CN110156944B - Four-arm star-shaped block polycarboxylic acid superplasticizer and preparation method and application thereof - Google Patents
Four-arm star-shaped block polycarboxylic acid superplasticizer and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention discloses a four-arm star-shaped segmented polycarboxylic acid superplasticizer, a preparation method and application thereof. The invention does not use the traditional unsaturated carboxylic acid polymerization, can improve the controllability of the structure and reduce the irritation of the unsaturated carboxylic acid in the production. The water reducing agent synthesized by the invention has excellent controllability of molecular structure. The product of the invention is solid, has the characteristics of low mixing amount, high dispersibility, high fluidity, convenient transportation and storage, and low water absorption and corrosivity.
Description
Technical Field
The invention belongs to the field of superplasticizers, and particularly relates to a four-arm star-shaped block polycarboxylic acid superplasticizer and a preparation method and application thereof.
Background
Because the polycarboxylate superplasticizer (PCE) has the characteristics of low mixing amount, high water reducing rate (> 40%) and the like, the working performance, mechanical property and durability of concrete can be obviously improved, and the PCE becomes one of the essential components in the mix proportion design of high-performance or ultrahigh-performance concrete.
The polycarboxylic acid series high-performance superplasticizer produced industrially at present is mainly prepared by copolymerizing unsaturated monomers containing carboxyl, unsaturated polyether and other monomers through free radicals, and is a linear multi-branched comb-shaped structure polymer containing a large amount of carboxylate, sulfonate, ammonium and polyether macromonomers.
The star carboxylic acid superplasticizer changes the structure of a polymer molecular chain from the aspect of relating a molecular structure, introduces a polymerizable group on a central molecule, and then polymerizes corresponding monomers through polymerization reaction.
The research on star-shaped polycarboxylic acid superplasticizers at present mainly focuses on the design of an initiation central body required in the synthesis process of the superplasticizers, so that the comb-shaped polycarboxylic acid superplasticizer is prepared and is different from the traditional comb-shaped polycarboxylic acid superplasticizer.
For example, longevity Chongqi et al (2011) synthesizes N-hydroxyethyl-3-amino-N, N-methyl propionate, introduces a bromine-containing end group through ester exchange, and finally obtains a four-arm polycarboxylic acid superplasticizer by initiating atom transfer radical polymerization, but the defect is obvious, the non-conjugated bromine-containing end group obtained through ester exchange has low polymerization initiating activity of a central initiator, so that the polymerization process has less initiation at the central molecule, the thermal initiation self-polymerization occupies a certain amount, and the steric hindrance advantage provided by the star initiator cannot be well exerted.
Pelizabeth et al (2018) catalyzed ethylene oxide polymerization using a bimetallic cyanide complex to obtain a high molecular weight isobutylene-based polyoxyethylene ether, copolymerized with acrylic acid to obtain a polymer having star-shaped side chains, the polymerization process used was still conventional free radical copolymerization, the structural design of the polymer was difficult to achieve, and reactivity remained.
Chinese patent ZL 201610122451.1 discloses a preparation method of a star polycarboxylic acid water reducer, which comprises the steps of carrying out esterification reaction on polyol, carboxyl-containing trithioester, dithioic acid and the like to obtain a central compound with RAFT reversible chain transfer groups, and copolymerizing the central compound with unsaturated acid and polyether to obtain the polycarboxylic acid water reducer with a controllable structure.
Chinese patent ZL 201610122454.5 discloses a preparation method of a star polycarboxylate water reducer with a controllable molecular structure, wherein a superplasticizer is prepared by reacting a polyhydroxy compound with acyl halide with a halogen end group to obtain a compound with a multi-halogen end group, then atom transfer radical polymerization is initiated on the compound to synthesize a copolymer by copolymerizing sodium methallylsulfonate, allyl polyoxyethylene ether, sodium allylsulfonate, sodium vinylbenzene sulfonate, sodium methallylsulfonate, sodium methoxyallylsulfonate, potassium allylsulfonate, potassium styrene sulfonate, potassium vinyl sulfonate, potassium methallylsulfonate, potassium methallyloxy sulfonate and the like, but the copolymer is limited in solubility of different monomers and initiators and complex of groups on the polymer to metal ions, the controllability of the molecular structure is limited, but the synthesized star polycarboxylate superplasticizer has low mixing amount, high water solubility and high water solubility, and can be used for preparing the star polycarboxylate water reducer with controllable molecular structure, High water reducing rate, small slump, good cement compatibility and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a four-arm star block polycarboxylic acid superplasticizer, which does not use unsaturated acid.
Another object of the present invention is to provide a four-arm star-block polycarboxylic acid superplasticizer prepared by the above method.
The invention further aims to provide application of the four-arm star block polycarboxylic acid superplasticizer.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a four-arm star block polycarboxylic acid superplasticizer comprises the following steps:
(1) mixing tetrahydroxy pentaerythritol, halogen-containing carboxylic acid derivatives and a catalyst, and reacting at normal temperature for 1-48 h to obtain halogen-containing terminated four-arm initiator micromolecules;
(2) fully mixing the product of the step (1) with a monomer A, a catalyst, a ligand and a solvent AAfter the synthesis, N is introduced2Adding O in the solution2Discharge at N2Carrying out atom transfer controlled free radical polymerization reaction under protection, wherein the reaction temperature is 20-80 ℃, the reaction time is 1-24 h, obtaining homopolymer macromolecular solution, adding solvent B for precipitation, and obtaining a macromolecular initiator;
(3) fully mixing the macroinitiator obtained in the step (2) with a monomer B, a catalyst, a ligand and a solvent C, and introducing N2Adding O in the solution2Discharge at N2Carrying out atom transfer controlled free radical polymerization reaction under the protection, wherein the reaction temperature is 20-80 ℃, the reaction time is 1-24 h, and adding a solvent D for precipitation to obtain a star-shaped four-arm block polymer;
(4) mixing the star-shaped four-arm block polymer obtained in the step (3) with the component 1, a catalyst and a solvent E, carrying out heat preservation and stirring reaction at the temperature of 0-120 ℃ for 1-24 h, cooling to room temperature after the reaction is finished, and adjusting the pH value of the solution to be neutral by using a dilute alkali solution to obtain a star-shaped four-arm block superplasticizer;
the halogen-containing carboxylic acid derivative in the step (1) is more than one of 2-bromoisobutyryl bromide, 2-bromoisobutyryl chloride, 2-chloroisobutyryl chloride, 2-chloropropionyl chloride, 2-bromopropionyl chloride, 2-chloroisobutyric acid, 2-bromoisobutyric acid, ethyl 2-bromoisobutyrate or ethyl 2-chloroisobutyrate; the method greatly improves the activity of the initiator at the center and relatively reduces the ratio of thermal initiation polymerization by introducing the conjugated halogen-containing terminal group.
The catalyst in the step (1) is more than one of pyridine, triethylamine, 4-dimethylaminopyridine, bipyridine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine tri (N, N-dimethylaminoethyl) amine, N-dimethylformamide, N-dimethylacetamide, dicyclohexylcarbodiimide, sodium polyphosphate, sodium hydroxide, sodium carbonate or sodium bicarbonate;
the monomer A in the step (2) is more than one of ethyl methacrylate, methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, ethyl acrylate, methyl acrylate, butyl acrylate, tert-butyl acrylate, benzyl methacrylate, benzyl acrylate, trityl methacrylate or trityl acrylate; the molar ratio of the monomer A to the small molecule initiator in the step (1) is (100- & lt 400- & gt) 1.
The invention uses indirect method to prepare the poly carboxyl superplasticizer, adopts monomer without complexing with metal to polymerize, and then reduces the monomer into carboxyl in the conventional poly carboxylic acid superplasticizer through chemical reaction.
The ligand in the step (2) is more than one of bipyridyl, tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltriethylenetetramine tri (N, N-dimethylaminoethyl) amine; the dosage of the catalyst is 1.0 to 1.2 times of the molar weight of the catalyst.
The solvent A in the step (2) is more than one of toluene, xylene, anisole, methanol, ethanol, propanol, dichloromethane, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, diethyl ether or tetrahydrofuran. The solvents adopted by the invention are all non-aqueous phase solvents, and the non-aqueous phase polymerization can reduce the defect of overlarge or undersize concentration of free radicals in the polymerization process caused by the solubility difference of monomers, initiators, complexing agents and the like.
The solvent B in the step (2) is more than one of methanol, ethanol, propanol, acetone, water, tetrahydrofuran, butanone, ethylene glycol monomethyl ether, N-dimethylformamide or N, N-dimethylacetamide.
The monomer B in the step (3) is more than one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, 3-methyl-3-butylene-1-polyethylene glycol, 2-methyl allyl polyethylene glycol, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate; the molecular weight of the monomer B is 600-1900 g/mol, and the molar ratio of the monomer B to the macroinitiator (50-200) is 1.
And (3) the solvent C is more than one of toluene, xylene, anisole, methanol, ethanol, propanol, dichloromethane, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, diethyl ether or tetrahydrofuran.
The catalyst in the steps (2) and (3) is copper halide, and the dosage of the catalyst is 1/100-1/30 of the molar weight of the monomer A; the method adopts a polymerization system catalyzed by copper halide and properly separates and purifies after polymerization, thereby breaking through the limitation that the common free radical polymerization can not regulate and control the polymer structure.
The copper halide is one of cuprous bromide, cupric chloride or cuprous chloride.
And (3) the solvent D is more than one of methanol, ethanol, propanol, acetone, water, tetrahydrofuran, butanone, ethylene glycol monomethyl ether, N-dimethylformamide or N, N-dimethylacetamide.
The ligand in the step (3) is more than one of bipyridyl, tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltriethylenetetramine tri (N, N-dimethylaminoethyl) amine, and the dosage of the ligand is 1-1.2 times of the molar weight of the catalyst.
The component 1 in the step (4) is more than one of oxalic acid, acetic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, trifluoroacetic acid, sulfuric acid, nitric acid, hydrochloric acid or hydrobromic acid; the dosage of the catalyst is 1-10 times of the molar weight of the product in the step (3).
The catalyst in the step (4) is more than one of cuprous bromide, cuprous chloride, cupric bromide, zinc chloride, sodium chloride, ferrous chloride, ferric chloride, aluminum chloride, boron trifluoride diethyl etherate, boron trichloride or cobalt chloride; the dosage of the (3) is 1/30-1/10 of the molar weight of the product.
In the step (4), the solvent E can be added or not added; the solvent E is one or two of toluene, xylene, anisole, methanol, ethanol, propanol, water, dichloromethane, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, diethyl ether or tetrahydrofuran.
The four-arm star block polycarboxylic acid superplasticizer prepared by the invention is white solid and is colorless liquid when dissolved in water.
The four-arm star block polycarboxylic acid superplasticizer can be used as a concrete water reducing agent.
The principle of the invention is as follows:
the invention provides a four-arm star-shaped segmented polycarboxylic acid superplasticizer, which is prepared by capping tetrahydroxy molecules with halogenated carboxylic acid derivatives, taking the four-arm molecules capped with the halogenated carboxylic acid as a structural core, taking non-traditional unsaturated carboxylic acid derivatives as polymers of arms, and finally synthesizing the star-shaped four-arm segmented superplasticizer through acidolysis, separation and purification; the arm takes micromolecules as the center, the interior takes carboxyl as a core, the polyether is taken as a shell, the arm extends towards the space, the whole star polymer is adsorbed on the surfaces of cement particles in a core-shell structure, the hydrophilic polyether of the shell reduces the adhesion force between the surfaces of the cement particles through larger steric hindrance, the particles are uniformly dispersed, and simultaneously, a large amount of free water generated by agglomeration is released, so that the aim of improving the fluidity of cement paste is fulfilled. The superplasticizer has the characteristics of low mixing amount, high fluidity of cement paste and the like.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention does not use the traditional unsaturated carboxylic acid polymerization, can improve the controllability of the structure and reduce the irritation of the unsaturated carboxylic acid in the production.
(2) The water reducing agent synthesized by the invention has excellent controllability of molecular structure.
(3) The reaction temperature of the invention can be carried out at normal temperature, and the invention has the advantages of low energy consumption, strong local adaptability and the like.
(4) The invention has low mixing amount, high dispersibility and high fluidity.
(5) The product of the invention is solid and has the characteristics of convenient transportation, storage and low water absorption and corrosivity.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a four-arm star block polycarboxylic acid superplasticizer comprises the following steps:
(1) 13.6g of pentaerythritol, 0.1g of 4-dimethylaminopyridine and 2-bromoisobutyryl bromide were stirred in a flask at room temperature for 24 hours.
(2) And (2) adding 35ml of acetone into 0.7g of the product obtained in the step (1), stirring and dissolving, adding 40g of benzyl methacrylate, 0.144g of cuprous bromide, 0.144g of pentamethyldiethylenetriamine, blowing nitrogen, freezing-air extraction-blowing nitrogen, reacting for 3h at normal temperature, and precipitating with methanol and water in a ratio of 1:1 to obtain the macroinitiator.
(3) 0.1g of macroinitiator in the step (2), 10g of polyethylene glycol methacrylate, 0.144g of cuprous bromide, 0.144g of tetramethylethylenediamine, 20ml of acetone, bubbling nitrogen, freezing-air extraction-bubbling nitrogen, reacting at normal temperature for 12h, and precipitating with N, N-dimethylformamide (1: 1).
(4) And (3) adding 10g of hydrobromic acid and 0.1g of aluminum trichloride into 0.1g of the product obtained in the step (3), and stirring at normal temperature for 24 hours. This gave a four-armed star-block polycarboxylic acid superplasticizer, designated PCE 1.
Example 2
A preparation method of a four-arm star block polycarboxylic acid superplasticizer comprises the following steps:
(1) 13.6g of pentaerythritol, 0.07g of triethylamine and 2-bromoisobutyryl bromide were stirred in a flask at room temperature for 24 hours.
(2) And (2) adding 0.7g of the product obtained in the step (1) into 30ml of tetrahydrofuran, stirring and dissolving, adding 56g of benzyl methacrylate, 0.144g of cuprous bromide, 0.144g of pentamethyldiethylenetriamine, blowing nitrogen, performing a freezing-air extraction-blowing nitrogen reaction at normal temperature for 3h, and precipitating with 3:1 of acetone and water to obtain the macroinitiator.
(3) 0.1g of macroinitiator in the step (2), 10g of acrylic acid polyethylene glycol ester, 0.144g of cuprous bromide, 0.144g of bipyridyl, 20ml of acetone, bubbling nitrogen, freezing-pumping-bubbling nitrogen, reacting at normal temperature for 12h, and precipitating in ethanol.
(4) And (3) adding 0.1g of the product in the step (3) into 20ml of tetrahydrofuran, 0.4g of p-toluenesulfonic acid and 0.1g of ferric chloride, and stirring at normal temperature for 24 hours. Thus obtaining the star-shaped four-arm block polycarboxylic acid superplasticizer which is marked as PCE 2.
Example 3
A preparation method of a four-arm star block polycarboxylic acid superplasticizer comprises the following steps:
(1) 13.6g of pentaerythritol, 0.1g of pentamethyldiethylenetriamine and 2-bromoisobutyryl bromide were stirred in a flask at room temperature for 13 hours.
(2) Adding 0.7g of the product obtained in the step (1) into 36ml of butanone, stirring and dissolving, then adding 20g of benzyl methacrylate, 10g of tert-butyl methacrylate, 0.144g of cuprous bromide, 0.144g of pentamethyldiethylenetriamine, blowing nitrogen, performing a freezing-air extraction-blowing nitrogen reaction at normal temperature for 6h, and precipitating with 5:1 of methanol and water to obtain the macroinitiator.
(3) 0.1g of macroinitiator in the step (2), 10g of polyethylene glycol methacrylate, 0.144g of cuprous bromide, 0.144g of pentamethyldiethylenetriamine, 20ml of ethanol, bubbling nitrogen, freezing-air extraction-bubbling nitrogen, reacting at normal temperature for 12h, and precipitating with 1:2 of ethanol and water.
(4) 0.1g of the product of step (3) was added to 25ml of methanol and 3ml of formic acid and stirred at 40 ℃ for 24 hours. This gave a four-armed star-block polycarboxylic acid superplasticizer, designated PCE 3.
Experimental example 4
A preparation method of a four-arm star block polycarboxylic acid superplasticizer comprises the following steps:
(1) 13.6g of pentaerythritol, 0.1g of pyridine and 2-bromoisobutyryl bromide were stirred in a flask at room temperature for 48 hours.
(2) Adding 0.7g of the product obtained in the step (1) into 36ml of acetone, stirring and dissolving, adding 40g of tert-butyl methacrylate, 0.144g of cuprous bromide, 0.144g of bipyridine, blowing nitrogen, freezing, exhausting and blowing nitrogen, reacting at normal temperature for 6h, and precipitating with methanol and water in a ratio of 1:1 to obtain the macroinitiator.
(3) 0.1g of macroinitiator in the step (2), 10g of polyethylene glycol methacrylate, 0.144g of cuprous bromide, 0.144g of pentamethyldiethylenetriamine, 20ml of methanol, bubbling nitrogen, freezing-air extraction-bubbling nitrogen, reacting at normal temperature for 12h, and precipitating with 1:3 of methanol and water.
(4) And (3) adding 0.1g of the product in the step (3) into 25ml of ethanol and 6ml of hydrochloric acid, and stirring at normal temperature for 24 hours. Thus obtaining the star-shaped four-arm block polycarboxylic acid superplasticizer which is marked as PCE 4.
Experimental example 5
A preparation method of a four-arm star block polycarboxylic acid superplasticizer comprises the following steps:
(1) 13.6g of pentaerythritol, 0.1g of 4-dimethylaminopyridine and 2-bromoisobutyryl bromide were stirred in a flask at room temperature for 48 hours.
(2) Adding 0.7g of the product obtained in the step (1) into 36ml of ethanol, stirring and dissolving, adding 40g of tert-butyl methacrylate, 0.09g of copper chloride, 0.144g of bipyridine, blowing nitrogen, freezing-pumping-blowing nitrogen, reacting for 6h at 45 ℃, and precipitating with methanol and water in a ratio of 1:1 to obtain the macroinitiator.
(3) 0.1g of macroinitiator in the step (2), 10g of acrylic acid polyethylene glycol ester, 0.09g of cuprous chloride, 0.144g of pentamethyldiethylenetriamine, bubbling nitrogen, freezing-air extraction-bubbling nitrogen, reacting at normal temperature for 12h, and precipitating with ethanol and water in a ratio of 1: 3.
(4) And (3) adding 0.1g of the product in the step (3) into 25ml of ethanol, 6ml of nitric acid and 0.2g of cobalt chloride, and stirring at normal temperature for 15 hours. Thus obtaining the star-shaped four-arm block polycarboxylic acid superplasticizer which is marked as PCE 5.
Experimental example 6
A preparation method of a four-arm star block polycarboxylic acid superplasticizer comprises the following steps:
(1) 13.6g of pentaerythritol, 0.1g of 4-dimethylaminopyridine and 2-bromoisobutyryl bromide were stirred in a flask at room temperature for 48 hours.
(2) 36ml of acetone, 40g of tert-butyl methacrylate, 0.144g of cuprous bromide, 0.144g of pentamethyldiethylenetriamine, bubbling nitrogen gas, freezing-air extraction-bubbling nitrogen gas, reacting at 60 ℃ for 6h, and precipitating with methanol and water in a ratio of 1:1 to obtain the macroinitiator, wherein 0.7g of the product obtained in the step (1) is added.
(3) 0.1g of macroinitiator in the step (2), 10g of polyethylene glycol methacrylate, 0.144g of cuprous bromide, 0.144g of pentamethyldiethylenetriamine, 20ml of ethanol, bubbling nitrogen, freezing-air extraction-bubbling nitrogen, reacting at normal temperature for 12h, and precipitating with 1:3 of acetone and water.
(4) And (3) adding 0.1g of the product in the step (3) into 20ml of trifluoroacetic acid and 2g of zinc chloride, and stirring at normal temperature for 24 h. Thus obtaining the star-shaped four-arm block polycarboxylic acid superplasticizer which is marked as PCE 6.
Experimental example 7
A preparation method of a four-arm star block polycarboxylic acid superplasticizer comprises the following steps:
(1) 13.6g pentaerythritol, 0.1g triethylamine, 2-bromoisobutyryl bromide were stirred in a flask at 0 ℃ for 48 hours.
(2) Adding 0.7g of the product obtained in the step (1) into 36ml of tetrahydrofuran, stirring and dissolving, then adding 30g of trityl methacrylate, 0.144g of copper bromide, 0.144g of tetramethyl ethylenediamine, blowing nitrogen, freezing-pumping-blowing nitrogen, reacting for 6h at 60 ℃, and precipitating with 1:1 of methanol and water to obtain the macroinitiator.
(3) 0.1g of macroinitiator, 10g of polyethylene glycol methacrylate, 0.144g of cuprous bromide, 0.144g of pentamethyldiethylenetriamine, 20ml of tetrahydrofuran, bubbling nitrogen, freezing-exhausting-bubbling nitrogen, reacting at normal temperature for 12h, and precipitating with ethanol and water in a ratio of 1: 3.
(4) Adding 0.1g of the product in the step (3) into 20ml of ethanol, 0.3g of sulfuric acid and 0.2g of boron trifluoride diethyl etherate, and stirring at normal temperature for 24 hours. Thus obtaining the star-shaped four-arm block polycarboxylic acid superplasticizer which is marked as PCE 7.
Comparative example 1
A preparation method of a four-arm star-shaped random polycarboxylic acid superplasticizer comprises the following steps:
(1) 13.6g pentaerythritol, 0.1g triethylamine, 2-bromoisobutyryl bromide were stirred in a flask at 0 ℃ for 48 hours.
(2) Adding 0.7g of the product obtained in the step (1) into 36ml of tetrahydrofuran, stirring and dissolving, adding 30g of tert-butyl methacrylate, 10g of polyethylene glycol methacrylate, 0.144g of cuprous bromide, 0.144g of bipyridine, blowing nitrogen, freezing, pumping air and blowing nitrogen, reacting at 60 ℃ for 6 hours, and precipitating with methanol and water in a ratio of 1: 1.
(3) 20ml of methanol, 0.3g of hydrobromic acid and 0.2g of boron trifluoride diethyl etherate were added to 0.1g of the product of step (2), and the mixture was stirred at room temperature for 24 hours. This gave a star-shaped four-armed random polycarboxylic acid superplasticizer, designated PCE 0.
Effects of the implementation
1. Degree of fluidity of the paste
The cement paste fluidity is tested according to GB/T8077-2000 'concrete admixture homogeneity test method' by adopting reference cement, the water cement ratio is 0.35, and the mixing amount (the folded solid mixing amount is 0.2%) of the superplasticizer is based on the mass of the cement. The four-arm random superplasticizer PCE0 was selected for testing, and the results are shown in the following table 1.
TABLE 1
2. Flow retention
The fluidity of the neat paste of the cement is tested according to GB/T8077-2000 concrete admixture homogeneity test method, the water cement ratio is 0.35, the mixing amount of the superplasticizer is variable, and the fluidity is tested after 0min, 30min, 60min, 90min and 120min, and the test results are shown in the following table 2.
TABLE 2
The data show that the four-arm block superplasticizer has good fluidity effect, and the fluidity is greatly improved compared with that of a random copolymerization superplasticizer; has better fluidity maintaining effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A preparation method of a four-arm star block polycarboxylic acid superplasticizer is characterized by comprising the following steps:
(1) mixing tetrahydroxy pentaerythritol, halogen-containing carboxylic acid derivatives and a catalyst, and reacting at normal temperature for 1-48 h to obtain halogen-containing terminated four-arm initiator micromolecules;
(2) fully mixing the product obtained in the step (1) with a monomer A, a catalyst, a ligand and a solvent A, and introducing N2Adding O in the solution2Discharge at N2Carrying out atom transfer controlled free radical polymerization reaction under the protection, wherein the reaction temperature is 20-80 ℃, the reaction time is 1-24 h, obtaining homopolymer macromolecular solution, adding solvent B for precipitation, obtaining macromolecule solutionA molecular initiator;
(3) fully mixing the macroinitiator obtained in the step (2) with a monomer B, a catalyst, a ligand and a solvent C, and introducing N2 Adding O in the solution2Discharge at N2Carrying out atom transfer controlled free radical polymerization reaction under the protection, wherein the reaction temperature is 20-80 ℃, the reaction time is 1-24 h, and adding a solvent D for precipitation to obtain a star-shaped four-arm block polymer;
(4) mixing the star-shaped four-arm block polymer obtained in the step (3) with the component 1, a catalyst and a solvent E, carrying out heat preservation and stirring reaction at the temperature of 0-120 ℃ for 1-24 h, cooling to room temperature after the reaction is finished, and adjusting the pH value of the solution to be neutral by using a dilute alkali solution to obtain a star-shaped four-arm block superplasticizer;
the halogen-containing carboxylic acid derivative in the step (1) is more than one of 2-bromoisobutyryl bromide, 2-bromoisobutyryl chloride, 2-chloroisobutyryl chloride, 2-chloropropionyl chloride, 2-bromopropionyl chloride, 2-chloroisobutyric acid, 2-bromoisobutyric acid, ethyl 2-bromoisobutyrate or ethyl 2-chloroisobutyrate;
the monomer A in the step (2) is more than one of ethyl methacrylate, methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, ethyl acrylate, methyl acrylate, butyl acrylate, tert-butyl acrylate, benzyl methacrylate, benzyl acrylate, trityl methacrylate or trityl acrylate;
the monomer B in the step (3) is more than one of allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether, 3-methyl-3-butylene-1-polyethylene glycol, 2-methyl allyl polyethylene glycol, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate;
the solvent A in the step (2) is more than one of toluene, xylene, anisole, methanol, ethanol, propanol, dichloromethane, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, diethyl ether or tetrahydrofuran;
the solvent B in the step (2) is more than one of methanol, ethanol, propanol, acetone, water, tetrahydrofuran, butanone, ethylene glycol monomethyl ether, N-dimethylformamide or N, N-dimethylacetamide;
the solvent C in the step (3) is more than one of toluene, xylene, anisole, methanol, ethanol, propanol, dichloromethane, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, diethyl ether or tetrahydrofuran;
the solvent D in the step (3) is more than one of methanol, ethanol, propanol, acetone, water, tetrahydrofuran, butanone, ethylene glycol monomethyl ether, N-dimethylformamide or N, N-dimethylacetamide;
the component 1 in the step (4) is more than one of oxalic acid, acetic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, trifluoroacetic acid, sulfuric acid, nitric acid, hydrochloric acid or hydrobromic acid.
2. The method of claim 1, wherein: the catalyst in the steps (2) and (3) is copper halide.
3. The method of claim 2, wherein: the copper halide is one of cuprous bromide, cupric chloride or cuprous chloride.
4. A four-arm star block polycarboxylic acid superplasticizer is characterized in that: is prepared by the method of any one of claims 1 to 3.
5. The use of the four-arm star-block polycarboxylic acid superplasticizer of claim 4 as a concrete water reducer.
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| CN114702683A (en) * | 2021-12-30 | 2022-07-05 | 江苏超力建材科技有限公司 | Hyperbranched polycarboxylic acid water reducer and preparation method thereof |
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| EP1260536A1 (en) * | 2001-05-22 | 2002-11-27 | Basf Aktiengesellschaft | Water-soluble polymers from esters of acrylic acid, methacrylic acid and alkyl polyalkylene glycols |
| CN103482897A (en) * | 2013-09-09 | 2014-01-01 | 江苏博特新材料有限公司 | Block poly-carboxylic acid concrete high-efficiency water reducing agent and preparation method thereof |
| CN105669913A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Preparation method of star polycarboxylate water reducing agent with controllable molecular structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1260536A1 (en) * | 2001-05-22 | 2002-11-27 | Basf Aktiengesellschaft | Water-soluble polymers from esters of acrylic acid, methacrylic acid and alkyl polyalkylene glycols |
| CN103482897A (en) * | 2013-09-09 | 2014-01-01 | 江苏博特新材料有限公司 | Block poly-carboxylic acid concrete high-efficiency water reducing agent and preparation method thereof |
| CN105669913A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Preparation method of star polycarboxylate water reducing agent with controllable molecular structure |
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