CN113754839A - Slow-release lignin-based polycarboxylic acid high-performance water reducing agent and preparation method thereof - Google Patents
Slow-release lignin-based polycarboxylic acid high-performance water reducing agent and preparation method thereof Download PDFInfo
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- CN113754839A CN113754839A CN202111082338.2A CN202111082338A CN113754839A CN 113754839 A CN113754839 A CN 113754839A CN 202111082338 A CN202111082338 A CN 202111082338A CN 113754839 A CN113754839 A CN 113754839A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
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- 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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- 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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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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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
A slow-release lignin-based polycarboxylic acid high-performance water reducer and a preparation method thereof are disclosed, wherein the synthesis raw materials of the slow-release lignin-based polycarboxylic acid high-performance water reducer contain a high-molecular-weight isopentenyl polyoxyethylene ether macromonomer, sodium lignosulfonate, an isomerate comonomer and a polyether comonomer. The slow-release lignin-based polycarboxylate superplasticizer has stable performance, can be combined with other compound components for better compatibility, meets the requirements of slump retaining performance of construction concrete, and solves the problems of poor slump retaining effect, bleeding, segregation, bottom scraping and the like in the practical application process of the polycarboxylate superplasticizer. Moreover, the preparation method has simple production process, easy operation and low requirement on reaction temperature, thereby reducing the production cost and being environment-friendly. The invention has the advantages of easily obtained raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained-release effect and the like, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a slow-release lignin-based polycarboxylic acid high-performance water reducing agent and a preparation method thereof.
Background
With the continuous development and improvement of concrete application technology, concrete is widely applied in more and more fields as one of common building base materials, and simultaneously, higher and higher requirements on the performance of the concrete are provided. Among them, the workability is excellent, the pumping construction is easy, and the slump loss resistance is good. Because the varieties of cement, sand and stone and admixture in China are more complex and have increasingly poor quality, the polycarboxylic acid water reducer also shows many defects in application, compounding is usually used as a means for solving the adaptability problem of the polycarboxylic acid water reducer in the concrete application process, however, the variety of the water reducer used in compounding has limited performance, and the problems of poor slump retaining effect, difficult adaptation to complex materials, bleeding, segregation, bottom scraping and the like in the practical application process of the polycarboxylic acid water reducer cannot be well solved.
Therefore, aiming at the defects of the prior art, the slow-release polycarboxylic acid high-performance water reducing agent with obvious slump retaining effect and excellent workability and the preparation method thereof are provided to overcome the defects of the prior art.
Disclosure of Invention
One of the purposes of the invention is to provide a slow-release lignin-based polycarboxylic acid high-performance water reducing agent which has the advantages of obvious slump loss prevention effect and excellent workability, and the defects of the prior art are avoided.
The above object of the present invention is achieved by the following technical measures:
the synthesis raw materials comprise a large-molecular-weight isopentenyl polyoxyethylene ether macromonomer, sodium lignosulfonate, an isomerous ester comonomer and a polyether comonomer.
Preferably, the chemical structural formula of the isomeric ester comonomer is as follows:
CH2＝C(CH3)-COO-(CH2-CH2-O-)m-(CH2-CH(CH3)-O-)n-(-CH2-CH2-O-)L-H，
wherein m is 3-8, n is 3-8, and L is 10-20.
Preferably, the molecular weight of the isomeric ester comonomer is 1000 to 5000.
Preferably, the molecular weight of the isopentenyl polyoxyethylene ether macromonomer is 1500-5000.
Preferably, the molecular weight of the sodium lignosulfonate is 4000-12000.
Preferably, the polyether comonomer comprises an unsaturated carboxylic acid comonomer and an unsaturated ester-based comonomer.
Preferably, the molecular weight of the isomeric ester comonomer is 800 to 1800.
Preferably, the molecular weight of the prenyl polyoxyethylene ether macromonomer is 2000-4000.
Preferably, the molecular weight of the sodium lignosulfonate is 5000-10000.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent also contains an initiator, a reducing agent, a chain transfer agent, liquid alkali and water;
the synthetic raw materials comprise the following components in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 200 to 500 portions;
sodium lignosulfonate: 6-25 parts;
isomeric ester comonomers: 3.0 to 15.0 parts;
unsaturated carboxylic acid comonomer: 10-40 parts;
unsaturated ester-based comonomer: 25-60 parts;
initiator: 0.5 to 3 parts;
reducing agent: 0.2 to 1.5 portions;
chain transfer agent: 0.5 to 5 parts;
liquid caustic soda: 2-15 parts;
water: 300 to 800 portions.
The synthetic raw materials comprise the following components in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 300 to 400 portions;
sodium lignosulfonate: 8-20 parts;
isomeric ester comonomers: 4.0 to 10.0 portions;
unsaturated carboxylic acid comonomer: 20-30 parts;
unsaturated ester-based comonomer: 35-50 parts;
initiator: 0.8 to 2 parts;
reducing agent: 0.3 to 1.0 portion;
chain transfer agent: 1-3 parts;
liquid caustic soda: 5-10 parts;
water: 450 to 600 portions.
Preferably, the unsaturated carboxylic acid comonomer is at least one of methacrylic acid or acrylic acid.
Preferably, the unsaturated ester-based comonomer is at least one of hydroxyethyl acrylate or hydroxypropyl acrylate.
Preferably, the initiator is at least one of hydrogen peroxide or ammonium persulfate;
preferably, the chain transfer agent is at least one of thioglycolic acid, 3-mercaptopropionic acid, or mercaptoethanol.
Preferably, the reducing agent is L-ascorbic acid, sodium formaldehyde sulfoxylate or a composite reducing agent, wherein the composite reducing agent is a mixture of L-ascorbic acid and sodium formaldehyde sulfoxylate.
The second purpose of the invention is to provide a preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent, which avoids the defects of the prior art. The preparation method can obtain the slow-release lignin-based polycarboxylic acid high-performance water reducer with the advantages of obvious slump retaining effect and excellent workability.
The above object of the present invention is achieved by the following technical measures:
the preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following steps:
step one, adding a large molecular weight isopentenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 15-35 ℃, adding an initiator, and stirring for 5-10 min;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is an aqueous solution of an unsaturated carboxylic acid comonomer, an unsaturated ester group comonomer and an isomeric ester comonomer, and the material solution B is an aqueous solution of a reducing agent and a chain transfer agent;
step three, controlling the addition of the material solution A within 2-5 h, and controlling the addition of the material solution B within 2.5-5.5 h;
step four, continuously preserving the heat for 0.5 to 3 hours at the temperature of between 30 and 40 ℃;
and fifthly, adding liquid alkali to enable the pH value to be 4.5-6.5, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
Preferably, the first step is to add the large molecular weight prenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into the reactor, stir, heat to 20-30 ℃, add the initiator, and stir for 5-10 min; .
Preferably, the third step is to control the addition of the material solution A within 3 to 4 hours and to control the addition of the material solution B within 3.5 to 4.5 hours.
Preferably, the fourth step is to keep the temperature at 35-38 ℃ for 1-2 h.
Preferably, the fifth step is to add liquid alkali to make the pH value 5-6, so as to obtain the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
The invention relates to a slow-release lignin-based polycarboxylic acid high-performance water reducer and a preparation method thereof, wherein the synthesis raw materials of the slow-release lignin-based polycarboxylic acid high-performance water reducer contain a high-molecular-weight isopentenyl polyoxyethylene ether macromonomer, sodium lignosulfonate, an isomerate comonomer and a polyether comonomer. The slow-release lignin-based polycarboxylic acid high-performance water reducing agent is characterized in that sodium lignosulfonate is creatively grafted on a prenyl polyoxyethylene ether macromonomer molecule, and the sodium lignosulfonate has active groups such as sulfonic groups, alcoholic hydroxyl groups, carboxyl groups and the like. The isomeric esterification monomer has special isomeric steric hindrance, and the slow release property of an ester group of the isomeric esterification monomer is utilized, so that the obtained slow release type lignin-based polycarboxylic acid water reducing agent has good slump retaining property and workability. The slow-release lignin-based polycarboxylate superplasticizer disclosed by the invention is stable in performance, can be combined with other compound components and has good compatibility, meets the requirements of slump retaining performance of construction concrete, and solves the problems of poor slump retaining effect, bleeding, segregation, bottom scraping and the like in the practical application process of the polycarboxylate superplasticizer. In addition, the invention has the advantages of easy acquisition of raw materials, good slow release effect and the like. The preparation method has simple production process, easy operation and low requirement on reaction temperature, thereby reducing the production cost and being environment-friendly. The invention has the advantages of easily obtained raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained-release effect and the like, and has wide application prospect.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, which are not intended to limit the present invention in any way. The starting reagents used in the examples of the present invention are all those conventionally purchased unless otherwise specified.
Example 1.
A slow-release lignin-based polycarboxylic acid high-performance water reducing agent is prepared from a large-molecular-weight isopentenyl polyoxyethylene ether macromonomer, sodium lignosulfonate, an isomerous ester comonomer and a polyether comonomer.
Wherein the chemical structural formula of the isomeric ester comonomer is as follows:
CH2＝C(CH3)-COO-(CH2-CH2-O-)m-(CH2-CH(CH3)-O-)n-(-CH2-CH2-O-)L-H，
wherein m is 3-8, n is 3-8, and L is 10-20.
The molecular weight of the isomeric ester comonomer is 500-2000. The molecular weight of the isopentenyl polyoxyethylene ether macromonomer is 1500-5000. The molecular weight of the sodium lignin sulfonate is 4000-12000.
The isomeric ester monomer is an ester macromonomer obtained by adding special alcohol head methyl acrylate and block propylene oxide ethylene oxide, has active activity, is similar to the polymerization reactivity of acrylic acid, and is very easy to generate free radical copolymerization reaction with methacrylic acid or acrylic acid in unsaturated carboxylic acid comonomer.
In addition, EO bonds in the isomeric ester monomers can promote the reaction of other macromonomers in a reaction system through the action of hydrogen bonds, so that a synergistic effect is achieved, the polyether molecules can be successfully grafted with sodium lignosulfonate molecules, and because the sulfonic acid groups and the phenolic hydroxyl groups in the sodium lignosulfonate molecules have higher contents, the methoxy groups in the molecules are replaced by active groups, so that the product has higher activity; meanwhile, an isomeric ester monomer, an unsaturated ester group comonomer and the like are introduced into the polyether side chain, and the ester monomer containing an ester group enhances the slow release effect, adaptability and stability of the water reducing agent under different materials.
The sustained-release lignin-based polycarboxylic acid high-performance water reducing agent disclosed by the invention utilizes the specific isomeric structure, higher activity and synergistic interaction of an isomeric ester monomer, so that a lignin-based structure can be successfully introduced into a prenyl polyoxyethylene ether macromonomer, and under the normal temperature condition and the action of an initiator, free radicals are copolymerized to synthesize the sustained-release lignin-based polycarboxylic acid water reducing agent.
The isomeric ester comonomer of the present invention is methacrylate polyoxyethylene polyoxypropylene ether obtained by esterifying a terminal hydroxyl group of an unsaturated carboxylic acid and an ethylene oxide-propylene oxide block copolyether, and the methacrylate polyoxyethylene polyoxypropylene ether is an isomeric ester comonomer. Isomeric ester comonomers are also available commercially.
The polyether comonomer comprises unsaturated carboxylic acid comonomer and unsaturated ester group comonomer. Wherein, the unsaturated carboxylic acid comonomer is at least one of methacrylic acid or acrylic acid; the unsaturated ester-based comonomer is at least one of hydroxyethyl acrylate or hydroxypropyl acrylate.
In the alkaline environment of cement, ester groups in molecules of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent are hydrolyzed and then gradually release carboxyl groups, so that a secondary dispersion effect can be achieved, the slump retaining performance of polycarboxylic acid molecules is improved, the synthesized water reducing agent has good workability and slump retaining performance, and the effect is particularly obvious on the condition of poor quality of sand and stone materials.
The sodium lignosulfonate is prepared into a 30% aqueous solution by dry powder, is kept stand for 48 hours, is taken out of supernatant liquid and is uniformly stirred, and the solid content is measured for later use.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent also contains an initiator, a reducing agent, a chain transfer agent, liquid alkali and water.
The synthetic raw materials comprise the following components in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 200 to 500 portions;
sodium lignosulfonate: 6-25 parts;
isomeric ester comonomers: 3.0 to 15.0 parts;
unsaturated carboxylic acid comonomer: 10-40 parts;
unsaturated ester-based comonomer: 25-60 parts;
initiator: 0.5 to 3 parts;
reducing agent: 0.2 to 1.5 portions;
chain transfer agent: 0.5 to 5 parts;
liquid caustic soda: 2-15 parts;
water: 300 to 800 portions.
The initiator is at least one of hydrogen peroxide or ammonium persulfate. The chain transfer agent is at least one of thioglycolic acid, 3-mercaptopropionic acid or mercaptoethanol. The reducing agent is L-ascorbic acid, sodium formaldehyde sulfoxylate or a composite reducing agent, wherein the composite reducing agent is a mixture of the L-ascorbic acid and the sodium formaldehyde sulfoxylate.
Wherein the concentration of the liquid alkali is 32 percent.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent is characterized in that a polycarboxylic acid molecular structure is designed, and sodium lignosulfonate is creatively grafted on a prenyl polyoxyethylene ether macromonomer molecule because the sodium lignosulfonate has active groups such as sulfonic groups, alcoholic hydroxyl groups, carboxyl groups and the like. The isomeric esterification monomer used in the invention has special isomeric steric hindrance, and the slow release property of the ester group of the isomeric esterification monomer is utilized, so that the obtained slow release type lignin-based polycarboxylic acid water reducing agent has good slump retaining property and workability. The slow-release lignin-based polycarboxylate superplasticizer disclosed by the invention is stable in performance, can be combined with other compound components and has good compatibility, meets the requirements of slump retaining performance of construction concrete, and solves the problems of poor slump retaining effect, bleeding, segregation, bottom scraping and the like in the practical application process of the polycarboxylate superplasticizer. In addition, the invention has the advantages of easily available raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained release effect and the like, and has wide application prospect.
Example 2.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 200 to 500 portions;
sodium lignosulfonate: 6-25 parts;
isomeric ester comonomers: 3.0 to 15.0 parts;
unsaturated carboxylic acid comonomer: 10-40 parts;
unsaturated ester-based comonomer: 25-60 parts;
initiator: 0.5 to 3 parts;
reducing agent: 0.2 to 1.5 portions;
chain transfer agent: 0.5 to 5 parts;
liquid caustic soda: 2-15 parts;
water: 300 to 800 portions.
Wherein the molecular weight of the isomeric ester comonomer is 800-1800; the molecular weight of the prenyl polyoxyethylene ether macromonomer is 2000-4000; the molecular weight of the sodium lignin sulfonate is 5000-10000.
Compared with the embodiment 1, by adopting the proportioning range of the prenyl polyoxyethylene ether macromonomer, the sodium lignosulfonate, the isomerate comonomer and the polyether comonomer, the slump retaining effect, the bleeding property and the workability of the slow-release type lignin-based polycarboxylic acid high-performance water reducer are better than those of the embodiment 1.
Example 3.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 200 parts and molecular weight of 5000;
sodium lignosulfonate: 6 parts and a molecular weight of 12000;
isomeric ester comonomers: 3.0 parts and molecular weight 2000;
unsaturated carboxylic acid comonomer: 40 parts of methacrylic acid;
unsaturated ester-based comonomer: 25 parts of hydroxypropyl acrylate;
initiator: 0.2 part of hydrogen peroxide and 0.3 part of ammonium persulfate;
reducing agent: 15 parts of a composite reducing agent;
chain transfer agent: 0.1 part of thioglycolic acid, 0.2 part of 3-mercaptopropionic acid and 0.2 part of mercaptoethanol;
liquid caustic soda: 2 parts of (1);
water: 800 parts.
Among them, the prenyl polyoxyethylene ether macromonomer was purchased from okay ltd. Sodium lignosulfonate was purchased from borly corporation, south africa. Isomeric ester comonomers are available from clariant, germany. Acrylic acid was purchased from Zhejiang satellite petrochemical. Hydroxypropyl acrylate was purchased from technical limited of Changsheng source, lotus, Shandong. The hydrogen peroxide is a commercial product and the content is 28 percent. Ammonium persulfate was purchased from Jiangsu Ke Industrial chemical Co., Ltd. The compound reducing agent is purchased from Nanjing chess honest. Thioglycolic acid was purchased from Asahi knob, Fuzhou. 3-mercaptopropionic acid was purchased from Nanjing, national morning chemical Co., Ltd. Mercaptoethanol was purchased from Nanjing national morning chemical Co.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent has good slump retaining effect, bleeding property and workability.
Example 4.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 500 parts and a molecular weight of 1000;
sodium lignosulfonate: 25 parts and a molecular weight of 4000;
isomeric ester comonomers: 15.0 parts and molecular weight 500;
unsaturated carboxylic acid comonomer: 10 parts of methacrylic acid;
unsaturated ester-based comonomer: 60 parts of hydroxypropyl acrylate;
initiator: 3 parts of hydrogen peroxide;
reducing agent: 0.2 part of L-ascorbic acid;
chain transfer agent: 5 parts of thioglycolic acid;
liquid caustic soda: 15 parts of (1);
water: 800 parts.
Among them, the prenyl polyoxyethylene ether macromonomer was purchased from okay ltd. Sodium lignosulfonate was purchased from the Jilin stone paper mill. Isomeric ester comonomers are available from clariant, germany. Methacrylic acid was purchased from Jiangsu Ke Industrial chemical Co. Hydroxypropyl acrylate was purchased from technical limited of Changsheng source, lotus, Shandong. The hydrogen peroxide is a commercial product and the content is 28 percent. L-ascorbic acid was purchased from Yangzhou pharmaceutical industry. Thioglycolic acid was purchased from Asahi knob, Fuzhou.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent has good slump retaining effect, bleeding property and workability.
Example 5.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 300 parts and a molecular weight of 4000;
sodium lignosulfonate: 8 parts and molecular weight of 5000;
isomeric ester comonomers: 4.0 parts and molecular weight 800;
unsaturated carboxylic acid comonomer: 20 parts of methacrylic acid;
unsaturated ester-based comonomer: 35 parts of hydroxypropyl acrylate;
initiator: 0.8 part of hydrogen peroxide;
reducing agent: 0.3 part of rongalite;
chain transfer agent: 1 part of thioglycolic acid;
liquid caustic soda: 5 parts of a mixture;
water: 450 parts of the raw materials.
Among them, the prenyl polyoxyethylene ether macromonomer was purchased from okay ltd. Sodium lignosulfonate was purchased from borly corporation, south africa. Isomeric ester comonomers are available from clariant, germany. Methacrylic acid was purchased from Jiangsu Ke Industrial chemical Co. Hydroxyethyl acrylate was purchased from technical limited of Changsheng source, lotus, Shandong. The hydrogen peroxide is a commercial product and the content is 28 percent. Thioglycolic acid was purchased from Asahi knob, Fuzhou.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent has good slump retaining effect, bleeding property and workability.
Example 6.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 400 parts and a molecular weight of 2000;
sodium lignosulfonate: 20 parts and molecular weight of 5000;
isomeric ester comonomers: 10.0 parts and a molecular weight of 2000;
unsaturated carboxylic acid comonomer: 30 parts of acrylic acid;
unsaturated ester-based comonomer: 50 parts of hydroxyethyl acrylate;
initiator: 2 parts of ammonium persulfate;
reducing agent: 1.0 part of rongalite;
chain transfer agent: 3 parts of mercaptoethanol;
liquid caustic soda: 10 parts of (A);
water: 600 parts.
Among them, the prenyl polyoxyethylene ether macromonomer was purchased from okay ltd. Sodium lignosulfonate was purchased from borly corporation, south africa. Isomeric ester comonomers are available from clariant, germany. Acrylic acid is available from Zhejiang satellite petrochemicals or Asahi Longman chemical Co., Ltd, Fuzhou. Hydroxyethyl acrylate was purchased from technical limited of Changsheng source, lotus, Shandong. Ammonium persulfate was purchased from Jiangsu Ke Industrial chemical Co., Ltd. Thioglycolic acid was purchased from Asahi knob, Fuzhou.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent has good slump retaining effect, bleeding property and workability.
Example 7.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 300 parts and a molecular weight of 2400;
sodium lignosulfonate: 20 parts and a molecular weight of 8400;
isomeric ester comonomers: 10.0 parts and a molecular weight of 1700;
unsaturated carboxylic acid comonomer: 30 parts of acrylic acid;
unsaturated ester-based comonomer: 50 parts of hydroxyethyl acrylate;
initiator: 2.0 parts of ammonium persulfate;
reducing agent: 1.0 part of L-ascorbic acid;
chain transfer agent: 3.0 parts of thioglycolic acid;
liquid caustic soda: 10 parts of (A);
water: 420 parts of (A).
Among them, the prenyl polyoxyethylene ether macromonomer was purchased from okay ltd. Sodium lignosulfonate was purchased from borly corporation, south africa. Isomeric ester comonomers are available from clariant, germany. Acrylic acid was purchased from Zhejiang satellite petrochemical. Hydroxyethyl acrylate was purchased from technical limited of Changsheng source, lotus, Shandong. Ammonium persulfate was purchased from Jiangsu Ke Industrial chemical Co., Ltd. L-ascorbic acid was purchased from Yangzhou pharmaceutical industry. Thioglycolic acid was purchased from Asahi knob, Fuzhou.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent has good slump retaining effect, bleeding property and workability.
Example 8.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 400 parts and a molecular weight of 2400;
sodium lignosulfonate: 8 parts and a molecular weight of 10000;
isomeric ester comonomers: 4.0 parts and a molecular weight of 700;
unsaturated carboxylic acid comonomer: 20 parts of acrylic acid;
unsaturated ester-based comonomer: 35 parts of hydroxyethyl acrylate;
initiator: 0.8 part of hydrogen peroxide;
reducing agent: 0.3 part of rongalite;
chain transfer agent: 1.0 part of 3-mercaptopropionic acid;
liquid caustic soda: 10 parts of (A);
water: 420 parts of (A).
Among them, the prenyl polyoxyethylene ether macromonomer was purchased from okay ltd. Sodium lignosulfonate was purchased from the Jilin stone paper mill. Isomeric ester comonomers are available from okay Limited. Methacrylic acid was purchased from Jiangsu Ke Industrial chemical Co. Acrylic acid was purchased from Zhejiang satellite petrochemical. Hydroxyethyl acrylate was purchased from technical limited of Changsheng source, lotus, Shandong. The hydrogen peroxide is a commercial product and the content is 28 percent. 3-mercaptopropionic acid was purchased from Nanjing, national morning chemical Co., Ltd.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent has good slump retaining effect, bleeding property and workability.
Example 9.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 350 parts and a molecular weight of 2400;
sodium lignosulfonate: 14 parts and a molecular weight of 9400;
isomeric ester comonomers: 6.0 parts and a molecular weight of 1500;
unsaturated carboxylic acid comonomer: 25 parts of acrylic acid;
unsaturated ester-based comonomer: 43 parts of hydroxyethyl acrylate;
initiator: 1.4 parts of hydrogen peroxide;
reducing agent: 0.6 part of composite reducing agent;
chain transfer agent: 2.0 parts of mercaptoethanol;
liquid caustic soda: 8 parts of a mixture;
water: 490 parts.
Among them, the prenyl polyoxyethylene ether macromonomer was purchased from okay ltd. Sodium lignosulfonate was purchased from borly corporation, south africa. Isomeric ester comonomers are available from clariant, germany. Acrylic acid was purchased from Asahi Longman chemical Co., Ltd, Fuzhou. Hydroxyethyl acrylate was purchased from technical limited of Changsheng source, lotus, Shandong. The hydrogen peroxide is a commercial product and the content is 28 percent. The compound reducing agent is purchased from Nanjing chess honest. Mercaptoethanol was purchased from Nanjing national morning chemical Co.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent has good slump retaining effect, bleeding property and workability.
Example 10.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following synthetic raw materials in parts by mass:
isopentenyl polyoxyethylene ether macromonomer: 320 parts and a molecular weight of 2400;
sodium lignosulfonate: 14 parts and a molecular weight of 6900;
isomeric ester comonomers: 6.0 parts and a molecular weight of 1400;
unsaturated carboxylic acid comonomer: 21 parts of acrylic acid;
unsaturated ester-based comonomer: 47 parts of hydroxyethyl acrylate;
initiator: 2.0 parts of hydrogen peroxide;
reducing agent: 0.4 part of composite reducing agent;
chain transfer agent: 0.6 part of mercaptoethanol and 1.1 parts of 3-mercaptopropionic acid;
liquid caustic soda: 7 parts;
water: 390 parts.
Among them, the prenyl polyoxyethylene ether macromonomer was purchased from okay ltd. Sodium lignosulfonate was purchased from borly corporation, south africa. Isomeric ester comonomers are available from Claiens or Okken GmbH, Germany. Acrylic acid was purchased from Zhejiang satellite petrochemical. Hydroxyethyl acrylate was purchased from technical limited of Changsheng source, lotus, Shandong. The hydrogen peroxide is a commercial product and the content is 28 percent. The compound reducing agent is purchased from Nanjing chess honest. 3-mercaptopropionic acid was purchased from Nanjing, national morning chemical Co., Ltd. Mercaptoethanol was purchased from Nanjing national morning chemical Co.
The slow-release lignin-based polycarboxylic acid high-performance water reducing agent has good slump retaining effect, bleeding property and workability.
Example 11.
A preparation method of a slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following step of proportioning synthetic raw materials according to any one of embodiments 3 to 10.
Step one, adding a large-molecular-weight prenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 15-35 ℃, adding an initiator, and stirring for 5-10 min, wherein the water amount is 60-80% of the total water amount;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is an aqueous solution of an unsaturated carboxylic acid comonomer, an unsaturated ester group comonomer and an isomeric ester comonomer, the material solution B is an aqueous solution of a reducing agent and a chain transfer agent, and the material solution A is 10-20% of the total water amount; the material B solution accounts for 10 to 20 percent of the total water amount;
step three, controlling the addition of the material solution A within 2-5 h, and controlling the addition of the material solution B within 2.5-5.5 h;
step four, continuously preserving the heat for 0.5 to 3 hours at the temperature of between 30 and 40 ℃;
and fifthly, adding liquid alkali to enable the pH value to be 4.5-6.5, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
The preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent has the advantages of simple production process, easiness in operation and low reaction temperature requirement, so that the production cost is reduced, and the preparation method is environment-friendly. The invention has the advantages of easily obtained raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained-release effect and the like, and has wide application prospect.
Example 12.
A preparation method of a slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following step of proportioning synthetic raw materials according to any one of embodiments 3 to 10.
Step one, adding a large-molecular-weight prenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 20-30 ℃, adding an initiator, and stirring for 5-10 min, wherein the water amount is 70% of the total water amount;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is an aqueous solution of an unsaturated carboxylic acid comonomer, an unsaturated ester group comonomer and an isomeric ester comonomer, the material solution B is an aqueous solution of a reducing agent and a chain transfer agent, and the material solution A is 15% of the total water amount; the water content of the material B solution is 15 percent of the total water content;
step three, controlling the adding of the material solution A within 3-4 h, and controlling the adding of the material solution B within 3.5-4.5 h;
step four, continuously preserving the heat for 1 to 2 hours at the temperature of between 35 and 38 ℃;
and fifthly, adding liquid alkali to enable the pH value to be 5-6, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
The preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent has the advantages of simple production process, easiness in operation and low reaction temperature requirement, so that the production cost is reduced, and the preparation method is environment-friendly. The invention has the advantages of easily obtained raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained-release effect and the like, and has wide application prospect.
Example 13.
A preparation method of a slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following step of proportioning synthetic raw materials according to any one of embodiments 3 to 10.
Step one, adding a large-molecular-weight prenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 20 ℃, adding an initiator, and stirring for 5min, wherein the water amount is 65% of the total water amount;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is an aqueous solution of an unsaturated carboxylic acid comonomer, an unsaturated ester group comonomer and an isomeric ester comonomer, the material solution B is an aqueous solution of a reducing agent and a chain transfer agent, and the material solution A is 15% of the total water amount; the material B solution accounts for 20 percent of the total water amount;
step three, controlling the adding of the material solution A within 3 hours, and controlling the adding of the material solution B within 3.5 hours;
step four, continuously preserving the heat for 1h at 38 ℃;
and fifthly, adding liquid alkali to enable the pH value to be 5-6, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
The preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent has the advantages of simple production process, easiness in operation and low reaction temperature requirement, so that the production cost is reduced, and the preparation method is environment-friendly. The invention has the advantages of easily obtained raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained-release effect and the like, and has wide application prospect.
Example 14.
A preparation method of a slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following step of proportioning synthetic raw materials according to any one of embodiments 3 to 10.
Step one, adding a large-molecular-weight prenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 30 ℃, adding an initiator, and stirring for 10min, wherein the water amount is 75% of the total water amount;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is an aqueous solution of an unsaturated carboxylic acid comonomer, an unsaturated ester group comonomer and an isomeric ester comonomer, the material solution B is an aqueous solution of a reducing agent and a chain transfer agent, and the material solution A is 15% of the total water amount; the material B solution accounts for 10 percent of the total water amount;
step three, controlling the addition of the material solution A within 4 hours, and controlling the addition of the material solution B within 4.5 hours;
step four, continuously preserving the heat for 1h at 42 ℃;
and fifthly, adding liquid alkali to enable the pH value to be 5-6, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
The preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent has the advantages of simple production process, easiness in operation and low reaction temperature requirement, so that the production cost is reduced, and the preparation method is environment-friendly. The invention has the advantages of easily obtained raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained-release effect and the like, and has wide application prospect.
Example 15.
A preparation method of a slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following step of proportioning synthetic raw materials according to any one of embodiments 3 to 10.
Step one, adding a large-molecular-weight prenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 25 ℃, adding an initiator, and stirring for 10min, wherein the water amount is 70% of the total water amount;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is an aqueous solution of an unsaturated carboxylic acid comonomer, an unsaturated ester group comonomer and an isomeric ester comonomer, the material solution B is an aqueous solution of a reducing agent and a chain transfer agent, and the material solution A is 15% of the total water amount; the water content of the material B solution is 15 percent of the total water content;
step three, controlling the adding of the material A solution within 3.5 hours, and controlling the adding of the material B solution within 4 hours;
step four, continuously preserving the heat for 1.5h at the temperature of 40 ℃;
and fifthly, adding liquid alkali to enable the pH value to be 5-6, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
The preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent has the advantages of simple production process, easiness in operation and low reaction temperature requirement, so that the production cost is reduced, and the preparation method is environment-friendly. The invention has the advantages of easily obtained raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained-release effect and the like, and has wide application prospect.
Example 16.
A preparation method of a slow-release lignin-based polycarboxylic acid high-performance water reducing agent comprises the following step of proportioning synthetic raw materials according to any one of embodiments 3 to 10.
Step one, adding a large-molecular-weight prenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 26 ℃, adding an initiator, and stirring for 10min, wherein the water amount is 70% of the total water amount;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is an aqueous solution of an unsaturated carboxylic acid comonomer, an unsaturated ester group comonomer and an isomeric ester comonomer, the material solution B is an aqueous solution of a reducing agent and a chain transfer agent, and the material solution A is 15% of the total water amount; the water content of the material B solution is 15 percent of the total water content;
step three, controlling the adding of the material A solution within 3.5 hours, and controlling the adding of the material B solution within 4 hours;
step four, continuously preserving the heat for 1h at the temperature of 41 ℃;
and fifthly, adding liquid alkali to enable the pH value to be 5-6, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
The preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent has the advantages of simple production process, easiness in operation and low reaction temperature requirement, so that the production cost is reduced, and the preparation method is environment-friendly. The invention has the advantages of easily obtained raw materials, simple preparation process, environmental protection, safety, easy mass production, good sustained-release effect and the like, and has wide application prospect.
The slow-release lignin-based polycarboxylic acid high-performance water reducer sample is prepared according to the raw material proportion and the preparation method shown in the table I.
TABLE I preparation protocol of samples of the invention
| Test group | Raw material ratio | Preparation method |
| Sample 1 | Example 4 | Example 13 |
| Sample 2 | Example 5 | Example 14 |
| Sample 3 | Example 6 | Example 15 |
| Sample No. 4 | Example 4 | Example 16 |
| Sample No. 5 | Example 7 | Example 13 |
| Sample No. 6 | Example 8 | Example 14 |
| Sample 7 | Example 9 | Example 15 |
| Sample 8 | Example 10 | Example 16 |
Comparative example 1
To compare the effects of the present invention, the following comparative sample 1 was prepared as follows:
step one, adding 350 parts of isopentenyl polyoxyethylene ether macromonomer with the molecular weight of 2400 into a reactor, adding 300 parts of water, stirring, heating to 25 ℃, adding 1.4 parts of hydrogen peroxide after the monomer is completely dissolved, and stirring for 10 min;
step two, simultaneously adding a material solution A and a material solution B into a reactor, wherein the material solution A is a solution prepared by uniformly stirring 25 parts of acrylic acid, 45 parts of hydroxyethyl acrylate, 6 parts of an isomeric esterification monomer and 100 parts of water; the material B solution is prepared by uniformly stirring 0.6 part of a mixture of L-ascorbic acid and sodium formaldehyde sulfoxylate, 1.0 part of 3-mercaptopropionic acid, 0.7 part of mercaptoethanol and 85 parts of water;
step three, controlling the material solution A to be added after 3 hours, and controlling the material solution B to be added after 3.5 hours;
step four, continuously preserving the heat at 40 ℃ for 1 h;
and step five, adding 7 parts of liquid alkali to neutralize until the pH value is 5-6 to obtain a reference sample 1 without sodium lignosulfonate.
Comparative example 2
To compare the effects of the present invention, the following comparative sample 2 was prepared as follows:
step one, adding 344 parts of prenyl polyoxyethylene ether macromonomer with the molecular weight of 2400 and 12 parts of sodium lignosulfonate into a reactor, adding 300 parts, stirring, heating to 25 ℃, adding 1.4 parts of hydrogen peroxide after the monomers are completely dissolved, and stirring for 10 min;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is a solution prepared by uniformly stirring 25 parts of acrylic acid, 45 parts of hydroxyethyl acrylate and 100 parts of water; the material B solution is prepared by uniformly stirring 0.6 part of a mixture of L-ascorbic acid and sodium formaldehyde sulfoxylate, 1.0 part of 3-mercaptopropionic acid, 0.7 part of mercaptoethanol and 85 parts of water;
step three, controlling the material solution A to be added after 3 hours, and controlling the material solution B to be added after 3.5 hours;
step three, continuing to keep the temperature at 40 ℃ for 1 h;
and step four, adding 7 parts of liquid alkali to neutralize until the pH value is 5-6 to obtain a reference sample 2 without the isomeric ester comonomer.
Comparative example 3
To compare the effects of the present invention, the following comparative sample 3 was prepared as follows:
step one, 355 parts of isopentenyl polyoxyethylene ether macromonomer with the molecular weight of 2400 is added into a reactor, 310 parts of water is added, stirring and heating are started to raise the temperature to 25 ℃, 1.4 parts of hydrogen peroxide is added after the monomer in a flask is completely dissolved, and stirring is carried out for 10 min;
step two, simultaneously dripping a material solution A and a material solution B, wherein the material solution A is a solution prepared by uniformly stirring 22 parts of acrylic acid, 50 parts of hydroxyethyl acrylate and 100 parts of water; the material B solution is prepared by uniformly stirring 0.6 part of high-efficiency reducing agent, 1.0 part of 3-mercaptopropionic acid, 0.7 part of mercaptoethanol and 80 parts of water;
step three, controlling the material solution A to be added after 3 hours, and controlling the material solution B to be added after 3.5 hours;
step four, continuing to keep the temperature at 40 ℃ for 1h after dripping;
and step five, adding 10 parts of liquid alkali to neutralize until the pH value is 5-6, and finally preparing a reference sample 3 which does not contain sodium lignosulfonate and isomeric ester comonomer.
The slow-release polycarboxylic acid high-performance water reducing agent synthesized by the samples 1 to 8 and the comparative examples 1 to 3 is subjected to performance detection by adopting Yuexiu 42.5R cement and detecting the water reducing rate, the fluidity, the slump and the like according to the test requirements in concrete admixture (GB8076-2008), and the results are shown in tables 2 and 3:
TABLE 2 neat and homogeneity
As can be seen from Table 2, the homogeneity of the slow-release polycarboxylic acid high-performance water reducing agent synthesized by the sodium lignosulfonate of the invention is better than that of the comparative samples 1 to 3, and the initial fluidity, the fluidity of 1h and the fluidity of 2h are better than that of the comparative samples 1 to 3.
TABLE 3 concrete Properties
As can be seen from Table 3, the water reducing rates of the slow-release polycarboxylic acid high-performance water reducing agent prepared by the invention are all higher than those of comparative samples 1 to 3, wherein the water reducing rate of sample 7 is nearly 4% higher than that of comparative sample 3. The slump and the expansion of the water reducing agent are both higher than those of the comparison samples 1 to 3. The workability of the water reducing agent is good, and the bleeding amount is less than that of the comparative samples 1 to 3.
In conclusion, the slow-release polycarboxylic acid high-performance water reducing agent prepared by the invention has high dispersibility and extremely strong slow-release performance. When the polycarboxylic acid molecule is in an alkaline environment of cement, the ester group in the polycarboxylic acid molecule is hydrolyzed and then gradually releases carboxyl, so that a secondary dispersion effect is achieved, the slump retaining performance of the polycarboxylic acid molecule is improved, the problems of slump loss and the like are effectively solved, bleeding of concrete is reduced, and the construction performance of the concrete is improved. Meanwhile, due to high dispersion, high slow release performance and good workability, the modified epoxy resin can effectively meet the construction performance of most of concrete by slightly compounding with water-reducing master batches, retarding components and the like.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A slow-release lignin-based polycarboxylic acid high-performance water reducing agent is characterized in that: the synthetic raw materials contain a large-molecular-weight isopentenyl polyoxyethylene ether macromonomer, sodium lignosulfonate, an isomeric ester comonomer and a polyether comonomer.
2. The slow-release lignin-based polycarboxylic acid high-performance water reducing agent according to claim 1, which is characterized in that: the chemical structural formula of the isomeric ester comonomer is as follows:
CH2＝C(CH3)-COO-(-CH2-CH2-O-)m-(-CH2-CH(CH3)-O-)n-(-CH2-CH2-O-)L-H，
wherein m is 3-8, n is 3-8, and L is 10-20.
3. The slow-release lignin-based polycarboxylic acid high-performance water reducing agent according to claim 2, characterized in that: the molecular weight of the isomeric ester comonomer is 500-2000;
the molecular weight of the isopentenyl polyoxyethylene ether macromonomer is 1500-5000;
the molecular weight of the sodium lignosulfonate is 4000-12000.
4. The slow-release lignin-based polycarboxylic acid high-performance water reducing agent according to claim 3, characterized in that: the polyether comonomer comprises an unsaturated carboxylic acid comonomer and an unsaturated ester group comonomer;
the molecular weight of the isomeric ester comonomer is 800-1800;
the molecular weight of the isopentenyl polyoxyethylene ether macromonomer is 2000-4000;
the molecular weight of the sodium lignosulfonate is 5000-10000.
5. The slow-release lignin-based polycarboxylic acid high-performance water reducing agent according to claim 4, characterized in that: also contains initiator, reducer, chain transfer agent, liquid alkali and water.
6. The slow-release lignin-based polycarboxylic acid high-performance water reducing agent according to claim 5, which is characterized in that the ratio of the synthetic raw materials is as follows by mass:
isopentenyl polyoxyethylene ether macromonomer: 200 to 500 portions;
sodium lignosulfonate: 6-25 parts;
isomeric ester comonomers: 3.0 to 15.0 parts;
unsaturated carboxylic acid comonomer: 10-40 parts;
unsaturated ester-based comonomer: 25-60 parts;
initiator: 0.5 to 3 parts;
reducing agent: 0.2 to 1.5 portions;
chain transfer agent: 0.5 to 5 parts;
liquid caustic soda: 2-15 parts;
water: 300 to 800 portions.
7. The slow-release lignin-based polycarboxylic acid high-performance water reducing agent according to claim 6, which is characterized in that the ratio of the synthetic raw materials is as follows by mass:
isopentenyl polyoxyethylene ether macromonomer: 300 to 400 portions;
sodium lignosulfonate: 8-20 parts;
isomeric ester comonomers: 4.0 to 10.0 portions;
unsaturated carboxylic acid comonomer: 20-30 parts;
unsaturated ester-based comonomer: 35-50 parts;
initiator: 0.8 to 2 parts;
reducing agent: 0.3 to 1.0 portion;
chain transfer agent: 1-3 parts;
liquid caustic soda: 5-10 parts;
water: 450 to 600 portions.
8. The slow-release lignin-based polycarboxylic acid high-performance water reducing agent according to claim 7, characterized in that: the unsaturated carboxylic acid comonomer is at least one of methacrylic acid or acrylic acid;
the unsaturated ester-based comonomer is at least one of hydroxyethyl acrylate or hydroxypropyl acrylate;
the initiator is at least one of hydrogen peroxide or ammonium persulfate;
the chain transfer agent is at least one of thioglycolic acid, 3-mercaptopropionic acid or mercaptoethanol;
the reducing agent is L-ascorbic acid, sodium formaldehyde sulfoxylate or a composite reducing agent, wherein the composite reducing agent is a mixture of the L-ascorbic acid and the sodium formaldehyde sulfoxylate.
9. The preparation method of the slow-release lignin-based polycarboxylic acid high-performance water reducing agent according to any one of claims 5 to 8, characterized by comprising the following steps:
step one, adding a large molecular weight isopentenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 15-35 ℃, adding an initiator, and stirring for 5-10 min;
step two, simultaneously adding a material solution A and a material solution B into the reactor, wherein the material solution A is an aqueous solution of an unsaturated carboxylic acid comonomer, an unsaturated ester group comonomer and an isomeric ester comonomer, and the material solution B is an aqueous solution of a reducing agent and a chain transfer agent;
step three, controlling the addition of the material solution A within 2-5 h, and controlling the addition of the material solution B within 2.5-5.5 h;
step four, continuously preserving the heat for 0.5 to 3 hours at the temperature of between 30 and 40 ℃;
and fifthly, adding liquid alkali to enable the pH value to be 4.5-6.5, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducing agent.
10. The method of claim 9, wherein:
adding a large-molecular-weight isopentenyl polyoxyethylene ether macromonomer, sodium lignosulfonate and water into a reactor, stirring, heating to 20-30 ℃, adding an initiator, and stirring for 5-10 min;
the third step is to control the adding of the material solution A within 3 to 4 hours and the adding of the material solution B within 3.5 to 4.5 hours;
the step four is to keep the temperature for 1 to 2 hours at the temperature of between 35 and 38 ℃;
and step five, adding liquid alkali to enable the pH value to be 5-6, and obtaining the slow-release lignin-based polycarboxylic acid high-performance water reducer.
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Application publication date: 20211207 |