CN108192044B - Preparation method of low-mud-content sensitive polycarboxylate superplasticizer for concrete - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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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 preparation method of a low-mud content sensitive polycarboxylate superplasticizer for concrete. According to the invention, silane groups are introduced into the molecular structure of the polycarboxylic acid, so that chemical bonding can be formed with cement particles, the molecular size can be increased, the polycarboxylic acid is prevented from being adsorbed by mud with an intercalation structure, the adaptability problem with cement is improved, and the sensitivity to mud content change can be reduced; by introducing the structure of the polyether ester into the molecular structure of the polycarboxylic acid, the shape and the branched structure of the long side chain of the polycarboxylic acid in a concrete multiphase system can be improved, so that the side chain is more relaxed, the workability of concrete is improved, and the sensitivity to the change of mud content is reduced.
Description
Technical Field
The invention belongs to the technical field of building additives, and particularly relates to a preparation method of a low-concrete-mud-content sensitive polycarboxylate superplasticizer.
Background
Concrete admixtures, particularly water reducing agents, are widely used in cement-based materials such as cement paste, mortar and concrete, and are essential in the field of engineering construction and building construction. The concrete admixture can increase the fluidity of the cement-based material and effectively improve the performance of hardened concrete such as strength, durability and the like.
With the development of high performance and multifunctionality of concrete, the concrete is required to have high workability, high strength and high durability and to be applicable to many special cases. Compared with the traditional admixtures such as naphthalene water reducers, aliphatic water reducers and the like, the polycarboxylic acid water reducer with the super-dispersion performance becomes an indispensable component in high-performance concrete.
The polycarboxylic acid water reducing agent has excellent dispersing performance, can enable concrete to achieve better fluidity under lower mixing amount, and is widely applied to the total construction engineering. In the preparation process of the polycarboxylic acid water reducing agent, a polymerizable structural unit can be synthesized into the water reducing agent with a preset structure and performance through radical copolymerization according to the principle of molecular design, and the polycarboxylic acid water reducing agent is generally synthesized from monomers containing some unsaturated groups such as carboxylic acid groups, sulfonic acid groups, ester groups, polyoxyethylene groups and the like through radical copolymerization. In the molecular combination process of the polymer, different monomers are randomly or regularly polymerized together, so that the molecule has a comb-shaped structure, and the special structure of the comb-shaped structure determines the excellent performance of the comb-shaped structure.
Because the application of the concrete admixture relates to the problems of the admixture itself, cement and sand and stone materials, although the excellent water reducing performance of the polycarboxylic acid water reducing agent is widely accepted by the industry at present, with the continuous expansion of the foundation construction of China, high-quality sand and stone materials are gradually reduced, and the sand and stone materials with higher mud content are gradually applied to the concrete industry. The problem that the traditional polycarboxylate superplasticizer product is too sensitive to mud content is gradually exposed, and the practical application is greatly limited. The introduction of silane groups into the molecular structure of the polycarboxylic acid water reducing agent is considered to be a feasible scheme. The introduction of silane groups, Fan W, and other researches suggest that the introduction of silane into the molecular structure of the water reducing agent can improve the sensitivity to sulfate radical concentration (center and condensation Research, 2012, 42 (1): 166-172); svegl F. et al believe that silane groups improve the workability of Concrete (center and Concrete Research, 2008, 38 (7): 945-954); witt J. et al believe that silane groups improve water reduction (ACI specific publication, 2012, 288: 1-14).
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a low-mud content sensitive polycarboxylate superplasticizer for concrete.
The technical scheme of the invention is as follows:
a preparation method of a low-sensitive polycarboxylate superplasticizer for concrete mud content comprises the following steps:
(1) adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether and 0.05-0.2 part by weight of 0.1mol/L chloroplatinic acid ethanol solution into a first reaction device provided with a condensation recovery device, introducing nitrogen for protection while stirring, heating to 40-50 ℃, adding 0.0005-0.001 part of triphenylphosphine, then beginning to dropwise add 10-20 parts of hydride-terminated poly (dimethylsiloxane), completing dropwise addition within 1-3 h, then heating to 80-85 ℃, distilling to remove ethanol, preparing a mixed solution from 2-6 parts of acrylic acid, 1-6 parts of dicyclohexylcarbodiimide, 0.05-0.2 part of 4-dimethylaminopyridine and 0.01-0.1 part of polymerization inhibitor, quickly dropping the mixed solution into a first reaction device within 5min, continuously reacting for 1-3 h, and then carrying out vacuum distillation to remove the solvent to obtain an intermediate;
(2) adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether, 1-3 parts by weight of a chain transfer agent, 0.5-2 parts by weight of sodium hypophosphite, 1-2 parts by weight of sodium hydroxide and 105-110 parts by weight of water into a second reaction device, heating to 30-50 ℃, starting dropwise adding a first solution consisting of 0.5-2 parts by weight of ammonium persulfate and 15 parts by weight of water and a second solution consisting of 2-3 parts by weight of methoxypolyethylene glycol methacrylate, 5-7 parts by weight of acrylic acid, 1-3 parts by weight of an intermediate and 1-3 parts by weight of unsaturated ester, finishing dropwise adding within 2-4 h, then supplementing 0.5-1.5 parts by weight of sodium hypophosphite, and continuing to keep the temperature for 0.5h to obtain the concrete low-sensitive polycarboxylate water reducer with the mud content;
the structural formula of the 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether is H (OCH)2CH2)p(OCH2CH2CH2)qOCH2CH2CH2CH2OCH＝CH2Wherein p is an integer of 6-10, and q is 1 or 2;
the structural formula of the hydride-terminated poly (dimethyl siloxane) is shown in the specification
Wherein n is 4, 5 or 6;
the structural formula of the 4-hydroxybutyl vinyl ether polyoxyethylene ether is H (OCH)2CH2)xOCH2CH2CH2CH2OCR＝CH2Wherein x is an integer of 80-90, and R is a hydrogen atom or a methyl group;
the structural formula of the methoxy polyethylene glycol methacrylate is CH2＝C(CH3)CH2OOCH2CH2(CH2CH2O)mCH2CH2OOCH2C(CH3)＝CH2Wherein m is4 to 8.
In a preferred embodiment of the invention, the polymerization inhibitor is hydroquinone, p-benzoquinone or phenothiazine.
In a preferred embodiment of the present invention, the chain transfer agent is thioglycolic acid, mercaptopropionic acid, or mercaptoethanol.
In a preferred embodiment of the invention, the unsaturated ester is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
The invention has the beneficial effects that:
1. according to the invention, silane groups are introduced into the molecular structure of the polycarboxylic acid, so that chemical bonding can be formed with cement particles, the molecular size can be increased, the polycarboxylic acid is prevented from being adsorbed by mud with an intercalation structure, the adaptability problem with cement is improved, and the sensitivity to mud content change can be reduced.
2. According to the invention, by introducing the structure of the polyether ester into the molecular structure of the polycarboxylic acid, the shape and the branched structure of the long side chain of the polycarboxylic acid in a concrete multiphase system can be improved, so that the side chain is more relaxed, the workability of concrete is improved, and the sensitivity to mud content change is reduced.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
In the following examples, 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether has the structural formula H (OCH)2CH2)p(OCH2CH2CH2)qOCH2CH2CH2CH2OCH＝CH2Wherein p is an integer of 6-10, and q is 1 or 2;
the structural formula of the hydride-terminated poly (dimethyl siloxane) is shown in the specification
Wherein n is 4, 5 or 6, CAS number 70900-21-9, see
https：//www.sigmaaldrich.com/catalog/product/aldrich/423785？lang＝zh®ion＝CN；
The structural formula of the 4-hydroxybutyl vinyl ether polyoxyethylene ether is H (OCH)2CH2)xOCH2CH2CH2CH2OCR＝CH2Wherein x is an integer of 80-90, and R is a hydrogen atom or a methyl group;
the structural formula of the methoxy polyethylene glycol methacrylate is CH2＝C(CH3)CH2OOCH2CH2(CH2CH2O)mCH2CH2OOCH2C(CH3)＝CH2Wherein m is an integer of 4-8.
Example 1
Adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether (wherein p is 6, q is 1) and 0.1 part by weight of 0.1mol/L chloroplatinic acid ethanol solution into a first reaction device provided with a condensation recovery device, introducing nitrogen for protection while stirring, heating to 40 ℃, adding 0.0008 part of triphenylphosphine, dropwise adding 10 parts of hydride-terminated poly (dimethylsiloxane) (wherein n is 4), dropwise adding within 1-3 h, heating to 80 ℃, and distilling to remove ethanol. Preparing a mixed solution from 2 parts of acrylic acid, 1 part of dicyclohexylcarbodiimide, 0.05 part of 4-dimethylaminopyridine and 0.01 part of hydroquinone, quickly dropwise adding the mixed solution into a first reaction device within 5min, continuously reacting for 2h, and then carrying out vacuum distillation to remove the solvent, thus obtaining the intermediate.
Adding 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether (wherein x is 80), 3 parts of thioglycollic acid, 2 parts of sodium hypophosphite, 2 parts of sodium hydroxide and 110 parts of water into a second reaction device, heating to 40 ℃, starting to dropwise add a first solution consisting of 1 part of ammonium persulfate and 15 parts of water and a second solution consisting of 3 parts of methoxypolyethylene glycol methacrylate (wherein m is 4), 7 parts of acrylic acid, 3 parts of intermediate and 3 parts of hydroxyethyl acrylate, finishing dropwise adding within 2h, and then supplementing 0.5 part of sodium hypophosphite and continuing to keep the temperature for 0.5h to obtain the product.
Example 2
Adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether (wherein p is 10 and q is =2) and 0.15 part by weight of 0.1mol/L chloroplatinic acid ethanol solution into a first reaction device provided with a condensation recovery device, introducing nitrogen for protection while stirring, heating to 50 ℃, adding 0.0006 part by weight of triphenylphosphine, then starting dropwise adding 16 parts by weight of hydride-terminated poly (dimethylsiloxane) (wherein n is 6), dropwise adding within 1-3 h, then heating to 80 ℃, and distilling to remove ethanol. Preparing a mixed solution from 3 parts of acrylic acid, 2 parts of dicyclohexylcarbodiimide, 1 part of 4-dimethylaminopyridine and 0.08 part of p-benzoquinone, quickly dripping the mixed solution into a first reaction device within 5min, continuously reacting for 2h, and then carrying out vacuum distillation to remove the solvent to obtain an intermediate.
Adding 100 parts of 4-hydroxybutyl vinyl ether polyoxyethylene ether (wherein x is 88), 1 part of thioglycolic acid, 1 part of sodium hypophosphite, 1 part of sodium hydroxide and 105 parts of water into a second reaction device, heating to 50 ℃, starting to dropwise add a first solution consisting of 1.5 parts of ammonium persulfate and 15 parts of water and a second solution consisting of 2 parts of methoxypolyethylene glycol methacrylate (wherein m is 5), 6 parts of acrylic acid, 2 parts of intermediate and 2 parts of hydroxypropyl acrylate, finishing dropwise adding within 4h, and then supplementing 0.6 part of sodium hypophosphite and continuing to keep the temperature for 0.5h to obtain the product.
Example 3
Adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether (wherein p is 8 and q is =2) and 0.2 part by weight of 0.1mol/L chloroplatinic acid ethanol solution into a first reaction device provided with a condensation recovery device, introducing nitrogen for protection while stirring, heating to 40 ℃, adding 0.0005 part of triphenylphosphine, then starting dropwise adding 20 parts of hydride-terminated poly (dimethylsiloxane) (wherein n is 6), dropwise adding within 1-3 h, then heating to 85 ℃, and distilling to remove ethanol. 6 parts of acrylic acid, 4 parts of dicyclohexylcarbodiimide, 0.15 part of 4-dimethylaminopyridine and 0.06 part of phenothiazine are prepared into a mixed solution, the mixed solution is quickly dripped into a first reaction device within 5min, the reaction is continued for 1h, and the solvent is removed through vacuum distillation to obtain an intermediate.
Adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether (wherein x is 90), 1 part by weight of mercaptopropionic acid, 1 part by weight of sodium hypophosphite, 1.5 parts by weight of sodium hydroxide and 105 parts by weight of water into a second reaction device, heating to 30 ℃, starting to dropwise add a first solution consisting of 2 parts by weight of ammonium persulfate and 15 parts by weight of water, and a second solution consisting of 3 parts by weight of methoxypolyethylene glycol methacrylate (wherein m is 7), 5 parts by weight of acrylic acid, 1 part by weight of intermediate and 1 part by weight of hydroxyethyl methacrylate, completing dropwise addition within 3h, and then supplementing 1.2 parts by weight of sodium hypophosphite and continuing to keep the temperature for 0.5h to obtain the product.
Example 4
Adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether (wherein p is 8, q is 1) and 0.05 part by weight of 0.1mol/L chloroplatinic acid ethanol solution into a first reaction device provided with a condensation recovery device, introducing nitrogen for protection while stirring, heating to 45 ℃, adding 0.001 part by weight of triphenylphosphine, dropwise adding 12 parts by weight of hydride-terminated poly (dimethylsiloxane) (wherein n is 5), dropwise adding within 1-3 h, heating to 85 ℃, and distilling to remove ethanol. 5 parts of acrylic acid, 6 parts of dicyclohexylcarbodiimide, 0.2 part of 4-dimethylaminopyridine and 0.1 part of phenothiazine are prepared into a mixed solution, the mixed solution is quickly dripped into a first reaction device within 5min, the reaction is continued for 3h, and the solvent is removed through vacuum distillation to obtain an intermediate.
Adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether (x is 86), 2 parts by weight of mercaptoethanol, 0.5 part by weight of sodium hypophosphite, 2 parts by weight of sodium hydroxide and 105 parts by weight of water into a second reaction device, heating to 50 ℃, starting to dropwise add a first solution consisting of 0.5 part by weight of ammonium persulfate and 15 parts by weight of water and a second solution consisting of 2 parts by weight of methoxypolyethylene glycol methacrylate (m is 8), 6 parts by weight of acrylic acid, 2 parts by weight of intermediate and 2 parts by weight of hydroxypropyl methacrylate, finishing dropwise adding within 3h, and then supplementing 1.5 parts by weight of sodium hypophosphite and continuing to keep the temperature for 0.5h to obtain the product.
The concrete properties of examples 1 to 4 and comparative examples (Point-S, Kojie group) were measured using standard cement according to GB 8076 to 2008 "concrete Admixture". The concrete mixing proportion is as follows: 320kg/m cement340kg/m of fly ash3760kg/m of sand31060kg/m of stones3165kg/m of water3. Wherein the cement is Huarun PO.42.5; the fly ash is II-grade fly ash; the sand is river sand washed by water, and the fineness modulus is 2.7; the stones are washed, impact and break broken gravels, and the particle size is 5-20 m; the experimental mud is prepared by grinding kaolin, montmorillonite and illite in a weight ratio of 1: 1. The sensitivity test method comprises the steps of adjusting the mixing amount of the polycarboxylic acid to enable the concrete expansion degree to reach (550 +/-10) mm when the mud content is 0%, fixing the mixing proportion of the concrete, adding experimental mud into the concrete, wherein the weight of the mud is 1%, 3%, 5%, 7% and 9% of the weight of sand in the mixing proportion of the concrete, and testing the corresponding concrete expansion degree when different mud contents are added. The mud content width value is used as an evaluation index, the lower the mud content width value is, the lower the sensitivity is, and the calculation formula is as follows:
Rm＝Rm1+Rm3+Rm5+Rm7+Rm9
in the formula:
rm-mud content width value;
Rm1the difference between the concrete expansion degree with 1% of mud content and (550 +/-10) mm, unit mm;
Rm3the difference between the concrete expansion degree with 3 percent of mud content and (550 +/-10) mm, and the unit is mm;
Rm5the difference between the concrete expansion degree with the mud content of 5% and (550 +/-10) mm, and the unit is mm;
Rm7the difference between the concrete expansion degree with the mud content of 7% and (550 +/-10) mm, and the unit is mm;
Rm9the difference between the concrete expansion degree containing 9% of mud and (550 +/-10) mm, and the unit is mm.
The mud content sensitivity evaluation data are shown in Table 1.
TABLE 1 sensitivity evaluation test results
| Sample (I) | Example 1 | Example 2 | Example 3 | Example 4 | Control sample |
| Rm | 470 | 510 | 420 | 390 | 820 |
It is obvious to those skilled in the art that the technical solution of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following scope, and still fall into the protection scope of the present invention:
a preparation method of a low-sensitive polycarboxylate superplasticizer for concrete mud content comprises the following steps:
(1) adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether and 0.05-0.2 part by weight of 0.1mol/L chloroplatinic acid ethanol solution into a first reaction device provided with a condensation recovery device, introducing nitrogen for protection while stirring, heating to 40-50 ℃, adding 0.0005-0.001 part of triphenylphosphine, then beginning to dropwise add 10-20 parts of hydride-terminated poly (dimethylsiloxane), completing dropwise addition within 1-3 h, then heating to 80-85 ℃, distilling to remove ethanol, preparing a mixed solution from 2-6 parts of acrylic acid, 1-6 parts of dicyclohexylcarbodiimide, 0.05-0.2 part of 4-dimethylaminopyridine and 0.01-0.1 part of polymerization inhibitor, quickly dropping the mixed solution into a first reaction device within 5min, continuously reacting for 1-3 h, and then carrying out vacuum distillation to remove the solvent to obtain an intermediate;
(2) adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether, 1-3 parts by weight of a chain transfer agent, 0.5-2 parts by weight of sodium hypophosphite, 1-2 parts by weight of sodium hydroxide and 105-110 parts by weight of water into a second reaction device, heating to 30-50 ℃, starting dropwise adding a first solution consisting of 0.5-2 parts by weight of ammonium persulfate and 15 parts by weight of water and a second solution consisting of 2-3 parts by weight of methoxypolyethylene glycol methacrylate, 5-7 parts by weight of acrylic acid, 1-3 parts by weight of an intermediate and 1-3 parts by weight of unsaturated ester, finishing dropwise adding within 2-4 h, then supplementing 0.5-1.5 parts by weight of sodium hypophosphite, and continuing to keep the temperature for 0.5h to obtain the concrete low-sensitive polycarboxylate water reducer with the mud content;
the structural formula of the 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether is H (OCH)2CH2)p(OCH2CH2CH2)qOCH2CH2CH2CH2OCH＝CH2Wherein p is an integer of 6-10, and q is 1 or 2;
the structural formula of the hydride-terminated poly (dimethyl siloxane) is shown in the specification
Wherein n is 4, 5 or 6;
the structural formula of the 4-hydroxybutyl vinyl ether polyoxyethylene ether is H (OCH)2CH2)xOCH2CH2CH2CH2OCR＝CH2Wherein x is an integer of 80-90, and R is a hydrogen atom or a methyl group;
the structural formula of the methoxy polyethylene glycol methacrylate is CH2＝C(CH3)CH2OOCH2CH2(CH2CH2O)mCH2CH2OOCH2C(CH3)＝CH2Wherein m is an integer of 4-8.
The polymerization inhibitor is hydroquinone, p-benzoquinone or phenothiazine. The chain transfer agent is thioglycolic acid, mercaptopropionic acid or mercaptoethanol. The unsaturated ester is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
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 (4)
1. A preparation method of a low-sensitive polycarboxylate superplasticizer for concrete mud content is characterized by comprising the following steps: the method comprises the following steps:
(1) adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether and 0.05-0.2 part by weight of 0.1mol/L chloroplatinic acid ethanol solution into a first reaction device provided with a condensation recovery device, introducing nitrogen for protection while stirring, heating to 40-50 ℃, adding 0.0005-0.001 part of triphenylphosphine, then beginning to dropwise add 10-20 parts of hydride-terminated poly (dimethylsiloxane), completing dropwise addition within 1-3 h, then heating to 80-85 ℃, distilling to remove ethanol, preparing a mixed solution from 2-6 parts of acrylic acid, 1-6 parts of dicyclohexylcarbodiimide, 0.05-0.2 part of 4-dimethylaminopyridine and 0.01-0.1 part of polymerization inhibitor, quickly dropping the mixed solution into a first reaction device within 5min, continuously reacting for 1-3 h, and then carrying out vacuum distillation to remove the solvent to obtain an intermediate;
(2) adding 100 parts by weight of 4-hydroxybutyl vinyl ether polyoxyethylene ether, 1-3 parts by weight of a chain transfer agent, 0.5-2 parts by weight of sodium hypophosphite, 1-2 parts by weight of sodium hydroxide and 105-110 parts by weight of water into a second reaction device, heating to 30-50 ℃, starting dropwise adding a first solution consisting of 0.5-2 parts by weight of ammonium persulfate and 15 parts by weight of water and a second solution consisting of 2-3 parts by weight of methoxypolyethylene glycol methacrylate, 5-7 parts by weight of acrylic acid, 1-3 parts by weight of an intermediate and 1-3 parts by weight of unsaturated ester, finishing dropwise adding within 2-4 h, then supplementing 0.5-1.5 parts by weight of sodium hypophosphite, and continuing to keep the temperature for 0.5h to obtain the concrete low-sensitive polycarboxylate water reducer with the mud content;
the structural formula of the 4-hydroxybutyl vinyl ether polyoxyethylene polyoxypropylene ether is H (OCH)2CH2）p（OCH2CH2CH2）qOCH2CH2CH2CH2OCH=CH2Wherein p is an integer of 6-10, and q is 1 or 2;
the structural formula of the hydride-terminated poly (dimethyl siloxane) is shown in the specification
Wherein n is 4, 5 or 6;
the structural formula of the 4-hydroxybutyl vinyl ether polyoxyethylene ether is H (OCH)2CH2）xOCH2CH2CH2CH2OCR=CH2Wherein x is an integer of 80-90, and R is a hydrogen atom or a methyl group;
the structural formula of the methoxy polyethylene glycol methacrylate is CH2=C(CH3)COOCH2CH2O(CH2CH2O)mCH2CH2OCH3Wherein m is an integer of 4-8.
2. The method of claim 1, wherein: the polymerization inhibitor is hydroquinone, p-benzoquinone or phenothiazine.
3. The method of claim 1, wherein: the chain transfer agent is thioglycolic acid, mercaptopropionic acid or mercaptoethanol.
4. The method of claim 1, wherein: the unsaturated ester is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
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| A new class of organosilane-modified polycarboxylate superplasticizers with low sulfate sensitivity;Wei Fan,etal.;《Cement and Concrete Research》;20110919;第42卷;第166-172页 * |
| 含硅烷官能团聚羧酸减水剂对水泥浆体流动性和力学性能的影响;孔祥明等;《硅酸盐学报》;20140531;第42卷(第5期);第635-641页 * |
| 有机硅烷改性聚羧酸减水剂的研究进展;张海姣等;《商品混凝土》;20160630(第6期);第29-31页 * |
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