CN109265052B - Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer - Google Patents

Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer Download PDF

Info

Publication number
CN109265052B
CN109265052B CN201811047602.7A CN201811047602A CN109265052B CN 109265052 B CN109265052 B CN 109265052B CN 201811047602 A CN201811047602 A CN 201811047602A CN 109265052 B CN109265052 B CN 109265052B
Authority
CN
China
Prior art keywords
dropwise adding
acid
parts
viscosity
tricarboxylic acid
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
CN201811047602.7A
Other languages
Chinese (zh)
Other versions
CN109265052A (en
Inventor
钟丽娜
方云辉
赖华珍
柯余良
张小芳
林艳梅
李格丽
赖广兴
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.)
SHAANXI KZJ NEW MATERIALS Co Ltd
Kezhijie New Material Group Co Ltd
Original Assignee
SHAANXI KZJ NEW MATERIALS Co Ltd
Kezhijie New Material Group Co Ltd
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 SHAANXI KZJ NEW MATERIALS Co Ltd, Kezhijie New Material Group Co Ltd filed Critical SHAANXI KZJ NEW MATERIALS Co Ltd
Priority to CN201811047602.7A priority Critical patent/CN109265052B/en
Priority to PCT/CN2019/072745 priority patent/WO2020048083A1/en
Publication of CN109265052A publication Critical patent/CN109265052A/en
Priority to PH12019500531A priority patent/PH12019500531B1/en
Application granted granted Critical
Publication of CN109265052B publication Critical patent/CN109265052B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688Copolymers containing at least three different monomers
    • C04B24/2694Copolymers containing at least three different monomers containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/38Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers

Landscapes

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

Abstract

The invention discloses a preparation method of a cross-linking viscosity-reduction type polycarboxylate superplasticizer, which comprises the following steps: (1) preparing an esterified monomer; (2) carrying out copolymerization reaction; (3) and (4) neutralizing. According to the preparation method, a product obtained by esterification reaction of allyl alcohol monomers and 2-butane phosphate-1, 2, 4-tricarboxylic acid and obtained by esterification reaction of carboxyl in 2-butane phosphate-1, 2, 4-tricarboxylic acid is copolymerized with a small amount of esterified monomers, polyether macromonomers, 2-methacryloyloxyethyl phosphorylcholine phosphate and unsaturated acid obtained by double esterification of carboxyl in 2-butane phosphate-1, 2, 4-tricarboxylic acid and three esterified products to prepare the cross-linking viscosity-reduction type polycarboxylate superplasticizer, and phosphate radicals, carboxylate radicals, quaternary ammonium salts and ester radicals are introduced into a polymer molecular structure, and the polymer structure is also lightly cross-linked. The crosslinking viscosity-reduction type polycarboxylate superplasticizer prepared by the invention has viscosity-reduction performance, water-reduction, slump-retaining and mud-resistance performances, and solves the problems of high viscosity, poor workability and excessive loss caused by large mud content in the existing concrete raw material.

Description

Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of a cross-linked viscosity-reducing type polycarboxylate superplasticizer.
Background
The polycarboxylic acid water reducing agent has the advantages of low mixing amount, high water reducing rate, strong designability, environmental friendliness and the like, and becomes a concrete admixture which is most widely applied. High-rise and super high-rise buildings require that concrete must reach a certain strength grade, pumping construction of the high-rise building concrete has high requirements on the workability of the concrete, in order to reach a high strength grade, the concrete can be generally realized by methods of reducing a water cement ratio, increasing the using amount of a cementing material, increasing the proportion of a mineral admixture and the like, but the measures can also cause the problems of increasing the viscosity of the concrete, reducing the fluidity and the like, and at present, the problems are generally solved by compounding an auxiliary agent such as a mud resistance agent, an air entraining agent and the like or adopting a viscosity-reducing polycarboxylic acid water reducing agent. However, with the drastic increase of the amount of capital construction projects, the consumption of gravels is huge, high-quality gravels resources are less and less, the mud content in the gravels is gradually increased, and the polycarboxylate superplasticizer is very sensitive to the mud content in the gravels, so that the dispersibility and the dispersion retentivity of the polycarboxylate superplasticizer are reduced. Therefore, the preparation method develops the cross-linking viscosity-reduction type polycarboxylate superplasticizer which can effectively adapt to the mud content in the sand and stone, and has important significance for the development of concrete admixtures and the concrete industry.
Disclosure of Invention
The invention aims to provide a preparation method of a crosslinking viscosity-reducing polycarboxylate superplasticizer.
The technical scheme of the invention is as follows:
a preparation method of a cross-linking viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) preparing an esterified monomer: adding allyl alcohol monomers, 2-butane phosphate-1, 2, 4-tricarboxylic acid, a catalyst and a polymerization inhibitor into a first reactor provided with a condensing device, reacting for 4-8 h at a constant temperature of 100-120 ℃ under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain esterified monomers; the allyl alcohol monomer has the structural formula
Figure BDA0001792801520000011
R1Is H or CH3;R2Is H or CnH2n+1,n=1~6;R3Is H, CH3Br, Cl or F; r4Is CnH2n、CnH2(n-1)Or CnH2nOmWherein n is 0-12, and m is 0-3; the structural formula of the 2-phosphobutane-1, 2, 4-tricarboxylic acid is shown in the specification
Figure BDA0001792801520000021
The catalyst is concentrated sulfuric acid, heteropoly acid, stannous oxide or dibutyl tin oxide; the polymerization inhibitor is p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or phenothiazine;
the esterification monomer mainly comprises a product of singly esterifying carboxyl of 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid and a small amount of esterification monomer of doubly esterifying carboxyl of 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid and three esterification products, and specifically, the structural formula of the esterification monomer is shown in the specification
Figure BDA0001792801520000022
R5Is R1CHR2=CR3-CH2-R4Or H; r6Is R1CHR2=CR3-CH2-R4Or H; r7Is R1CHR2=CR3-CH2-R4Or H; wherein R is5、R6Or R7At least one is R1CHR2=CR3-CH2-R4
(2) And (3) copolymerization reaction: adding 200 parts by weight of polyether macromonomer and 145-160 parts by weight of water into a second reaction device, stirring and dissolving at normal temperature, and directly adding 1.0-3 parts by weight of reducing agent; uniformly mixing 5-15 parts of the esterified monomer prepared in the step (1), 3-10 parts of 2-methacryloyloxyethyl phosphorylcholine and 20-30 parts of water, and placing the mixture in a first dripping device; uniformly mixing 1.5-3.5 parts of oxidant and 30 parts of water in a second dripping device; 5 to 20Uniformly mixing 0.5-2 parts of unsaturated acid, 0.5-2 parts of chain transfer agent and 30 parts of water in a third dripping device; dropwise adding 0-50% of the material of the third dropwise adding device into the second reaction device at room temperature, adding a proper amount of accelerator, then dropwise adding the materials in the second dropwise adding device, the first dropwise adding device and the rest of the third dropwise adding devices in sequence, finishing the dropwise adding of the materials in the first dropwise adding device, the third dropwise adding device and the second dropwise adding device in sequence, and continuously reacting for at least 1h after 1-1.5 h of complete dropwise adding; the polyether macromonomer has the structure of
Figure BDA0001792801520000023
R8Is H or CH3,R9Is CnH2nWherein n is 0-4, x is 40-120, and y is 0-20;
(3) and (3) neutralization reaction: and (3) adjusting the pH value of the material obtained in the step (2) to 6.0-7.0 by using sodium hydroxide with the mass concentration of 32%, so as to obtain the cross-linked viscosity-reducing polycarboxylic acid water reducer.
In a preferred embodiment of the present invention, the allyl alcohol monomer is allyl alcohol, 2-methallyl alcohol, 3-methallyl alcohol, 2-chloro-2-propen-1-ol, 3-chloroallyl alcohol, 2-bromo-2-propen-1-ol, 2-fluoroallyl alcohol, allyl hydroxyethyl ether, monomethylallyl glycol ether, diethylene glycol monoallyl ether, 4- (allyloxy) -1-butanol, 1-allylcyclohexanol, (2-vinylcyclopropyl) methanol, 2-methyl-2-buten-1-ol, or 3-methyl-3-buten-1-ol.
In a preferred embodiment of the present invention, the polyether macromonomer is at least one of allyl polyoxyethylene ether, methallyl polyoxyethylene polyoxypropylene ether, isopentenyl polyoxyethylene ether, and isopentenyl polyoxyethylene polyoxypropylene ether.
In a preferred embodiment of the present invention, the unsaturated acid is acrylic acid or methacrylic acid.
In a preferred embodiment of the invention, the oxidizing agent is hydrogen peroxide, sodium persulfate or ammonium persulfate.
In a preferred embodiment of the invention, the chain transfer is thioglycolic acid, mercaptopropionic acid or mercaptopropanol.
In a preferred embodiment of the invention, the promoter is ferrous sulfate, ferrous nitrate or copper sulfate.
Further preferably, in the step (1), the molar ratio of the allyl alcohol monomer to the 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid is 1.1-1.5: 1.
More preferably, in the step (1), the amount of the catalyst is 0.5-5% of the mass of the 2-phosphobutane-1, 2, 4-tricarboxylic acid.
More preferably, in the step (1), the amount of the polymerization inhibitor is 0.01-1% of the mass of the 2-phosphobutane-1, 2, 4-tricarboxylic acid.
The invention has the beneficial effects that:
1. according to the preparation method, a product obtained by esterification reaction of allyl alcohol monomers and 2-butane phosphate-1, 2, 4-tricarboxylic acid and obtained by esterification reaction of carboxyl in 2-butane phosphate-1, 2, 4-tricarboxylic acid is copolymerized with a small amount of esterified monomers, polyether macromonomers, 2-methacryloyloxyethyl phosphorylcholine phosphate and unsaturated acid obtained by double esterification of carboxyl in 2-butane phosphate-1, 2, 4-tricarboxylic acid and three esterified products to prepare the cross-linking viscosity-reduction type polycarboxylate superplasticizer, and phosphate radicals, carboxylate radicals, quaternary ammonium salts and ester radicals are introduced into a polymer molecular structure, and the polymer structure is also lightly cross-linked.
2. Phosphate radicals in the polymer structure of the viscosity-reducing polycarboxylate superplasticizer prepared by the method have strong adsorption capacity on cement, and can improve SO in the cement under the synergistic effect with carboxylate radicals4 2-The competitive adsorption capacity of the concrete greatly improves the dispersibility of the concrete; meanwhile, the ester group is continuously hydrolyzed in the cement hydration process to release 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid sodium salt and phosphate radical, and the ester group continuously reacts with cement hydration products to inhibit Ca (OH)2The AFt crystal nucleus grows, the hydration speed is slowed down, and the hydration induction period of the cement is prolonged, so that the effect of improving the dispersion retentivity is achieved; the slightly crosslinked structure of the polymer is combined with the positive and negative charge characteristics of phosphorylcholine, so that the polymer structure is more stretched, and a hydrated film is thickerThe product has larger steric hindrance and better intercalation resistance, and has good mud resistance and viscosity reduction performance.
3. The crosslinking viscosity-reduction type polycarboxylate superplasticizer prepared by the invention has viscosity-reduction performance, water-reduction, slump-retaining and mud-resistance performances, and solves the problems of high viscosity, poor workability and excessive loss caused by large mud content in the existing concrete raw material.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Preparation of esterified monomer
Example 1
Adding 25g of allyl alcohol, 80g of 2-butane phosphate-1, 2, 4-tricarboxylic acid, 1g of dibutyltin oxide and 0.15g of hydroquinone into a first reactor provided with a condensing device, keeping the temperature at 120 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer A1, wherein the esterified monomer A is mainly a product obtained by singly esterifying carboxyl of 2-butane phosphate-1, 2, 4-tricarboxylic acid and a small amount of esterified monomer A1 obtained by doubly esterifying carboxyl in 2-butane phosphate-1, 2, 4-tricarboxylic acid.
Example 2
Adding 3-chloroallyl alcohol, 80g 2-butane phosphate-1, 2, 4-tricarboxylic acid, 1.2g concentrated sulfuric acid and 0.1g of p-hydroxyanisole into a first reactor provided with a condensing device, keeping the temperature of 110 ℃ constant for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer A2 mainly comprising a product obtained by singly esterifying carboxyl of the 2-butane phosphate-1, 2, 4-tricarboxylic acid and a small amount of esterified monomer A2 obtained by doubly esterifying carboxyl in the 2-butane phosphate-1, 2, 4-tricarboxylic acid.
Example 3
Adding 40g of allyl hydroxyethyl ether, 80g of 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid, 0.9g of heteropoly acid and 0.1g of phenothiazine into a first reactor provided with a condensing device, keeping the temperature at 110 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer A3, wherein the esterified monomer is mainly a product obtained by singly esterifying carboxyl of 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid and a small amount of esterified monomer A3 obtained by doubly esterifying carboxyl in 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid.
Example 4
Adding 1-allyl cyclohexanol, 80g 2-butane phosphate-1, 2, 4-tricarboxylic acid, 0.9g stannous oxide and 0.1g phenothiazine into a first reactor provided with a condensing device, keeping the temperature at 110 ℃ for 6 hours under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain an esterified monomer A4, wherein the esterified monomer is mainly a product obtained by singly esterifying carboxyl of 2-butane phosphate-1, 2, 4-tricarboxylic acid and a small amount of esterified monomer A4 obtained by doubly esterifying carboxyl in 2-butane phosphate-1, 2, 4-tricarboxylic acid.
Di, copolymerization and neutralization reaction
Example 5
And (3) copolymerization reaction: 200g of methyl allyl polyoxyethylene ether with the molecular weight of 2400 and 155g of water are added into a second reaction device, and 1.6g of sodium formaldehyde sulfoxylate is directly added after stirring and dissolving under the condition of normal temperature; uniformly mixing 12g of esterified monomer A1, 5.5g of 2-methacryloyloxyethyl phosphorylcholine and 20-30 g of water, and placing the mixture in a first dripping device; 2g of hydrogen peroxide and 30 parts of water are uniformly mixed in a second dripping device; mixing 15g of acrylic acid, 1.0g of thioglycolic acid and 30g of water uniformly in a third dripping device; and (3) dropwise adding 30% of materials of the third dropwise adding device into the second reaction device at room temperature, adding a proper amount of ferrous sulfate, then dropwise adding the materials in the second dropwise adding device, the first dropwise adding device and the residual third dropwise adding device in sequence, finishing the dropwise adding of the materials in the first dropwise adding device, the third dropwise adding device and the second dropwise adding device in sequence, and continuously reacting for at least 1h after 1-1.5 h of complete dropwise adding.
And (3) neutralization reaction: and (3) adjusting the pH value of the material obtained in the step (2) to 6.0-7.0 by using sodium hydroxide with the mass concentration of 32%, so as to obtain the cross-linked viscosity-reducing polycarboxylic acid water reducer.
Example 6
And (3) copolymerization reaction: adding 150g of methylallyl polyoxyethylene ether with the molecular weight of 2400, 50g of methylallyl polyoxyethylene polyoxypropylene ether with the molecular weight of 3000 and 155g of water into a second reaction device, stirring and dissolving at normal temperature, and directly adding 2g of sodium hypophosphite; uniformly mixing 11g of esterified monomer A2, 6g of 2-methacryloyloxyethyl phosphorylcholine and 20-30 parts of water, and placing the mixture in a first dripping device; 2g of sodium persulfate and 30g of water are uniformly mixed in a second dripping device; 13g of acrylic acid, 5g of methacrylic acid, 1.2g of mercaptopropionic acid and 30g of water are uniformly mixed in a third dripping device; and (3) dropwise adding 30% of materials of the third dropwise adding device into the second reaction device at room temperature, adding a proper amount of ferrous sulfate, then dropwise adding the materials in the second dropwise adding device, the first dropwise adding device and the residual third dropwise adding device in sequence, finishing the dropwise adding of the materials in the first dropwise adding device, the third dropwise adding device and the second dropwise adding device in sequence, and continuously reacting for at least 1h after 1-1.5 h of complete dropwise adding.
And (3) neutralization reaction: and (3) adjusting the pH value of the material obtained in the step (2) to 6.0-7.0 by using sodium hydroxide with the mass concentration of 32%, so as to obtain the cross-linked viscosity-reducing polycarboxylic acid water reducer.
Example 7
Copolymerization reaction, 200g of isopentenyl polyoxyethylene ether with the molecular weight of 2400 and 150g of water are added into a second reaction device, and 1.5g of Br ü ggolit is directly added after stirring and dissolving under the condition of normal temperatureTMFF 6; uniformly mixing 12g of esterified monomer A2, 6g of 2-methacryloyloxyethyl phosphorylcholine and 20-30 parts of water, and placing the mixture in a first dripping device; 2g of hydrogen peroxide and 30 parts of water are uniformly mixed in a second dripping device; uniformly mixing 16g of acrylic acid, 0.7g of mercaptoethanol and 30g of water in a third dripping device; at room temperature, dropwise adding 35% of materials of the third dropwise adding device into the second reaction device, adding a proper amount of ferrous nitrate, then dropwise adding the materials in the second dropwise adding device, the first dropwise adding device and the residual third dropwise adding device in sequence, finishing dropwise adding the materials in the first dropwise adding device, the third dropwise adding device and the second dropwise adding device in sequence, and continuously reacting for at least 1h after finishing dropwise adding in 1-1.5 h.
And (3) neutralization reaction: and (3) adjusting the pH value of the material obtained in the step (2) to 6.0-7.0 by using sodium hydroxide with the mass concentration of 32%, so as to obtain the cross-linked viscosity-reducing polycarboxylic acid water reducer.
Example 8
And (3) copolymerization reaction: 160g of isopentenyl polyoxyethylated ethylene having a molecular weight of 2400Adding vinyl ether, 40g of isopentenyl polyoxyethylene polyoxypropylene ether with the molecular weight of 3000 and 155g of water into a second reaction device, stirring and dissolving at normal temperature, and directly adding 1.5g of Br ü ggolitTMFF 6; uniformly mixing 13g of esterified monomer A4, 4g of 2-methacryloyloxyethyl phosphorylcholine and 20-30 parts of water, and placing the mixture in a first dripping device; 2g of hydrogen peroxide and 30 parts of water are uniformly mixed in a second dripping device; 14g of acrylic acid, 0.8g of mercaptoethanol and 30g of water are uniformly mixed in a third dripping device; and (3) dropwise adding 40% of the material of the third dropwise adding device into the second reaction device at room temperature, adding a proper amount of ferrous nitrate, then dropwise adding the materials in the second dropwise adding device, the first dropwise adding device and the residual third dropwise adding device in sequence, finishing the dropwise adding of the materials in the first dropwise adding device, the third dropwise adding device and the second dropwise adding device in sequence, and continuously reacting for at least 1h after 1-1.5 h of complete dropwise adding.
And (3) neutralization reaction: and (3) adjusting the pH value of the material obtained in the step (2) to 6.0-7.0 by using sodium hydroxide with the mass concentration of 32%, so as to obtain the cross-linked viscosity-reducing polycarboxylic acid water reducer.
The samples of the cross-linked viscosity-reducing polycarboxylic acid water reducing agent synthesized in examples 5 to 8 and a commercially available polycarboxylic acid water reducing agent (standard) were mixed with standard cement, and the mixing amount of the solid and the concrete initial slump and expansion, the concrete slump bucket emptying time and the concrete slump bucket emptying time were measured according to GB8076-2008 "concrete admixture" and JGJ281-2012 "high-strength concrete application technical Specification". The concrete mixing proportion is as follows: the results are shown in Table 1, wherein the expansion degrees of the cement, the fly ash (grade II), the fly ash and the stone are 430kg/m3, 30kg/m3, 90kg/m3, 700kg/m3 and 1050kg/m3 respectively, and the expansion degrees are controlled to be 650 +/-10 mm.
Table 1 comparison of the properties of the examples
Figure BDA0001792801520000071
The test results of examples 5 to 8 show that the viscosity-reducing polycarboxylate superplasticizer disclosed by the invention has a good viscosity-reducing effect.
It is obvious to those skilled in the art that the technical solution of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following scope, and still fall into the protection scope of the present invention:
a preparation method of a cross-linking viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) preparing an esterified monomer: adding allyl alcohol monomers, 2-butane phosphate-1, 2, 4-tricarboxylic acid, a catalyst and a polymerization inhibitor into a first reactor provided with a condensing device, reacting for 4-8 h at a constant temperature of 100-120 ℃ under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain esterified monomers; the allyl alcohol monomer has the structural formula
Figure BDA0001792801520000072
R1Is H or CH3;R2Is H or CnH2n+1,n=1~6;R3Is H, CH3Br, Cl or F; r4Is CnH2n、CnH2(n-1)Or CnH2nOmWherein n is 0-12, and m is 0-3; the structural formula of the 2-phosphobutane-1, 2, 4-tricarboxylic acid is shown in the specification
Figure BDA0001792801520000073
The catalyst is concentrated sulfuric acid, heteropoly acid, stannous oxide or dibutyl tin oxide; the polymerization inhibitor is p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or phenothiazine;
the esterification monomer mainly comprises a product of singly esterifying carboxyl of 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid and a small amount of esterification monomer of doubly esterifying carboxyl of 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid and three esterification products, and specifically, the structural formula of the esterification monomer is shown in the specification
Figure BDA0001792801520000081
R5Is R1CHR2=CR3-CH2-R4Or H; r6Is R1CHR2=CR3-CH2-R4Or H;R7is R1CHR2=CR3-CH2-R4Or H; wherein R is5、R6Or R7At least one is R1CHR2=CR3-CH2-R4
(2) And (3) copolymerization reaction: adding 200 parts by weight of polyether macromonomer and 145-160 parts by weight of water into a second reaction device, stirring and dissolving at normal temperature, and directly adding 1.0-3 parts by weight of reducing agent; uniformly mixing 5-15 parts of the esterified monomer prepared in the step (1), 3-10 parts of 2-methacryloyloxyethyl phosphorylcholine and 20-30 parts of water, and placing the mixture in a first dripping device; uniformly mixing 1.5-3.5 parts of oxidant and 30 parts of water in a second dripping device; uniformly mixing 5-20 parts of unsaturated acid, 0.5-2 parts of chain transfer agent and 30 parts of water in a third dripping device; dropwise adding 0-50% of the material of the third dropwise adding device into the second reaction device at room temperature, adding a proper amount of accelerator, then dropwise adding the materials in the second dropwise adding device, the first dropwise adding device and the rest of the third dropwise adding devices in sequence, finishing the dropwise adding of the materials in the first dropwise adding device, the third dropwise adding device and the second dropwise adding device in sequence, and continuously reacting for at least 1h after 1-1.5 h of complete dropwise adding; the polyether macromonomer has the structure of
Figure BDA0001792801520000082
R8Is H or CH3,R9Is CnH2nWherein n is 0-4, x is 40-120, and y is 0-20;
(3) and (3) neutralization reaction: and (3) adjusting the pH value of the material obtained in the step (2) to 6.0-7.0 by using sodium hydroxide with the mass concentration of 32%, so as to obtain the cross-linked viscosity-reducing polycarboxylic acid water reducer.
The allyl alcohol monomer is allyl alcohol, 2-methallyl alcohol, 3-methallyl alcohol, 2-chloro-2-propen-1-ol, 3-chloroallyl alcohol, 2-bromo-2-propen-1-ol, 2-fluoroallyl alcohol, allyl hydroxyethyl ether, monomethylallyl glycol ether, diethylene glycol monoallyl ether, 4- (allyloxy) -1-butanol, 1-allylcyclohexanol, (2-vinylcyclopropyl) methanol, 2-methyl-2-buten-1-ol or 3-methyl-3-buten-1-ol. The polyether macromonomer is at least one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene polyoxypropylene ether, isopentenyl polyoxyethylene ether and isopentenyl polyoxyethylene polyoxypropylene ether. The unsaturated acid is acrylic acid or methacrylic acid. The oxidant is hydrogen peroxide, sodium persulfate or ammonium persulfate. The chain transfer is thioglycolic acid, mercaptopropionic acid or mercaptopropanol. The promoter is ferrous sulfate, ferrous nitrate or copper sulfate.
In the step (1), the molar ratio of the allyl alcohol monomer to the 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid is 1.1-1.5: 1, the dosage of the catalyst is 0.5-5% of the mass of the 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid, and the dosage of the polymerization inhibitor is 0.01-1% of the mass of the 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (10)

1. A preparation method of a cross-linking viscosity-reduction type polycarboxylate superplasticizer is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing an esterified monomer: adding allyl alcohol monomers, 2-butane phosphate-1, 2, 4-tricarboxylic acid, a catalyst and a polymerization inhibitor into a first reactor provided with a condensing device, reacting for 4-8 h at a constant temperature of 100-120 ℃ under the protection of nitrogen, and cooling to 40 ℃ after the reaction is finished to obtain esterified monomers;
the allyl alcohol monomer has the structural formula
Figure FDA0002265893200000011
R1Is H or CH3;R2Is H or CnH2n+1,n=1~6;R3Is H, CH3Br, Cl or F; r4Is CnH2n、CnH2(n-1)Or CnH2nOmWherein n is 0 to 12, m is 0 to up3; the structural formula of the 2-phosphobutane-1, 2, 4-tricarboxylic acid is shown in the specification
Figure FDA0002265893200000012
The catalyst is concentrated sulfuric acid, heteropoly acid, stannous oxide or dibutyl tin oxide; the polymerization inhibitor is p-hydroxyanisole, hydroquinone, p-tert-butyl catechol or phenothiazine;
(2) and (3) copolymerization reaction: adding 200 parts by weight of polyether macromonomer and 145-160 parts by weight of water into a second reaction device, stirring and dissolving at normal temperature, and directly adding 1.0-3 parts by weight of reducing agent; uniformly mixing 5-15 parts of the esterified monomer prepared in the step (1), 3-10 parts of 2-methacryloyloxyethyl phosphorylcholine and 20-30 parts of water, and placing the mixture in a first dripping device; uniformly mixing 1.5-3.5 parts of oxidant and 30 parts of water in a second dripping device; uniformly mixing 5-20 parts of unsaturated acid, 0.5-2 parts of chain transfer agent and 30 parts of water in a third dripping device; dropwise adding 0-50% of the material of the third dropwise adding device into the second reaction device at room temperature, adding a proper amount of accelerator, then dropwise adding the materials in the second dropwise adding device, the first dropwise adding device and the rest of the third dropwise adding devices in sequence, finishing the dropwise adding of the materials in the first dropwise adding device, the third dropwise adding device and the second dropwise adding device in sequence, and continuously reacting for at least 1h after 1-1.5 h of complete dropwise adding; the polyether macromonomer has the structure of
Figure FDA0002265893200000013
R8Is H or CH3,R9Is CnH2nWherein n is 0-4, x is 40-120, and y is 0-20;
(3) and (3) neutralization reaction: and (3) adjusting the pH value of the material obtained in the step (2) to 6.0-7.0 by using sodium hydroxide with the mass concentration of 32%, so as to obtain the cross-linked viscosity-reducing polycarboxylic acid water reducer.
2. The method of claim 1, wherein: the allyl alcohol monomer is allyl alcohol, 2-methallyl alcohol, 3-methallyl alcohol, 2-chloro-2-propen-1-ol, 3-chloroallyl alcohol, 2-bromo-2-propen-1-ol, 2-fluoroallyl alcohol, allyl hydroxyethyl ether, monomethylallyl glycol ether, diethylene glycol monoallyl ether, 4- (allyloxy) -1-butanol, 1-allylcyclohexanol, (2-vinylcyclopropyl) methanol, 2-methyl-2-buten-1-ol or 3-methyl-3-buten-1-ol.
3. The method of claim 1, wherein: the polyether macromonomer is at least one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene polyoxypropylene ether, isopentenyl polyoxyethylene ether and isopentenyl polyoxyethylene polyoxypropylene ether.
4. The method of claim 1, wherein: the unsaturated acid is acrylic acid or methacrylic acid.
5. The method of claim 1, wherein: the oxidant is hydrogen peroxide, sodium persulfate or ammonium persulfate.
6. The method of claim 1, wherein: the chain transfer agent is thioglycolic acid, mercaptopropionic acid or mercaptopropanol.
7. The method of claim 1, wherein: the promoter is ferrous sulfate, ferrous nitrate or copper sulfate.
8. The production method according to any one of claims 1 to 7, characterized in that: in the step (1), the molar ratio of the allyl alcohol monomer to the 2-phosphoric acid butane-1, 2, 4-tricarboxylic acid is 1.1-1.5: 1.
9. The production method according to any one of claims 1 to 7, characterized in that: in the step (1), the amount of the catalyst is 0.5-5% of the mass of the 2-phosphobutane-1, 2, 4-tricarboxylic acid.
10. The production method according to any one of claims 1 to 7, characterized in that: in the step (1), the amount of the polymerization inhibitor is 0.01-1% of the mass of the 2-phosphobutane-1, 2, 4-tricarboxylic acid.
CN201811047602.7A 2018-09-07 2018-09-07 Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer Active CN109265052B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201811047602.7A CN109265052B (en) 2018-09-07 2018-09-07 Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer
PCT/CN2019/072745 WO2020048083A1 (en) 2018-09-07 2019-01-23 Preparation method for crosslinked viscosity-reducing polycarboxylic acid water reducer
PH12019500531A PH12019500531B1 (en) 2018-09-07 2019-03-12 Method for preparing cross-linked viscosity reducing polycarboxylate superplasticizer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811047602.7A CN109265052B (en) 2018-09-07 2018-09-07 Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer

Publications (2)

Publication Number Publication Date
CN109265052A CN109265052A (en) 2019-01-25
CN109265052B true CN109265052B (en) 2020-03-20

Family

ID=65188207

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811047602.7A Active CN109265052B (en) 2018-09-07 2018-09-07 Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer

Country Status (2)

Country Link
CN (1) CN109265052B (en)
WO (1) WO2020048083A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112708070B (en) * 2020-12-22 2021-12-28 科之杰新材料集团有限公司 Ether-type polycarboxylic acid water reducer with rust resistance function and preparation method thereof
CN112694574B (en) * 2021-01-11 2022-09-23 中国铁道科学研究院集团有限公司铁道建筑研究所 Polycarboxylate superplasticizer with high mud resistance and high slump loss resistance and preparation method thereof
CN113201101A (en) * 2021-05-26 2021-08-03 山西佳维新材料股份有限公司 Viscosity-reducing water reducer and preparation method and application thereof
CN113968695B (en) * 2021-09-24 2023-01-10 中核混凝土股份有限公司 Method for manufacturing viscosity-reducing dispersive concrete
CN114163464B (en) * 2021-12-15 2023-08-29 科之杰新材料集团有限公司 Esterification product, low-hydration heat ether polycarboxylate water reducer and preparation method thereof
CN115368552A (en) * 2022-10-08 2022-11-22 武汉中彭化学科技有限公司 Preparation method and application of polyether macromonomer

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8821630B2 (en) * 2011-05-06 2014-09-02 W. R. Grace & Co.-Conn. Carboxylated-carboxylic polyglycerol compositions for use in cementitious compositions
CN104177557B (en) * 2014-08-22 2017-09-15 科之杰新材料集团有限公司 A kind of low temperature preparation method of high-adaptability ethers polycarboxylic acid water reducing agent
CN104231183A (en) * 2014-09-23 2014-12-24 江苏奥莱特新材料有限公司 Preparation method for polycarboxylate-type water reducer
CN104311752B (en) * 2014-10-10 2017-09-22 科之杰新材料集团有限公司 A kind of polycarboxylate water-reducer and preparation method thereof
CN105236806B (en) * 2015-10-22 2017-03-22 石家庄市长安育才建材有限公司 Phosphoric-acid-base modified polycarboxylic-acid water reducer with high adaptability and preparation method thereof
CN106046274B (en) * 2016-08-17 2018-01-09 广州市建筑科学研究院有限公司 A kind of netted polycarboxylate water-reducer and preparation method thereof
CN108276533B (en) * 2018-01-24 2020-06-23 武汉优城科技有限公司 High-adaptability polycarboxylate superplasticizer and preparation method thereof
CN108484842B (en) * 2018-05-03 2020-05-12 科之杰新材料集团有限公司 Ester low-sensitivity polycarboxylate superplasticizer and preparation method thereof

Also Published As

Publication number Publication date
CN109265052A (en) 2019-01-25
WO2020048083A1 (en) 2020-03-12

Similar Documents

Publication Publication Date Title
CN109265052B (en) Preparation method of crosslinking viscosity-reduction type polycarboxylate superplasticizer
CN109180876B (en) Preparation method of viscosity-reducing polycarboxylate superplasticizer
CN109312032B (en) Rapid low-temperature preparation method of low-doping-amount sensitive polycarboxylic acid
US9453097B2 (en) Method for preparation of polycarboxylate superplasticizer by graft copolymerization of fatty acid vinyl ester onto acrylate polymer
CN112694574B (en) Polycarboxylate superplasticizer with high mud resistance and high slump loss resistance and preparation method thereof
WO2014085996A1 (en) Slump retaining polycarboxylic acid superplasticizer
CN108948288B (en) Preparation method of crosslinking type polycarboxylate superplasticizer by adopting carboxyl functional monomer
CN109627397B (en) Polycarboxylate superplasticizer for improving rheological property of cement paste and preparation method thereof
CN108047396B (en) Multi-cation mud-resistant polycarboxylate superplasticizer and preparation method thereof
WO2020001169A1 (en) Preparation method for retarding ether type polycarboxylic acid water reducing agent
CN110845672A (en) Polycarboxylic acid series concrete gel reducing agent and preparation method thereof
CN109232828B (en) Preparation method of ester ether copolymerization type viscosity reduction type polycarboxylate superplasticizer
CN115960322A (en) Polycarboxylic acid viscosity reducer and preparation method thereof
CN109942754B (en) Method for preparing delayed coagulation type superplasticizer by atom transfer radical polymerization
CN108192010B (en) Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof
CN110643003B (en) Preparation method of retarding type ester polycarboxylate superplasticizer
CN112708054B (en) Polycarboxylate superplasticizer for concrete member and preparation method thereof
CN108218278B (en) Preparation method of ester high-dispersion high-slump-retaining polycarboxylate superplasticizer
CN109293847A (en) A kind of preparation method of ethers viscosity reduction type polycarboxylate water-reducer
CN108218282B (en) Preparation method of anti-mud viscosity-reducing polycarboxylic acid plasticizer
CN114195953B (en) Low-sensitivity high-water-retention polycarboxylate superplasticizer and preparation method thereof
CN110643005B (en) Preparation method of ester viscosity-reducing polycarboxylic acid superplasticizer
CN112608424B (en) Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof
CN113896845A (en) Low-sensitivity slow-release polycarboxylic slump retaining agent and preparation method thereof
CN114195956A (en) High-strength concrete viscosity-reducing water reducer and preparation method thereof

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