CN110643005A - Preparation method of ester viscosity-reducing polycarboxylic acid superplasticizer - Google Patents
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- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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Abstract
The invention discloses a preparation method of an ester viscosity-reducing polycarboxylic acid superplasticizer, which comprises the following steps: (1) preparing unsaturated hyperbranched small monomers; (2) performing esterification reaction; (3) and (3) carrying out copolymerization reaction. The invention synthesizes an unsaturated high-branching small monomer, and introduces the unsaturated high-branching small monomer and benzene-containing rigid small monomer 4-vinylmethyl benzoate into the polycarboxylic acid superplasticizer together, so that the molecular conformation of the polycarboxylic acid superplasticizer can be more extended, the steric hindrance effect of a side chain of the polycarboxylic acid superplasticizer is further improved, and the viscosity of concrete is greatly reduced. The preparation method has the advantages of simple preparation process, convenient production, low cost and little pollution.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of an ester viscosity-reducing type polycarboxylic acid superplasticizer.
Background
The polycarboxylate superplasticizer serving as a third-generation water reducer 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 superplasticizer in the current market can well meet the construction requirements of concrete with low water-cement ratio due to higher water reducing rate, but with the development of concrete technology towards the functionalization directions of high strength, high durability, self-leveling and the like, the water-cement ratio of the polycarboxylic acid superplasticizer is continuously reduced, the viscosity of the concrete is increased along with the water-cement ratio, the flowing speed is slowed down, the conventional polycarboxylic acid superplasticizer is continuously used, and the difficult problem of the concrete construction performance brought by the low water-cement ratio cannot be well solved. Therefore, the development of polycarboxylic acid superplasticizers capable of reducing the viscosity of concrete is urgently needed to solve the engineering application problem.
At home and abroad, researchers have focused on the development and application of viscosity-reducing polycarboxylic acid superplasticizers. 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 patent reports about viscosity reducers are reported at home and abroad, in 2004, a Japanese catalyst company applies for polycarboxylic acid additive patents for reducing the viscosity of concrete, and compared with the traditional polycarboxylic acid superplasticizer, 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 disclosed by the patent is doped into concrete by 10-30%, and the effect can be exerted only by a high 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 a preparation method of an ester viscosity-reducing polycarboxylic acid superplasticizer.
The technical scheme of the invention is as follows:
a preparation method of an ester viscosity-reducing polycarboxylic acid superplasticizer comprises the following steps:
(1) preparation of unsaturated hyperbranched small monomer: 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;
(2) esterification reaction: placing polyethylene glycol monomethyl ether, unsaturated monocarboxylic acid, concentrated sulfuric acid and copper acetate in a first reaction device, and reacting at a constant temperature of 100-130 ℃ for 3-6 h to obtain an esterified monomer MP;
(3) and (3) copolymerization reaction: placing the unsaturated hyperbranched small monomer prepared in the step (1) and water in a second reaction device; mixing unsaturated carboxylic acid hydroxyalkyl ester, esterified monomer MP, unsaturated monocarboxylic acid, 4-vinyl methyl benzoate and water to obtain a monomer mixed water solution; mixing an initiator with water to obtain an initiator aqueous solution; when the temperature in the second reaction device reaches 55-95 ℃, dropwise adding the monomer mixed aqueous solution and the initiator aqueous solution in 3-4 h, continuing to react for 1-2 h after dropwise adding, and adding a proper amount of sodium hydroxide aqueous solution for neutralization to obtain the ester viscosity-reducing polycarboxylic acid water reducer;
the polymerization inhibitor is at least one of N-nitroso-N-phenylhydroxylamine aluminum, 4-oxo-2, 2, 6, 6-tetramethyl-4-piperidine and copper N, N-dibutyl dithiocarbamate, the unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid, and the unsaturated hydroxyalkyl carboxylate is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
In a preferred embodiment of the invention, in the step (1), 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.
In a preferred embodiment of the present invention, in the step (2), the molar ratio of the methoxypolyethylene glycol to the unsaturated monocarboxylic acid is 1: 2-6, and the concentrated sulfuric acid and the polymerization inhibitor are respectively used in an amount of 1.5-5% and 0.5-2% of the total mass of the methoxypolyethylene glycol and the methacrylic acid.
In a preferred embodiment of the invention, in the second reaction of the step (3), the mass ratio of the unsaturated hyperbranched small monomer prepared in the step (1) and water is 1-5: 45-55.
In a preferred embodiment of the invention, in the step (3), in the monomer mixed aqueous solution, the mass ratio of the unsaturated carboxylic acid hydroxyalkyl ester, the esterified monomer MP, the unsaturated monocarboxylic acid, the 4-vinyl methyl benzoate and the water is 4-20: 50-80: 5-15: 1-3: 25-35; in the initiator aqueous solution, the mass ratio of the initiator to the water is 1-5: 25-35.
In a preferred embodiment of the present invention, the water-carrying agent is at least one of petroleum ether, cyclohexane and toluene.
In a preferred embodiment of the present invention, the polyethylene glycol monomethyl ether has a molecular weight of 5000 to 8000.
In a preferred embodiment of the present invention, the initiator is at least one of hydrogen peroxide, sodium persulfate, and ammonium persulfate.
The invention has the beneficial effects that:
1. after the polycarboxylic acid superplasticizer is adsorbed on the surface of the cement particles, a water film layer can be formed on the surface 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 the concrete is reduced. The invention synthesizes the methoxy polyethylene glycol methacrylate (MPEGMAA) with ultrahigh molecular weight by esterification, improves the length of the side chain of the polycarboxylic superplasticizer, enlarges the steric hindrance, thickens the water film layer and has more obvious viscosity reduction effect.
2. The invention synthesizes an unsaturated high-branching small monomer, and introduces the unsaturated high-branching small monomer and benzene-containing rigid small monomer 4-vinylmethyl benzoate into the polycarboxylic acid superplasticizer together, so that the molecular conformation of the polycarboxylic acid superplasticizer can be more extended, the steric hindrance effect of a side chain of the polycarboxylic acid superplasticizer is further improved, and the viscosity of concrete is greatly reduced.
3. The preparation method has the advantages of simple preparation process, convenient production, low cost and little pollution.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Unless otherwise specified, the parts are by weight in the following examples.
Example 1
(1) Preparation of unsaturated hyperbranched small monomer:
under the condition of normal pressure, 100 parts of cyclohexanehexol and 185 parts of itaconic acid are added into a reactor, and simultaneously 0.32 part of toluenesulfonic acid, 0.63 part of N-nitroso-N-phenylhydroxylamine aluminum and 32 parts of petroleum ether are added for esterification reaction at the temperature of 130 ℃ for 4 hours, so that the unsaturated hyperbranched small monomer is obtained.
(2) Esterification reaction: 100.00 parts by weight of polyethylene glycol monomethyl ether with the molecular weight of 5000, 51.65 parts by weight of methacrylic acid, 2.27 parts by weight of concentrated sulfuric acid and 0.76 part by weight of copper acetate are placed in a first reaction device, and the temperature is kept at 130 ℃ for 3 hours to obtain the esterified monomer MP. Wherein the molar ratio of the polyethylene glycol monomethyl ether to the methacrylic acid is 1: 6, and the dosage of the concentrated sulfuric acid and the cupric acetate is 1.5 percent and 0.5 percent of the total mass of the polyethylene glycol monomethyl ether and the methacrylic acid respectively.
(3) And (3) copolymerization reaction: placing 2 parts by weight of unsaturated hyperbranched small monomer and 50 parts by weight of water in a second reaction device; mixing 4 parts of hydroxyethyl acrylate monomer, 50 parts of esterified monomer MP, 6 parts of acrylic acid, 1 part of methyl 4-vinylbenzoate and 30 parts of water to obtain a monomer mixed aqueous solution; mixing 2 parts of ammonium persulfate and 30 parts of water to obtain an initiator aqueous solution; when the temperature in the second reaction device reaches 55 ℃, dropwise adding the monomer mixed aqueous solution and the initiator aqueous solution within 3 hours respectively; after the dropwise addition, continuously reacting for 1h, and adding 20 parts of 30% sodium hydroxide aqueous solution for neutralization to obtain the ester viscosity-reducing polycarboxylate superplasticizer PCE-1.
Example 2
(1) Preparation of unsaturated hyperbranched small monomer:
under the condition of normal pressure, 100 parts of cyclohexanehexol and 250 parts of itaconic acid are added into a reactor, and simultaneously 0.47 part of sodium acetate, 0.60 part of 4-oxo-2, 2, 6, 6-tetramethyl-4-piperidine and 47 parts of cyclohexane are added for esterification reaction at the temperature of 140 ℃ for 5 hours, so as to obtain the unsaturated hyperbranched small monomer.
(2) Esterification reaction: according to the parts by weight, 120.00 parts of polyethylene glycol monomethyl ether with the molecular weight of 6000, 43.05 parts of methacrylic acid, 4.08 parts of concentrated sulfuric acid and 1.63 parts of copper acetate are placed in a first reaction device, and the temperature is kept at 120 ℃ for 5 hours to obtain the esterified monomer MP. Wherein the molar ratio of the polyethylene glycol monomethyl ether to the methacrylic acid is 1: 5, and the dosages of the concentrated sulfuric acid and the cupric acetate are respectively 2.5 percent and 1 percent of the total mass of the polyethylene glycol monomethyl ether and the methacrylic acid.
(3) And (3) copolymerization reaction: 3 parts of unsaturated high-branching small monomer and 50 parts of water are placed in a second reaction device according to parts by weight; mixing 4-20 parts of hydroxypropyl acrylate, 60 parts of esterified monomer MP, 8 parts of methacrylic acid, 2 parts of methyl 4-vinylbenzoate and 30 parts of water to obtain a monomer mixed aqueous solution; mixing 3 parts of sodium persulfate and 30 parts of water to obtain an initiator aqueous solution; when the temperature in the second reaction device reaches 60 ℃, dropwise adding the monomer mixed aqueous solution and the initiator aqueous solution within 3.5 hours respectively; after the dropwise addition, continuously reacting for 1h, and adding 20 parts of 30% sodium hydroxide aqueous solution for neutralization to obtain the ester viscosity-reducing polycarboxylate superplasticizer PCE-2.
Example 3
(1) Preparation of unsaturated hyperbranched small monomer:
under the condition of normal pressure, 100 parts of cyclohexanehexol and 200 parts of itaconic acid are added into a reactor, and simultaneously 0.52 part of sodium bisulfate, 0.40 part of N-nitroso-N-phenylhydroxylamine aluminum and 52 parts of petroleum ether are added for esterification reaction at the temperature of 125 ℃ for 6 hours, thus obtaining the unsaturated hyperbranched small monomer.
(2) Esterification reaction: 200.00 parts by weight of polyethylene glycol monomethyl ether with the molecular weight of 7000, 34.44 parts by weight of acrylic acid, 8.21 parts by weight of concentrated sulfuric acid and 3.52 parts by weight of copper acetate are placed in a first reaction device, and the temperature is kept constant at 110 ℃ for 4 hours to obtain the esterified monomer MP. Wherein the molar ratio of the polyethylene glycol monomethyl ether to the acrylic acid is 1: 4, and the dosages of the concentrated sulfuric acid and the cupric acetate are respectively 3.5 percent and 1.5 percent of the total mass of the polyethylene glycol monomethyl ether and the acrylic acid.
(3) And (3) copolymerization reaction: placing 4 parts of unsaturated high-branching small monomer and 50 parts of water in a second reaction device according to parts by weight; mixing 4-20 parts of hydroxyethyl methacrylate, 70 parts of esterified monomer MP, 12 parts of acrylic acid, 2.5 parts of methyl 4-vinylbenzoate and 30 parts of water to obtain a monomer mixed aqueous solution; mixing 4 parts of ammonium persulfate and 30 parts of water to obtain an initiator aqueous solution; when the temperature in the second reaction device reaches 75 ℃, dropwise adding the monomer mixed aqueous solution and the initiator aqueous solution within 3 hours; after the dropwise addition, continuously reacting for 1h, and adding 20 parts of 30% sodium hydroxide aqueous solution for neutralization to obtain the ester viscosity-reducing polycarboxylate superplasticizer PCE-3.
Example 4
(1) Preparation of unsaturated hyperbranched small monomer:
under the condition of normal pressure, 100 parts of cyclohexanehexol and 220 parts of itaconic acid are added into a reactor, and simultaneously 0.68 part of sodium acetate, 0.40 part of copper N, N-dibutyl dithiocarbamate and 68 parts of cyclohexane are added for esterification reaction at the temperature of 120 ℃ for 7 hours, so as to obtain the unsaturated hyperbranched small monomer.
(2) Esterification reaction: 240.00 parts by weight of polyethylene glycol monomethyl ether with molecular weight of 8000, 17.22 parts by weight of acrylic acid, 12.86 parts by weight of concentrated sulfuric acid and 5.14 parts by weight of copper acetate are placed in a reaction kettle B, and the temperature is kept constant at 100 ℃ for 6 hours to obtain the esterified monomer MP. Wherein the molar ratio of the polyethylene glycol monomethyl ether to the acrylic acid is 1: 2, and the dosages of the concentrated sulfuric acid and the cupric acetate are respectively 5 percent and 2 percent of the total mass of the polyethylene glycol monomethyl ether and the acrylic acid.
(3) And (3) copolymerization reaction: placing 5 parts by weight of unsaturated hyperbranched small monomer and 50 parts by weight of water in a second reaction device; mixing 4-20 parts of hydroxypropyl methacrylate, 80 parts of esterified monomer MP, 15 parts of methacrylic acid, 3 parts of methyl 4-vinylbenzoate and 30 parts of water to obtain a monomer mixed aqueous solution; mixing 5 parts of hydrogen peroxide and 30 parts of water to obtain an initiator aqueous solution; when the temperature in the second reaction device reaches 95 ℃, dropwise adding the monomer mixed aqueous solution and the initiator aqueous solution in 4 hours respectively; after the dropwise addition, continuously reacting for 1h, and adding 20 parts of 30% sodium hydroxide aqueous solution for neutralization to obtain the ester viscosity-reducing polycarboxylate superplasticizer PCE-4.
Concrete performance measurement is carried out on the ester viscosity-reducing polycarboxylic acid superplasticizer synthesized in the embodiment 1-4 and a comparison sample (a commercially available common polycarboxylic acid superplasticizer), according to JGJ/T281 and 2012 'high-strength concrete application technical specification', the admixture mixing amount is adjusted to ensure that the initial slump of fresh concrete is 220 +/-10 mm and the initial concrete expansion is 520 +/-10 mm, the viscosity of the concrete is measured by the emptying time of initial and 1h slump barrels, and the less time is used, the lower the viscosity of the concrete is, the more remarkable the viscosity-reducing effect of the admixture is. The concrete raw materials and the mixing ratio are shown in Table 1, and the obtained results are shown in Table 2:
TABLE 1 concrete raw materials and mixing ratio
Table 2 example performance comparison
From the results, the concrete added with the viscosity-reducing polycarboxylic acid 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-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 an ester viscosity-reducing polycarboxylic acid superplasticizer comprises the following steps:
(1) preparation of unsaturated hyperbranched small monomer: 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;
(2) esterification reaction: placing polyethylene glycol monomethyl ether, unsaturated monocarboxylic acid, concentrated sulfuric acid and a polymerization inhibitor in a first reaction device, and reacting at a constant temperature of 100-130 ℃ for 3-6 hours to obtain an esterified monomer MP;
(3) and (3) copolymerization reaction: placing the unsaturated hyperbranched small monomer prepared in the step (1) and water in a second reaction device; mixing unsaturated carboxylic acid hydroxyalkyl ester, esterified monomer MP, unsaturated monocarboxylic acid, 4-vinyl methyl benzoate and water to obtain a monomer mixed water solution; mixing an initiator with water to obtain an initiator aqueous solution; when the temperature in the second reaction device reaches 55-95 ℃, dropwise adding the monomer mixed aqueous solution and the initiator aqueous solution in 3-4 h, continuing to react for 1-2 h after dropwise adding, and adding a proper amount of sodium hydroxide aqueous solution for neutralization to obtain the ester viscosity-reducing polycarboxylic acid water reducer;
the polymerization inhibitor is at least one of N-nitroso-N-phenylhydroxylamine aluminum, 4-oxo-2, 2, 6, 6-tetramethyl-4-piperidine and copper N, N-dibutyl dithiocarbamate, the unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid, and the unsaturated hydroxyalkyl carboxylate is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
In the step (1), 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. In the step (2), the molar ratio of the polyethylene glycol monomethyl ether to the unsaturated monocarboxylic acid is 1: 2-6, and the dosages of the concentrated sulfuric acid and the polymerization inhibitor are respectively 1.5-5% and 0.5-2% of the total mass of the polyethylene glycol monomethyl ether and the methacrylic acid. In the second reaction in the step (3), the mass ratio of the unsaturated hyperbranched small monomer prepared in the step (1) to water is 1-5: 45-55; in the monomer mixed water solution, the mass ratio of unsaturated carboxylic acid hydroxyalkyl ester, esterified monomer MP, unsaturated monocarboxylic acid, 4-vinyl methyl benzoate and water is 4-20: 50-80: 5-15: 1-3: 25-35; in the initiator aqueous solution, the mass ratio of the initiator to the water is 1-5: 25-35.
The water-carrying agent is at least one of petroleum ether, cyclohexane and toluene. The molecular weight of the polyethylene glycol monomethyl ether is 5000-8000. The initiator is at least one of hydrogen peroxide, sodium persulfate and ammonium persulfate.
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. A preparation method of an ester viscosity-reducing polycarboxylic acid superplasticizer is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of unsaturated hyperbranched small monomer: 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;
(2) esterification reaction: placing polyethylene glycol monomethyl ether, unsaturated monocarboxylic acid, concentrated sulfuric acid and copper acetate in a first reaction device, and reacting at a constant temperature of 100-130 ℃ for 3-6 h to obtain an esterified monomer MP;
(3) and (3) copolymerization reaction: placing the unsaturated hyperbranched small monomer prepared in the step (1) and water in a second reaction device; mixing unsaturated carboxylic acid hydroxyalkyl ester, esterified monomer MP, unsaturated monocarboxylic acid, 4-vinyl methyl benzoate and water to obtain a monomer mixed water solution; mixing an initiator with water to obtain an initiator aqueous solution; when the temperature in the second reaction device reaches 55-95 ℃, dropwise adding the monomer mixed aqueous solution and the initiator aqueous solution in 3-4 h, continuing to react for 1-2 h after dropwise adding, and adding a proper amount of sodium hydroxide aqueous solution for neutralization to obtain the ester viscosity-reducing polycarboxylic acid water reducer;
the polymerization inhibitor is at least one of N-nitroso-N-phenylhydroxylamine aluminum, 4-oxo-2, 2, 6, 6-tetramethyl-4-piperidine and copper N, N-dibutyl dithiocarbamate, the unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid, and the unsaturated hydroxyalkyl carboxylate is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
2. The method of claim 1, wherein: in the step (1), 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.
3. The method of claim 1, wherein: in the step (2), the molar ratio of the polyethylene glycol monomethyl ether to the unsaturated monocarboxylic acid is 1: 2-6, and the dosages of the concentrated sulfuric acid and the polymerization inhibitor are respectively 1.5-5% and 0.5-2% of the total mass of the polyethylene glycol monomethyl ether and the methacrylic acid.
4. The method of claim 1, wherein: in the second reaction in the step (3), the mass ratio of the unsaturated hyperbranched small monomer prepared in the step (1) to water is 1-5: 45-55.
5. The method of claim 1, wherein: in the step (3), in the monomer mixed water solution, the mass ratio of unsaturated carboxylic acid hydroxyalkyl ester, esterified monomer MP, unsaturated monocarboxylic acid, 4-vinyl methyl benzoate and water is 4-20: 50-80: 5-15: 1-3: 25-35; in the initiator aqueous solution, the mass ratio of the initiator to the water is 1-5: 25-35.
6. The method of claim 1, wherein: the water-carrying agent is at least one of petroleum ether, cyclohexane and toluene.
7. The method of claim 1, wherein: the molecular weight of the polyethylene glycol monomethyl ether is 5000-8000.
8. The method of claim 1, wherein: the initiator is at least one of hydrogen peroxide, sodium persulfate and ammonium persulfate.
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| CN114456371A (en) * | 2021-12-16 | 2022-05-10 | 厦门市建筑科学研究院有限公司 | Esterified monomer, low-drainage-type polycarboxylate superplasticizer suitable for machine-made sand and preparation method of polycarboxylate superplasticizer |
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