium tert-butoxide is added to adjust the pH value to 7, and the super-strong adsorption type concrete rheological agent (R of which is the R of the super-strong adsorption type concrete rheological agent) is obtained1Is methyl, R2Is a diisoprenyl radical, R3Is propyl, R4、R5、R6Is H; x is Br, Z is N, m is 0, N is 4, p is 40, q is 25, k is 9, and the weight average molecular weight is 70000).
Example 6:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1Stirring m is 4, n is 0, p is 50, weight average molecular weight is 2400), 0.5mol dicyclopentadiene diepoxide for 1.5h at normal temperature and pressure to carry out amino-epoxy ring-opening polymerization reaction, thus realizing amine-terminated polyetherGrafting a polymer with a side chain on a main chain, dehydrating and drying after the reaction is finished, and adding 20.8mol of 2-bromoisobutyryl bromide to carry out esterification reaction for 0.5h to obtain the end bromo polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of bromine-terminated polyether (ATRP initiator), 60mol of N-methacrylamide, 0.6mol of CuBr/HMTETA, react for 240min at 75 ℃, and sodium tert-butoxide is added to adjust the pH value to be 6, thus obtaining the super-strong adsorption type concrete rheological agent (R of the super-strong adsorption type concrete rheological agent)1Is hydrogen, R2Is pentylene, R3Is isobutyl, R4Is methyl, R5、R6Is H, X is Br, Z is N, m is 4, N is 0, p is 50, q is 30, k is 8, weight average molecular weight 80000).
Example 7:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1The preparation method comprises the steps of stirring 3, 4-epoxy-6-methyl cyclohexyl formate-3 ', 4' -epoxy-6 '-methyl cyclohexyl methyl ester at normal temperature and pressure for 2.5 hours to carry out amino-epoxy ring-opening polymerization reaction, wherein m is 3, n is 5, p is 55, the weight average molecular weight is 3000), 10.6mol of 3, 4-epoxy-6-methyl cyclohexyl formate-3', 4 '-epoxy-6' -methyl cyclohexyl methyl ester is grafted to a main chain to form a polymer of a side chain, and after the reaction is finished, 20.7mol of 2-bromoisobutyryl chloride is added to carry out esterification reaction for 1 hour to obtain the bromine-terminated polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of bromine-terminated polyether (ATRP initiator), 36mol of hydroxyethyl acrylate, small monomer and 0.7mol of CuBr/tris [2- (dimethylamino) ethyl]Amine (Me)6TREN) reacting at 80 deg.C for 210min, adding sodium methoxide to adjust pH to 7 to obtain super-strong adsorption type concrete rheological agent (R thereof)1Is methyl, R2Is 6-methylcyclohexanecarboxylic acid-6' -methylcyclohexylmethylcarboxylate, R3Is isobutyl, R4Is H, R5Is ethyl, free of R6X is Br, Z is O, m is 3, n is 5, p is 55, p is 10, q is 13, k is 5, and the weight average molecular weight is 45000).
Example 8:
1) preparation of the halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1The polyether is methyl, m is 6, n is 0, p is 17, the weight average molecular weight is 1200), 10.7mol of 3, 4-epoxy-6-cyclohexyl formic acid-3 ', 4 ' -epoxy-6 ' -methyl cyclohexyl methyl ester is stirred for 3.5h at normal temperature and normal pressure to carry out amino-epoxy ring-opening polymerization reaction, the end amino polyether is grafted to a polymer of a side chain on a main chain, and after the reaction is finished, 20.6mol of 2-chloroisobutyryl chloride is added to carry out esterification reaction for 0.9h to obtain the chlorine-terminated polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of chlorine-terminated polyether (ATRP initiator), 18mol of hydroxypropyl acrylate and 0.8mol of CuBr/tetra [ (2-pyridyl) methyl]Reacting ethylenediamine (TPEN) at 50 deg.C for 180min, adding sodium hydroxide to adjust pH to 6 to obtain super-strong adsorption type concrete rheological agent (R of the agent)1Is methyl, R2Is 6-cyclohexanecarboxylic acid-3 ', 4 ' -epoxy-6 ' -methylcyclohexylmethane radical, R3Is isobutyl, R4Is H, R5Is propyl, free of R6X is Cl, Z is O, m is 6, n is 0, p is 17, q is 9, k is 6, and the weight average molecular weight is 35000).
Example 9:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1The method comprises the following steps of stirring m & lt2 & gt, n & lt5 & gt, p & lt3 & gt, the weight-average molecular weight of 600) and 10.8mol of adipic acid bis (3, 4-epoxy-6-methyl cyclohexyl methyl ester) for 5 hours at normal temperature and normal pressure to carry out amino-epoxy ring-opening polymerization reaction, grafting amine-terminated polyether to form a polymer of a side chain on a main chain, dehydrating and drying the polymer after the reaction is finished, and adding 20.5mol of 2-bromopropionyl chloride to carry out esterification reaction for 0.8 hour to obtain the bromine-terminated polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of bromine-terminated polyether (ATRP initiator), 20mol of 2-vinyl phenylacetic acid and 0.9mol of transition metal complex are reacted for 150min at 60 ℃, and potassium hydroxide is added to adjust the pH value to 7 to obtain the catalystSuper-strong adsorption type concrete rheological agent (R of super-strong adsorption type concrete rheological agent)1Is hydrogen, R2Is adipic acid di (6-methylcyclohexylmethyl) ester, R3Is propyl, R4、R5Is H, no R6(ii) a X is Br, Z is O, m is 2, n is 5, p is 3, q is 10, k is 7, and weight average molecular weight is 25000).
Example 10:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1The method is characterized in that m is 4, n is 19, p is 30, the weight average molecular weight is 2900), 10.9mol of diglycidyl phthalate is stirred for 3.5h at normal temperature and normal pressure to carry out amino-epoxy ring-opening polymerization reaction, the end amino polyether is grafted to a polymer of a side chain on a main chain, and after the reaction is finished, 20.4mol of 2-bromopropionyl chloride is added for esterification reaction for 0.7h to obtain the end bromo polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
reacting 10mol of bromine-terminated polyether (ATRP initiator), 50mol of acrylic acid and 0.2mol of CuCl/HMTETA at 55 ℃ for 120min, and adding sodium methoxide to adjust the pH value to be 6 to obtain the super-strong adsorption type concrete rheological agent (R of the super-strong adsorption type concrete rheological agent)1Is methyl, R2Is phthalic acid radical, R3Is propyl, R4、R5Is H, no R6X is Cl, Z is O, m is 4, n is 19, p is 30, p is 10, q is 25, k is 9, and the weight average molecular weight is 50000).
Example 11:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1The method comprises the steps of stirring for 4 hours at normal temperature and pressure to carry out amino-epoxy ring opening polymerization reaction on methyl, wherein m is 3, n is 7, p is 40, the weight average molecular weight is 2500 and 11mol of adipic acid bis (3, 4-epoxy-6-methyl cyclohexyl methyl ester) to realize that amine-terminated polyether is grafted to a polymer of a side chain on a main chain, and after the reaction is finished, adding 20.3mol of 2-chloroisobutyryl chloride to carry out esterification reaction for 0.6 hour to obtain chlorine-terminated polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of chlorine-terminated polyether (ATRP initiator), 40mol of 4-vinyl benzoic acid and 0.2mol of CuBr/HMTETA are reacted for 90min at 60 ℃, and sodium hydroxide is added to adjust the pH value to be 6, thus obtaining the super-strong adsorption type concrete rheological agent (R of the super-strong adsorption type concrete rheological agent)1Is methyl, R2Is adipic acid di (6-methylcyclohexylmethyl) ester, R3Is isobutyl, R4Is H, R5Is 4-vinylphenyl, R being absent6X is Br, Z is O, m is 3, n is 7, p is 40, q is 20, k is 8, and the weight average molecular weight is 40000).
Example 12:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1The polymer is methyl, m is 6, n is 0, p is 0, the weight average molecular weight is 500, 10.1mol of 3, 4-epoxy-6-methyl cyclohexyl formic acid-3 ', 4 ' -epoxy-6 ' -methyl cyclohexyl methyl ester is stirred for 4.5h at normal temperature and normal pressure to carry out amino-epoxy ring-opening polymerization reaction, the end amino polyether is grafted to a polymer of a side chain on a main chain, and after the reaction is finished, 20.2mol of 2-bromopropionyl chloride is added to carry out esterification reaction for 0.5h to obtain the end bromo polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of bromine-terminated polyether (ATRP initiator), 20mol of acrylic acid and 0.3mol of CuCl/tetrakis [ (2-pyridyl) methyl group]Ethylenediamine (TPEN) reacts for 60min at 70 ℃, potassium tert-butoxide is added to adjust the pH value to 6, and the super-strong adsorption type concrete rheological agent (R of the super-strong adsorption type concrete rheological agent) is obtained1Is methyl, R2Is 6-methylcyclohexanecarboxylic acid-6' -methylcyclohexylmethylcarboxylate, R3Is propyl, R4、R5Is H, no R6X is Br, Z is O, m is 6, n is 0, p is 0, q is 1, k is 110, and has a weight average molecular weight of 80000).
Example 13:
1) preparation of halogen-terminated polyether (ATRP initiator):
10mol of amine-terminated polyether (R thereof)1Hydrogen, m and n are zero, p is 68, weight average molecular weight is 3000), 10.8mol phthalic acid diglycidylAnd (3) stirring the ester at normal temperature and pressure for 5 hours to carry out amido-epoxy ring-opening polymerization reaction to graft the terminal amido polyether on the main chain to form a side chain polymer, and after the reaction is finished, adding 20.1mol of 2-chloropropionyl chloride to carry out esterification reaction for 1 hour to obtain the terminal chlorine-based polyether (ATRP initiator).
2) Preparing a super-strong adsorption concrete rheological agent:
10mol of chlorine-terminated polyether (ATRP initiator), 20mol of ethyl 4-vinylbenzoate and 0.5mol of CuCl/tris [2- (dimethylamino) ethyl ] ethyl]Amine (Me)6TREN) reacting at 80 deg.C for 30min, adding sodium hydroxide to adjust pH to 7 to obtain super-strong adsorption type concrete rheological agent (R of the agent1Is hydrogen, R2Is phthalic acid radical, R3Is propyl, R4Is H, R5Is ethyl, free of R6X is Cl, Z is O, m, n are all zero, p is 68, q is 20, k is 5, and the weight average molecular weight is 30000).
Performance testing
1. And (3) testing the net slurry fluidity:
the samples obtained in examples 1 to 13 were subjected to a net flow test with reference to GB8077-2000 "method for testing homogeneity of concrete admixtures". The W/C is 0.29, the broken solid content of the admixture is 0.10 percent of the cement dosage, and the commercial high water-reducing polycarboxylic acid water reducing agent ART-M16 of the company is selected as a reference sample.
TABLE 1 Net pulp fluidity and loss over time for different samples
Figure BDA0001747568460000091
Figure BDA0001747568460000101
2. Testing of concrete Properties
The samples obtained in examples 1 to 13 were tested for slump loss and concrete strength with reference to GB8076-2008 "concrete Admixture". When the folded-solid admixture content of the admixture was 1.5 wt% (based on the amount of cement used), a commercially available polycarboxylic acid water reducing agent ART-M16 for high water reduction type from this company was selected as a reference.
TABLE 2 concrete slump retaining and mechanical properties of different samples
Figure BDA0001747568460000102
3. Concrete rheology test
By means of FANN rotational viscometer (r)Rotor＝1.8415，rStator＝1.8415，hStator＝1.8415，dAnnular gap＝1.8415，rRotor1.8415, the viscosity reducing effect of the cement paste was measured on the samples obtained in examples 1 to 13 with an instrument constant K of 300.0 (spring F1)), and ART-M16, which is a commercially available water reducing polycarboxylic acid water reducing agent.
TABLE 3 Cement neat paste viscosity for different samples
Figure BDA0001747568460000111

Claims (6)

1. A preparation method of a super-strong adsorption type concrete rheological agent is characterized by comprising the following specific steps:
1) preparation of the halogen-terminated polyether:
stirring the amine-terminated polyether and the diepoxide for 1-5 hours at normal temperature and normal pressure to perform an amine-epoxy ring-opening polymerization reaction, grafting the amine-terminated polyether on a main chain to form a polymer of a side chain, dehydrating and drying the amine-terminated polyether after the reaction is finished, and adding halogenated alkyl acyl halide to perform an esterification reaction to obtain the halogen-terminated polyether, wherein the molar ratio of the amine-terminated polyether to the diepoxide to the halogenated alkyl acyl halide is 1: 1.01-1.1: 2.01-2.2; the amine-terminated polyether has the following structure:
Figure 348049DEST_PATH_IMAGE001
wherein R is1The polyether is H or methyl, m, n and p are integers which are more than or equal to zero, m + n + p is more than or equal to 6 and less than or equal to 68, m, n and p are not 0 at the same time, and the weight average molecular weight of the amine-terminated polyether is 500-3000;
2) preparing a super-strong adsorption concrete rheological agent:
reacting the end halogen-based polyether obtained in the step 1), the carbonyl-containing unsaturated small monomer and the transition metal complex at 50-80 ℃ for 30-240 min, and adding alkali to adjust the pH value to 6-7 to obtain the super-strong adsorption type concrete rheological agent; wherein the mol ratio of the end halogen group polyether, the carbonyl-containing unsaturated small monomer and the transition metal complex is 1: 2-60: 0.01-0.1, wherein the weight-average molecular weight of the super-adsorption type concrete rheological agent is 20000-plus 80000.
2. The process according to claim 1, wherein the diepoxide in the step 1) is 1, 3-butadiene diepoxide, 1, 5-hexadiene diepoxide, bis (2, 3-epoxycyclopentyl) ether, vinylcyclohexene oxide, diisoprenyl diepoxide, one or more of dicyclopentadiene diepoxide, 3, 4-epoxy-6-methyl cyclohexyl formic acid-3 ', 4' -epoxy-6 'methyl cyclohexyl methyl ester, 3, 4-epoxy-6-cyclohexyl formic acid-3', 4 '-epoxy-6' methyl cyclohexyl methyl ester, adipic acid di (3, 4-epoxy-6 methyl cyclohexyl methyl ester) and phthalic acid diglycidyl ester.
3. The method according to claim 1, wherein the alkyl halide in step 1) is one or more selected from the group consisting of 2-bromoisobutyryl bromide, 2-bromoisobutyryl chloride, 2-chloroisobutyryl chloride, 2-chloropropionyl chloride and 2-bromopropionyl chloride.
4. The method according to claim 1, wherein the carbonyl group-containing unsaturated small monomer of step 2) is acrylic acid, sodium acrylate, methacrylic acid, sodium methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, propyl methacrylate, ethyl methacrylate, methyl methacrylate, hydroxy-N-butyl methacrylate, acrylamide, N-methacrylamide, N-ethylacrylamide, N-dimethylacrylamide, N-diethyl 2-acrylamide, 2-vinylbenzoic acid, methyl 2-vinylbenzoate, 2-vinylphenylacetic acid, or a mixture thereof, 4-vinyl benzoic acid, 4-vinyl methyl benzoate and 4-vinyl ethyl benzoate.
5. The method according to claim 1, wherein the transition metal complex in step 2) is one or more selected from the group consisting of CuBr/pentamethyldiethylenetriamine, CuCl/HMTETA, CuBr/tetrakis [ (2-pyridyl) methyl ] ethylenediamine, CuBr/tris [2- (dimethylamino) ethyl ] amine, CuCl/pentamethyldiethylenetriamine, CuBr/HMTETA, CuCl/tetrakis [ (2-pyridyl) methyl ] ethylenediamine, and CuCl/tris [2- (dimethylamino) ethyl ] amine.
6. The method according to claim 1, wherein the base in step 2) is one or a combination of two or more selected from the group consisting of sodium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, sodium tert-butoxide, and potassium tert-butoxide.
CN201810851245.3A 2018-07-30 2018-07-30 Super-strong adsorption type concrete rheological agent and preparation method thereof Active CN109369858B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810851245.3A CN109369858B (en) 2018-07-30 2018-07-30 Super-strong adsorption type concrete rheological agent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810851245.3A CN109369858B (en) 2018-07-30 2018-07-30 Super-strong adsorption type concrete rheological agent and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109369858A CN109369858A (en) 2019-02-22
CN109369858B true CN109369858B (en) 2021-06-25

Family

ID=65403715

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810851245.3A Active CN109369858B (en) 2018-07-30 2018-07-30 Super-strong adsorption type concrete rheological agent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109369858B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117165270B (en) * 2023-10-31 2024-01-09 新疆春华石油科技有限责任公司 Plugging anti-collapse agent for drilling fluid and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU833995A1 (en) * 1979-07-24 1981-05-30 Отделение Ордена Ленина Институтахимической Физики Ah Cccp Method of preparing copolymers of highest alkylacrylates with acrylamide
US5393343A (en) * 1993-09-29 1995-02-28 W. R. Grace & Co.-Conn. Cement and cement composition having improved rheological properties
CN1135207A (en) * 1993-09-29 1996-11-06 格雷斯公司 Impoved cement admixture product having improved rheolgical properties and process of forming same
CN105542090A (en) * 2015-12-08 2016-05-04 江苏苏博特新材料股份有限公司 Rheology modifier for concrete and preparation method thereof
CN107200829A (en) * 2017-07-07 2017-09-26 江苏中铁奥莱特新材料股份有限公司 Controllable, regular polyether amine water reducer of a kind of molecular structure and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU833995A1 (en) * 1979-07-24 1981-05-30 Отделение Ордена Ленина Институтахимической Физики Ah Cccp Method of preparing copolymers of highest alkylacrylates with acrylamide
US5393343A (en) * 1993-09-29 1995-02-28 W. R. Grace & Co.-Conn. Cement and cement composition having improved rheological properties
CN1135207A (en) * 1993-09-29 1996-11-06 格雷斯公司 Impoved cement admixture product having improved rheolgical properties and process of forming same
CN105542090A (en) * 2015-12-08 2016-05-04 江苏苏博特新材料股份有限公司 Rheology modifier for concrete and preparation method thereof
CN107200829A (en) * 2017-07-07 2017-09-26 江苏中铁奥莱特新材料股份有限公司 Controllable, regular polyether amine water reducer of a kind of molecular structure and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis, characterization and working mechanism of a novel;Shanshan Qian等;《Construction and building materials》;20180320;第169卷;第452-461页 *

Also Published As

Publication number Publication date
CN109369858A (en) 2019-02-22

Similar Documents

Publication Publication Date Title
JP6074517B2 (en) Method for producing slump retention type polycarboxylate-based high performance fluidizing agent
WO2021027174A1 (en) Water-retaining type polycarboxylate superplasticizer and preparation method therefor
CN109734833B (en) Short-side-chain anti-mud polycarboxylate superplasticizer and preparation method thereof
CN110218022B (en) Chitosan oligosaccharide graft modified polycarboxylate superplasticizer and preparation method thereof
CN104817663B (en) A kind of application of polycarboxylate water-reducer in montmorillonite side effect is suppressed
KR19990006835A (en) Cement admixture and cement composition
CN106832154B (en) A kind of thickening type function polycarboxylate water-reducer and preparation method thereof
CN109369858B (en) Super-strong adsorption type concrete rheological agent and preparation method thereof
CN107602782B (en) Preparation method of polycarboxylic acid water reducing agent containing polyurea structure
CN108373523A (en) Polycarboxylate water-reducer of organic inorganic hybridization and preparation method thereof
CN108373522B (en) Polycarboxylate superplasticizer with modified cyclodextrin side chain structure and preparation method thereof
CN108948283B (en) Phthalic anhydride modified polycarboxylate superplasticizer and preparation method thereof
CN105968266B (en) The preparation method of superpower decentralized polycarboxylic acid series high efficiency water reducing agent
CN109734847B (en) Viscosity reduction type polycarboxylate superplasticizer containing three viscosity reduction functional groups, and preparation method and application thereof
CN111087552A (en) Synthetic method of polycarboxylic acid water reducer with high water reducing rate and mud resistance
CN116041630A (en) Quaternary ammonium salt polyether ester monomer, EPEG type polycarboxylate superplasticizer and preparation method thereof
CN104927065A (en) Preparation method of high-branching retardation type polycarboxylic acid water reducing agent
CN111363159A (en) Sulfonated styrene-maleic anhydride grafted polyether type reduction type polycarboxylate superplasticizer
CN109721722B (en) Viscosity-reducing type polycarboxylate superplasticizer containing double viscosity-reducing functional groups, and preparation method and application thereof
CN113980203B (en) Polycarboxylate superplasticizer with controllable structure based on EPEG polyether macromonomer and preparation method thereof
CN106883358A (en) A kind of four arm star polycarboxylic acid super-plasticizers and its preparation method and application
CN106365493B (en) Anti- chamotte mould dispersant of a kind of guarantor's modeling and preparation method thereof
CN111039973B (en) Organic silicon modified enol compound and preparation method thereof
CN114516938A (en) Non-chlorine double-comb type amphoteric polycarboxylate superplasticizer and preparation method thereof
CN109776034B (en) Application of viscosity-reducing water reducer containing alkyl in preparation of C100 concrete

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant