CN110642987B - Ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof - Google Patents

Ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof Download PDF

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CN110642987B
CN110642987B CN201810673216.2A CN201810673216A CN110642987B CN 110642987 B CN110642987 B CN 110642987B CN 201810673216 A CN201810673216 A CN 201810673216A CN 110642987 B CN110642987 B CN 110642987B
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赖广兴
方云辉
郭元强
赖华珍
林艳梅
李格丽
柯余良
钟丽娜
张小芳
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Kezhijie New Material Group Co Ltd
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    • 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
    • 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
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses an ether ester copolymerization viscosity reduction type polycarboxylate superplasticizer and a preparation method thereof, wherein the raw materials comprise the following components: 4-hydroxybutyl vinyl polyoxyethylene ether, methoxy polyethylene glycol methacrylate, unsaturated monocarboxylic acid, unsaturated carboxylic ester monomer, 4- (1-carboxyvinyl) benzoic acid, unsaturated hyperbranched small monomer, oxidant, reducing agent, chain transfer agent, proper amount of potassium hydroxide aqueous solution, proper amount of sodium hydroxide aqueous solution and deionized water. The unsaturated high-branching small monomer is synthesized and is introduced into the polycarboxylate superplasticizer together with the benzene-containing rigid small monomer 4- (1-carboxyvinyl) benzoic acid, so that the molecular conformation of the polycarboxylate superplasticizer can be more extended, the steric hindrance effect of a side chain of the polycarboxylate superplasticizer is further improved, and the viscosity of concrete is greatly reduced.

Description

Ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to an ether ester copolymerization viscosity reduction type polycarboxylate superplasticizer and a preparation method thereof.
Background
The polycarboxylate superplasticizer serving as a third-generation superplasticizer has the outstanding advantages of high water reducing rate, good slump retaining effect, low mixing amount and strong designability of a molecular structure. The polycarboxylic acid water reducing agent in the current market has higher water reducing rate, can well meet the construction requirements of concrete with low water-cement ratio, but along with the development of concrete technology to the functionalization directions of high strength, high durability, self-leveling and the like, the water-cement ratio of the polycarboxylic acid water reducing agent is continuously reduced, the viscosity of the concrete is increased along with the water-cement ratio, the flowing speed is reduced, and the difficult problem in the aspect of concrete construction performance brought by the low water-cement ratio cannot be well solved by continuously using the conventional polycarboxylic acid water reducing agent. Therefore, the development of the polycarboxylic acid water reducing agent capable of reducing the viscosity of concrete is urgently needed, and the engineering application problem of the polycarboxylic acid water reducing agent is solved.
At home and abroad, researchers have focused on the development and application of the viscosity-reducing polycarboxylic acid water reducer. Zhang ming et al found that: with the increase of the proportion of Methyl Methacrylate (MMA) in the PCE molecular structure, the flow time of concrete stirred by the Methyl Methacrylate (MMA) is reduced obviously, namely the viscosity of concrete mixture is reduced continuously. The MMA molecule structure contains a large proportion of hydrophobic methyl, so that the hydrophile lipophilicity (HLB value) of the PCE molecule structure is improved, and free water bound by a polyoxyethylene side chain is released, so that the viscosity of the concrete mixture is effectively reduced. Similarly, as the molecular weight of methoxypolyethylene glycol methacrylate (MPEGMA) is increased, the content of hydrophilic ethylene oxide groups in the molecular structure of the synthesized PCE is increased, a large amount of free water is bound, and the viscosity of the concrete mixture is increased.
Some patents about viscosity reducers are reported at home and abroad, in 2004, a Japanese catalyst company applies for polycarboxylic acid admixture patents for reducing the viscosity of concrete, and compared with the traditional polycarboxylic acid water reducer, the polymer viscosity reducer has richer branched chain structures and more excellent adsorption performance, so that the adsorption density of a polymer on the surface of cement particles is higher, the thickness of an adsorption layer is increased, the yield stress can be obviously reduced, and the effect of improving the viscosity of concrete is achieved. CN 103145360A discloses a high-strength or ultra-high-strength concrete viscosity regulator, which reduces the concrete viscosity by optimizing the grain composition of a cementing material and the appearance effect and the surface charge effect of powder particles. However, the viscosity regulator in the technical scheme is doped into concrete by 10-30%, and the effect can be exerted only by higher doping amount, so that the wide application of the viscosity regulator is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ether ester copolymerization viscosity reduction type polycarboxylate superplasticizer.
The invention also aims to provide a preparation method of the ether ester copolymerization viscosity-reducing type polycarboxylate superplasticizer.
The technical scheme of the invention is as follows:
an ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer has the pH value of 6.0-7.0 and the solid content of 45-55%, and is prepared from the following raw materials in parts by weight: 10-100 parts by weight of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 4000-6000, 10-100 parts by weight of methoxy polyethylene glycol methacrylate, 6-10 parts by weight of unsaturated monocarboxylic acid, 3-6 parts by weight of unsaturated carboxylic ester monomer, 2-5 parts by weight of 4- (1-carboxyvinyl) benzoic acid, 1-5 parts by weight of unsaturated hyperbranched small monomer, 0.2-0.8 part by weight of oxidant, 0.2-1.0 part by weight of reducing agent, 0.2-0.6 part by weight of chain transfer agent, a proper amount of potassium hydroxide aqueous solution, a proper amount of sodium hydroxide aqueous solution and 106-130 parts by weight of deionized water, wherein the unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid, and the unsaturated carboxylic ester monomer is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate and methyl methacrylate.
The preparation method of the unsaturated hyperbranched small monomer comprises the following steps:
adding inositol and itaconic acid into a reactor under normal pressure, and simultaneously adding a catalyst, a polymerization inhibitor and a water-carrying agent to perform esterification reaction at the temperature of 100-140 ℃ for 4-9 hours to obtain an unsaturated high-branching small monomer; the catalyst is at least one of toluenesulfonic acid, sodium acetate and sodium bisulfate, and the polymerization inhibitor is at least one of 4-oxo-2, 2, 6, 6-tetramethyl-4-piperidine, N-nitroso-N-phenylhydroxylamine aluminum and N, N-copper dibutyldithiocarbamate.
In a preferred embodiment of the invention, the molar ratio of the cyclohexanehexol to the itaconic acid is 1: 2.5-3.5, the amount of the catalyst is 0.1-0.2 wt% of the total material amount, the amount of the polymerization inhibitor is 0.05-0.2 wt% of the total material amount, the amount of the water-carrying agent is 10-20 wt% of the total material amount, and the total material amount is the total amount of the cyclohexanehexol, the itaconic acid, the catalyst, the polymerization inhibitor and the water-carrying agent.
In a preferred embodiment of the present invention, the methoxypolyethylene glycol methacrylate is prepared by the following steps: polyethylene glycol monomethyl ether with the molecular weight of 5000-6000, methacrylic acid, concentrated sulfuric acid and copper N, N-dibutyl dithiocarbamate are placed in a reaction device and react for 3-6 hours at a constant temperature of 100-130 ℃ to obtain the copper-based catalyst.
Further preferably, the molar ratio of the polyethylene glycol monomethyl ether to the methacrylic acid is 1: 2-6, and the use amounts of the concentrated sulfuric acid and the copper N, N-dibutyldithiocarbamate are 1.5-5% and 0.5-2% of the total mass of the polyethylene glycol monomethyl ether and the methacrylic acid, respectively.
Still more preferably, the oxidizing agent is at least one of hydrogen peroxide, sodium persulfate, and ammonium persulfate.
Still more preferably, the reducing agent is at least one of hydrazine dihydrochloride, sodium triacetoxyborohydride, and sodium tris (1, 1, 1, 3, 3, 3-hexafluoroisopropoxy) borohydride.
Still more preferably, the chain transfer agent is at least one of 2-methylhexyl 3-mercaptoacetate and 2, 4-diphenyl-4-methyl-1-pentene.
The preparation method of the ether ester copolymerization viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) dissolving unsaturated monocarboxylic acid and a chain transfer agent in 10-15 parts by weight of deionized water, and adjusting the pH to 5.5-6.0 by using a potassium hydroxide aqueous solution to obtain a first solution; dissolving a reducing agent in 10-15 parts by weight of deionized water to obtain a second solution; dissolving unsaturated carboxylic ester monomers and 4- (1-carboxyvinyl) benzoic acid in 6-10 parts by weight of deionized water to obtain a third solution;
(3) dissolving 4-hydroxybutyl vinyl polyoxyethylene ether, methoxy polyethylene glycol methacrylate and an unsaturated hyperbranched small monomer in 80-90 parts by weight of deionized water, sequentially adding 35-55% of a first solution, a proper amount of a sodium hydroxide aqueous solution and an oxidant, and adjusting the reaction temperature to 10-30 ℃ for reaction;
(4) simultaneously dripping the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dripping is finished within 0.5-1.5 h, and preserving heat for 0.5-1.5 h after the dripping is finished;
(5) and (3) adjusting the pH value of the material obtained in the step (4) to 6.0-7.0 by using a proper amount of sodium hydroxide aqueous solution to obtain the ether ester copolymerization viscosity reduction type polycarboxylate superplasticizer.
The invention has the beneficial effects that:
1. after the polycarboxylate water reducing agent is adsorbed on the surfaces of the cement particles, a water film layer can be formed on the surfaces of the cement particles, and the friction among the cement particles is reduced by the lubricating action of the water film layer, so that the viscosity of concrete is reduced. According to the invention, by adopting the 4-hydroxybutyl vinyl polyoxyethylene ether macromonomer (VPEG) with ultrahigh molecular weight, high double bond retention rate and high activity, the length of the side chain of the polycarboxylic acid water reducing agent is increased, the steric hindrance effect is increased, the thickness of the water film layer is increased, and the viscosity reduction effect is more remarkable. And methoxy polyethylene glycol methacrylate (MPEGMAA) with ultrahigh molecular weight is introduced for copolymerization, so that the viscosity of the concrete can be further reduced, and the workability and bleeding property of the concrete can be improved.
2) The unsaturated high-branching small monomer is synthesized and is introduced into the polycarboxylate superplasticizer together with the benzene-containing rigid small monomer 4- (1-carboxyvinyl) benzoic acid, so that the molecular conformation of the polycarboxylate superplasticizer can be more extended, the steric hindrance effect of a side chain of the polycarboxylate superplasticizer is further improved, and the viscosity of concrete is greatly reduced.
3) The viscosity-reducing polycarboxylate superplasticizer disclosed by the invention is simple in preparation process, convenient to produce, low in cost and small in pollution.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
In the following examples, the unsaturated hyperbranched small monomers were prepared as follows: adding inositol and itaconic acid into a reactor under normal pressure, and simultaneously adding a catalyst, a polymerization inhibitor and a water-carrying agent to perform esterification reaction at the temperature of 100-140 ℃ for 4-9 hours to obtain an unsaturated high-branching small monomer; the catalyst is at least one of toluenesulfonic acid, sodium acetate and sodium bisulfate, and the polymerization inhibitor is at least one of 4-oxo-2, 2, 6, 6-tetramethyl-4-piperidine, N-nitroso-N-phenylhydroxylamine aluminum and N, N-copper dibutyldithiocarbamate. The molar ratio of the cyclohexanehexol to the itaconic acid is 1: 2.5-3.5, the amount of the catalyst is 0.1-0.2 wt% of the total material amount, the amount of the polymerization inhibitor is 0.05-0.2 wt% of the total material amount, and the amount of the water-carrying agent is 10-20 wt% of the total material amount, wherein the total material amount is the total amount of the cyclohexanehexol, the itaconic acid, the catalyst, the polymerization inhibitor and the water-carrying agent in the step.
The preparation method of the methoxy polyethylene glycol methacrylate comprises the following steps: polyethylene glycol monomethyl ether with the molecular weight of 5000-6000, methacrylic acid, concentrated sulfuric acid and copper N, N-dibutyl dithiocarbamate are placed in a reaction device and react for 3-6 hours at a constant temperature of 100-130 ℃ to obtain the copper-based catalyst. The molar ratio of the polyethylene glycol monomethyl ether to the methacrylic acid is 1: 2-6, and the use amounts of the concentrated sulfuric acid and the N, N-dibutyl copper dithiocarbamate are respectively 1.5-5% and 0.5-2% of the total mass of the polyethylene glycol monomethyl ether and the methacrylic acid.
Example 1
(1) Weighing the following raw material components in parts by weight: 70 parts of 4-hydroxybutyl vinyl polyoxyethylene ether (VPEG molecular weight 4000), 40 parts of methoxypolyethylene glycol methacrylate, 8 parts of acrylic acid, 6 parts of hydroxyethyl acrylate, 2 parts of 4- (1-carboxyvinyl) benzoic acid, 2 parts of unsaturated hyperbranched small monomer, 0.5 part of hydrogen peroxide, 0.7 part of sodium triacetoxyborohydride, 0.35 part of 3-mercaptoacetic acid-2-methylhexyl ester, 4 parts of 50 wt% potassium hydroxide aqueous solution, 5 parts of 32 wt% sodium hydroxide aqueous solution and the balance of deionized water, and the solid content is adjusted to 50%.
(2) Dissolving acrylic acid and 3-mercaptoacetic acid-2-methyl hexyl ester in 15 parts by weight of deionized water, and adjusting the pH to 5.5-6.0 by using 50 wt% of potassium hydroxide aqueous solution to obtain a first solution; dissolving sodium triacetoxyborohydride in 15 parts by weight of deionized water to obtain a second solution; dissolving hydroxyethyl acrylate and 4- (1-carboxyvinyl) benzoic acid in 10 parts by weight of deionized water to obtain a third solution;
(3) dissolving the 4-hydroxybutyl vinyl polyoxyethylene ether, the methoxy polyethylene glycol methacrylate and the unsaturated hyperbranched small monomer in the residual deionized water, sequentially adding 35% of first solution, 32 wt% of sodium hydroxide aqueous solution and hydrogen peroxide, and adjusting the reaction temperature to 10 ℃;
(4) simultaneously dripping the first solution, the second solution and the third solution into the material obtained in the step (3), finishing dripping all the three solutions within 1h, and preserving heat for 1.5h after finishing dripping;
(5) and (3) after the heat preservation is finished, adjusting the pH value to 6.0-7.0 by using 32 wt% of sodium hydroxide aqueous solution to obtain the ester ether copolymerization viscosity reduction type polycarboxylate superplasticizer PCE-1.
Example 2
(1) The raw material components of 60 parts by weight of 4-hydroxybutyl vinyl polyoxyethylene ether (VPEG molecular weight 4500), 50 parts by weight of methoxy polyethylene glycol methacrylate, 6 parts by weight of acrylic acid, 3 parts by weight of hydroxyethyl methacrylate, 3 parts by weight of 4- (1-carboxyvinyl) benzoic acid, 1 part by weight of unsaturated hyperbranched small monomer, 0.6 part by weight of sodium persulfate, 0.8 part by weight of hydrazine dihydrochloride, 0.4 part by weight of 3-thioglycolic acid-2-methyl hexyl ester, 2 parts by weight of 50 wt% potassium hydroxide aqueous solution, 6 parts by weight of 32 wt% sodium hydroxide aqueous solution and the balance of deionized water are weighed according to the following parts by weight, and the solid content is adjusted to 50%.
(2) Dissolving acrylic acid and 3-mercaptoacetic acid-2-methyl hexyl ester in 15 parts by weight of deionized water, and adjusting the pH to 5.5-6.0 by using 50 wt% of potassium hydroxide aqueous solution to obtain a first solution; dissolving hydrazine dihydrochloride in 15 parts by weight of deionized water to obtain a second solution; dissolving hydroxyethyl methacrylate and 4- (1-carboxyvinyl) benzoic acid in 10 parts by weight of deionized water to obtain a third solution;
(3) dissolving the 4-hydroxybutyl vinyl polyoxyethylene ether, the methoxy polyethylene glycol methacrylate and the unsaturated hyperbranched small monomer in the residual deionized water, sequentially adding 45% of first solution, 32 wt% of sodium hydroxide aqueous solution and sodium persulfate, and adjusting the reaction temperature to 15 ℃;
(4) simultaneously dripping the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the three solutions are completely dripped within 0.5h, and preserving heat for 1h after the dripping is finished;
(5) and (3) after the heat preservation is finished, adjusting the pH value to 6.0-7.0 by using 32 wt% of sodium hydroxide aqueous solution to obtain the ester ether copolymerization viscosity reduction type polycarboxylate superplasticizer PCE-2.
Example 3
(1) Weighing the following raw material components in parts by weight: 80 parts of 4-hydroxybutyl vinyl polyoxyethylene ether (VPEG molecular weight 6000), 25 parts of methoxy polyethylene glycol methacrylate, 7 parts of methacrylic acid, 3 parts of hydroxypropyl acrylate, 5 parts of 4- (1-carboxyvinyl) benzoic acid, 3 parts of unsaturated hyperbranched small monomer, 0.4 part of ammonium persulfate, 0.7 part of sodium triacetoxyborohydride, 0.5 part of 2, 4-diphenyl-4-methyl-1-pentene, 3 parts of 50 wt% potassium hydroxide aqueous solution, 4 parts of 32 wt% sodium hydroxide aqueous solution and the balance of deionized water, and the solid content is adjusted to 50%.
(2) Dissolving methacrylic acid and 2, 4-diphenyl-4-methyl-1-pentene in 15 parts by weight of deionized water, and adjusting the pH to 5.5-6.0 by using a 50 wt% potassium hydroxide aqueous solution to obtain a first solution; dissolving sodium triacetoxyborohydride in 15 parts by weight of deionized water to obtain a second solution; dissolving hydroxypropyl acrylate and 4- (1-carboxyvinyl) benzoic acid in 10 parts by weight of deionized water to obtain a third solution;
(3) dissolving the 4-hydroxybutyl vinyl polyoxyethylene ether, the methoxy polyethylene glycol methacrylate and the unsaturated hyperbranched small monomer in the rest deionized water, sequentially adding 40% of first solution, 32 wt% of sodium hydroxide aqueous solution and ammonium persulfate, and adjusting the reaction temperature to 20 ℃;
(4) simultaneously dripping the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the three solutions are completely dripped within 0.75h, and keeping the temperature for 0.5h after the dripping is finished;
(5) and (3) after the heat preservation is finished, adjusting the pH value to 6.0-7.0 by using 32 wt% of sodium hydroxide aqueous solution to obtain the ester ether copolymerization viscosity reduction type polycarboxylate superplasticizer PCE-3.
Example 4
(1) Weighing the following raw material components in parts by weight: 30 parts of 4-hydroxybutyl vinyl polyoxyethylene ether (VPEG molecular weight 5000), 70 parts of methoxy polyethylene glycol methacrylate, 9 parts of methacrylic acid, 5 parts of methyl acrylate, 2 parts of 4- (1-carboxyvinyl) benzoic acid, 4 parts of unsaturated hyperbranched small monomer, 0.7 part of hydrogen peroxide, 1.0 part of sodium tris (1, 1, 1, 3, 3, 3-hexafluoroisopropoxy) borohydride, 0.6 part of 3-mercaptoacetic acid-2-methylhexyl ester, 5 parts of 50 wt% potassium hydroxide aqueous solution, 5 parts of 32 wt% sodium hydroxide aqueous solution and the balance of deionized water, wherein the solid content is adjusted to 50%.
(2) Dissolving methacrylic acid and 3-mercaptoacetic acid-2-methylhexyl ester in 15 parts by weight of deionized water, and adjusting the pH to 5.5-6.0 by using 50 wt% of potassium hydroxide aqueous solution to obtain a first solution; dissolving sodium tris (1, 1, 1, 3, 3, 3-hexafluoroisopropoxy) borohydride in 15 parts by weight of deionized water to obtain a second solution; dissolving methyl acrylate and 4- (1-carboxyvinyl) benzoic acid in 10 parts by weight of deionized water to obtain a third solution;
(3) dissolving the 4-hydroxybutyl vinyl polyoxyethylene ether, the methoxy polyethylene glycol methacrylate and the unsaturated hyperbranched small monomer in the residual deionized water, sequentially adding 55% of first solution, 32 wt% of sodium hydroxide aqueous solution and hydrogen peroxide, and adjusting the reaction temperature to 30 ℃;
(4) simultaneously dripping the first solution, the second solution and the third solution into the material obtained in the step (3), finishing dripping all the three solutions within 1h, and preserving heat for 0.75h after finishing dripping;
(5) and (3) after the heat preservation is finished, adjusting the pH value to 6.0-7.0 by using 32 wt% of sodium hydroxide aqueous solution to obtain the ester ether copolymerization viscosity reduction type polycarboxylate superplasticizer PCE-4.
Example 5
Concrete performances of the ether ester copolymerization viscosity reduction type polycarboxylate superplasticizers (PCE-1, PCE-2, PCE-3 and PCE-4) synthesized in the embodiments 1-4 and a certain commercially available polycarboxylate superplasticizer (PCE-0) are compared, according to JGJ/T281-.
Fujian cement (P.O 42.5.5R) is adopted, and the concrete mixing ratio is as follows: 440kg/m cement330kg/m of fly ash380kg/m of mineral powder3720kg/m of sand31030kg/m of stones3150kg/m of water3The results obtained are shown in table 2:
table 2 example performance comparison
Figure BDA0001708411560000071
As can be seen from Table 2, the concrete added with the low-sensitivity viscosity-reduction type polycarboxylate superplasticizer prepared by the invention has shorter emptying time of the initial and 1h slump barrels than that of a comparative sample, can obviously reduce the viscosity of high-grade concrete, and has obvious viscosity reduction 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:
an ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer has the pH value of 6.0-7.0 and the solid content of 45-55%, and is prepared from the following raw materials in parts by weight: 10-100 parts by weight of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 4000-6000, 10-100 parts by weight of methoxy polyethylene glycol methacrylate, 6-10 parts by weight of unsaturated monocarboxylic acid, 3-6 parts by weight of unsaturated carboxylic ester monomer, 2-5 parts by weight of 4- (1-carboxyvinyl) benzoic acid, 1-5 parts by weight of unsaturated hyperbranched small monomer, 0.2-0.8 part by weight of oxidant, 0.2-1.0 part by weight of reducing agent, 0.2-0.6 part by weight of chain transfer agent, a proper amount of potassium hydroxide aqueous solution, a proper amount of sodium hydroxide aqueous solution and 106-130 parts by weight of deionized water, wherein the unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid, and the unsaturated carboxylic ester monomer is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate and methyl methacrylate.
The preparation method of the unsaturated hyperbranched small monomer comprises the following steps:
adding inositol and itaconic acid into a reactor under normal pressure, and simultaneously adding a catalyst, a polymerization inhibitor and a water-carrying agent to perform esterification reaction at the temperature of 100-140 ℃ for 4-9 hours to obtain an unsaturated high-branching small monomer; the catalyst is at least one of toluenesulfonic acid, sodium acetate and sodium bisulfate, and the polymerization inhibitor is at least one of 4-oxo-2, 2, 6, 6-tetramethyl-4-piperidine, N-nitroso-N-phenylhydroxylamine aluminum and N, N-copper dibutyldithiocarbamate. The molar ratio of the cyclohexanehexol to the itaconic acid is 1: 2.5-3.5, the amount of the catalyst is 0.1-0.2 wt% of the total material amount, the amount of the polymerization inhibitor is 0.05-0.2 wt% of the total material amount, the amount of the water-carrying agent is 10-20 wt% of the total material amount, and the total material amount is the total amount of the cyclohexanehexol, the itaconic acid, the catalyst, the polymerization inhibitor and the water-carrying agent.
The preparation method of the methoxy polyethylene glycol methacrylate comprises the following steps: polyethylene glycol monomethyl ether with the molecular weight of 5000-6000, methacrylic acid, concentrated sulfuric acid and copper N, N-dibutyl dithiocarbamate are placed in a reaction device and react for 3-6 hours at a constant temperature of 100-130 ℃ to obtain the copper-based catalyst. The molar ratio of the polyethylene glycol monomethyl ether to the methacrylic acid is 1: 2-6, and the use amounts of the concentrated sulfuric acid and the N, N-dibutyl copper dithiocarbamate are respectively 1.5-5% and 0.5-2% of the total mass of the polyethylene glycol monomethyl ether and the methacrylic acid.
The oxidant is at least one of hydrogen peroxide, sodium persulfate and ammonium persulfate. The reducing agent is at least one of hydrazine dihydrochloride, sodium triacetoxyborohydride and sodium tris (1, 1, 1, 3, 3, 3-hexafluoroisopropoxy) borohydride. The chain transfer agent is at least one of 3-mercaptoacetic acid-2-methylhexyl ester and 2, 4-diphenyl-4-methyl-1-pentene.
The preparation method of the ether ester copolymerization viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) dissolving unsaturated monocarboxylic acid and a chain transfer agent in 10-15 parts by weight of deionized water, and adjusting the pH to 5.5-6.0 by using a potassium hydroxide aqueous solution to obtain a first solution; dissolving a reducing agent in 10-15 parts by weight of deionized water to obtain a second solution; dissolving unsaturated carboxylic ester monomers and 4- (1-carboxyvinyl) benzoic acid in 6-10 parts by weight of deionized water to obtain a third solution;
(3) dissolving 4-hydroxybutyl vinyl polyoxyethylene ether, methoxy polyethylene glycol methacrylate and an unsaturated hyperbranched small monomer in 80-90 parts by weight of deionized water, sequentially adding 35-55% of a first solution, a proper amount of a sodium hydroxide aqueous solution and an oxidant, and adjusting the reaction temperature to 10-30 ℃ for reaction;
(4) simultaneously dripping the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dripping is finished within 0.5-1.5 h, and preserving heat for 0.5-1.5 h after the dripping is finished;
(5) and (3) adjusting the pH value of the material obtained in the step (4) to 6.0-7.0 by using a proper amount of sodium hydroxide aqueous solution to obtain the ether ester copolymerization viscosity reduction type polycarboxylate superplasticizer.
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 (8)

1. An ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer is characterized in that: the pH value is 6.0-7.0, the solid content is 45-55%, and the raw materials comprise the following components in parts by weight: 10-100 parts by weight of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 4000-6000, 10-100 parts by weight of methoxy polyethylene glycol methacrylate, 6-10 parts by weight of unsaturated monocarboxylic acid, 3-6 parts by weight of unsaturated carboxylic ester monomer, 2-5 parts by weight of 4- (1-carboxyvinyl) benzoic acid, 1-5 parts by weight of unsaturated hyperbranched small monomer, 0.2-0.8 part by weight of oxidant, 0.2-1.0 part by weight of reducing agent, 0.2-0.6 part by weight of chain transfer agent, a proper amount of potassium hydroxide aqueous solution, a proper amount of sodium hydroxide aqueous solution and 106-130 parts by weight of deionized water, wherein the unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid, and the unsaturated carboxylic ester monomer is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, methyl acrylate and methyl methacrylate.
The preparation method of the unsaturated hyperbranched small monomer comprises the following steps:
adding inositol and itaconic acid into a reactor under normal pressure, and simultaneously adding a catalyst, a polymerization inhibitor and a water-carrying agent to perform esterification reaction at the temperature of 100-140 ℃ for 4-9 hours to obtain an unsaturated high-branching small monomer; the catalyst is at least one of toluenesulfonic acid, sodium acetate and sodium bisulfate, and the polymerization inhibitor is at least one of 4-oxo-2, 2, 6, 6-tetramethyl-4-piperidine, N-nitroso-N-phenylhydroxylamine aluminum and N, N-copper dibutyldithiocarbamate.
2. The ether ester copolymerization viscosity-reducing type polycarboxylate superplasticizer according to claim 1, wherein: the molar ratio of the cyclohexanehexol to the itaconic acid is 1: 2.5-3.5, the amount of the catalyst is 0.1-0.2 wt% of the total material amount, the amount of the polymerization inhibitor is 0.05-0.2 wt% of the total material amount, the amount of the water-carrying agent is 10-20 wt% of the total material amount, and the total material amount is the total amount of the cyclohexanehexol, the itaconic acid, the catalyst, the polymerization inhibitor and the water-carrying agent.
3. The ether ester copolymerization viscosity-reducing type polycarboxylate superplasticizer according to claim 1, wherein: the preparation method of the methoxy polyethylene glycol methacrylate comprises the following steps: polyethylene glycol monomethyl ether with the molecular weight of 5000-6000, methacrylic acid, concentrated sulfuric acid and copper N, N-dibutyl dithiocarbamate are placed in a reaction device and react for 3-6 hours at a constant temperature of 100-130 ℃ to obtain the copper-based catalyst.
4. The ether ester copolymerization viscosity-reducing type polycarboxylate superplasticizer according to claim 3, wherein: the molar ratio of the polyethylene glycol monomethyl ether to the methacrylic acid is 1: 2-6, and the use amounts of the concentrated sulfuric acid and the N, N-dibutyl copper dithiocarbamate are respectively 1.5-5% and 0.5-2% of the total mass of the polyethylene glycol monomethyl ether and the methacrylic acid.
5. The ether ester copolymerization viscosity-reducing polycarboxylate superplasticizer according to any one of claims 1 to 4, wherein: the oxidant is at least one of hydrogen peroxide, sodium persulfate and ammonium persulfate.
6. The ether ester copolymerization viscosity-reducing polycarboxylate superplasticizer according to any one of claims 1 to 4, wherein: the reducing agent is at least one of hydrazine dihydrochloride, sodium triacetoxyborohydride and sodium tris (1, 1, 1, 3, 3, 3-hexafluoroisopropoxy) borohydride.
7. The ether ester copolymerization viscosity-reducing polycarboxylate superplasticizer according to any one of claims 1 to 4, wherein: the chain transfer agent is at least one of 3-mercaptoacetic acid-2-methylhexyl ester and 2, 4-diphenyl-4-methyl-1-pentene.
8. The preparation method of the ether ester copolymerization viscosity-reducing type polycarboxylate superplasticizer according to any one of claims 1 to 7, characterized by comprising the following steps: the method comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) dissolving unsaturated monocarboxylic acid and a chain transfer agent in 10-15 parts by weight of deionized water, and adjusting the pH to 5.5-6.0 by using a potassium hydroxide aqueous solution to obtain a first solution; dissolving a reducing agent in 10-15 parts by weight of deionized water to obtain a second solution; dissolving unsaturated carboxylic ester monomers and 4- (1-carboxyvinyl) benzoic acid in 6-10 parts by weight of deionized water to obtain a third solution;
(3) dissolving 4-hydroxybutyl vinyl polyoxyethylene ether, methoxy polyethylene glycol methacrylate and an unsaturated hyperbranched small monomer in 80-90 parts by weight of deionized water, sequentially adding 35-55% of a first solution, a proper amount of a sodium hydroxide aqueous solution and an oxidant, and adjusting the reaction temperature to 10-30 ℃ for reaction;
(4) simultaneously dripping the first solution, the second solution and the third solution into the material obtained in the step (3), wherein the dripping is finished within 0.5-1.5 h, and preserving heat for 0.5-1.5 h after the dripping is finished;
(5) and (3) adjusting the pH value of the material obtained in the step (4) to 6.0-7.0 by using a proper amount of sodium hydroxide aqueous solution to obtain the ether ester copolymerization viscosity reduction type polycarboxylate superplasticizer.
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