CN108034027B - Comb-shaped polycarboxylate superplasticizer and preparation method thereof - Google Patents
Comb-shaped polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN108034027B CN108034027B CN201711499367.2A CN201711499367A CN108034027B CN 108034027 B CN108034027 B CN 108034027B CN 201711499367 A CN201711499367 A CN 201711499367A CN 108034027 B CN108034027 B CN 108034027B
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
A comb-shaped polycarboxylate superplasticizer and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Placing the ether macromonomer and the ester macromonomer in a reaction container, and heating and stirring uniformly; (2) Dropwise adding (methyl) acrylic acid, an initiator and a small molecular nitrogen-containing monomer M1 and a small molecular sulfur-containing monomer M2 into a reaction container, and heating for reaction; (3) And (3) after the solution in the step (2) is kept warm, adding alkali liquor to adjust the pH value to 7, and cooling to room temperature. The water reducer has excellent slump and expansion degree.
Description
Technical Field
The invention relates to the field of polycarboxylate water reducers.
Background
From the investigation of long side chain macromonomers, polycarboxylic acid high-efficiency water reducing agents applied to the current market are classified into three types, namely polyether high-efficiency water reducing agents with APEG (allyl polyethylene glycol) as a long side chain; polyester type high-efficiency water reducer with MPEG (methoxy polyethylene glycol) as long side chain; and thirdly, simultaneously polymerizing two polyether macromonomers of APEG and MPEG or derivatives thereof to obtain the carboxylic acid high-efficiency water reducer.
From the aspect of molecular structural design, the water reducer can be divided into a star-shaped polycarboxylate water reducer and a comb-shaped polycarboxylate water reducer. The branch bifurcation structure can fully exert the steric hindrance effect, effectively prevent the consumption of the macromolecule of the water reducer by the package of the cement hydration product, and can show better effect in preventing the aggregation of cement and improving the stability of cement paste.
CN101602834a discloses a preparation method of polycarboxylic acid concrete dispersant, comprising the following steps: (1) Free radical copolymerization, monomer A and monomer C are carried out according to the molar ratio of 1.01:1-1.5:1 under the condition of taking monomer B as solvent, wherein monomer A is (alkyl) vinyl alkyl acid ester CH 2=C (R1) OC (=O) (CH 2) nCH3, R1 represents hydrogen atom or methyl, n is the number of methylene and is 0-2, monomer B is monoalkoxy polyalkylene glycol ether HO- (CH 2-CH 2-O) p- (CH (CH 3) -CH 2-O) q-R2, R2 represents alkyl of 1-20 carbon atoms, p represents addition number of ethylene oxide and is 1-200, q represents addition number of propylene oxide and is 0-25; monomer C is maleic anhydride; the mole ratio of the monomer B to the monomer C is 0.1:1-1:1, (2) the polymer prepared in the step 1 is heated for esterification after esterification grafting reaction so as to graft the monomer B on the anhydride group introduced by the monomer C; (3) After the esterification reaction is finished, a diluent is added into the reaction product, and an alkaline substance is added to adjust the pH value to 6-8. The method avoids volatile organic solvent, and has simple process.
CN103482897a discloses a block polycarboxylic acid concrete high-efficiency water reducing agent with an ordered structure and a preparation method thereof, comprising the following steps: 1) After the monomer A is fully mixed with the catalyst, the ligand and the solvent, nitrogen N is introduced 2 O in solution 2 Discharging, then adding the initiator into the solution rapidly at one time, and adding the initiator into the solution at the same time 2 Under the protection of the reaction, atom transfer controllable free radical polymerization reaction is carried out, the reaction temperature is 30-90 ℃ and the reaction time is 0.5-12h, thus obtaining a homopolymer macromolecular solution, and the molecular structure of the monomer A accords with the general formula (1) 2 ＝C(R 1 )COO(AO)nR 2 The molecular structure of the homopolymer accords with the general formula (2)Wherein R is 1 ＝CH 3 Or H, R 2 =h or alkyl of 1-4 carbon atoms; AO is an oxyalkylene group of 2 to 4 carbon atoms or a mixture of two or more such oxyalkylene groups, and n is an average addition mole number of AO, which is an integer of 5 to 50. 2) Adding the homopolymer macromolecular solution prepared in the step 1 into a monomer B, and mixing and copolymerizing under the protection of nitrogen to generate a block polycarboxylic acid, wherein the monomer B is unsaturated carboxylic acid, and the structure of the monomer B is consistent with the general formula (3) CH 2 ＝C(R 3 ) COOM; the structure of the block polycarboxylic acid is in accordance with the general formula (4)>The document considers that the molecular weight of the polymer is monodisperse and can improve the flowability of the concrete within a very low blending amount range, namely 0.08-0.2% of the cementing material.
CN105754045a discloses a silane coupling agent modified polycarboxylate superplasticizer and a preparation method thereof: 1) Placing 350 parts of polyether macromonomer into a reaction vessel, adding 5-15 parts of acrylic acid, uniformly stirring, adding 0.5-5 parts of double bond-containing silane coupling agent, and stirring until the solution has no obvious block or sheet material; the polyether macromonomer is one or more of methyl allyl polyoxyethylene ether, isopentenyl alcohol polyoxyethylene ether and modified isopentenyl alcohol polyoxyethylene ether; 2) Dropwise adding 2.5-6 parts of oxidant, 2.5-3.5 parts of initiator and 20-37 parts of small monomer into the solution obtained in the step 1) in sequence under stirring, wherein the dropwise adding time of the small monomer solution is 1-4h; the small monomer is one or more of acrylic acid, sodium methacrylate sulfonate, 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, fumaric acid and maleic anhydride; 3) And 2) curing the solution obtained in the step 2) for 1-2h, adding liquid alkali for neutralization, stabilizing the pH value to 6, and adding 1-3 parts of silane coupling agent without double bonds for stirring uniformly. According to the application, the functional group containing the siloxane structure is introduced into the main chain of the polycarboxylic acid molecule, so that the anchoring capability of performing strong chemical bonding interaction with the cementing material particles is provided for the branched chain of the comb-shaped polycarboxylic acid water reducer, the increase of the anchoring capability can promote the adaptability and slump retention of the water reducer to be obviously enhanced, and the application of the water reducer in the field of mineral micropowder dispersion is expanded to a certain extent.
CN106146859a relates to a four-arm polycarboxylic acid high-efficiency water reducing agent and a preparation method thereof, and the conditions and steps for synthesizing the high-efficiency polycarboxylic acid water reducing agent with a four-arm structure and excellent mud resistance by adopting an atom transfer radical polymerization method are as follows: (1) Adding a certain amount of tetraol into a 50mL single-port bottle, cooling to 0 ℃ through ice water bath, dropwise adding a proper amount of alpha-bromo-isobutyryl bromide through a dropping funnel, heating to room temperature after the dropwise adding is finished, reacting for 16 hours, and separating and drying to obtain a product which is a small molecular initiator with four functional groups; (2) Adding the small molecular initiator, the monomer A and the ligand prepared in the step (1) into a 50mL single-port bottle respectively, stirring and dissolving, completing the three freezing and vacuumizing and thawing processes under the protection of nitrogen, adding a catalyst, uniformly stirring, repeating the three freezing and vacuumizing and thawing processes, thawing, and heating to a certain temperature and stirring for 18 hours; after the reaction is finished, separating and drying under vacuum condition to obtain a polymerization product I; (3) Continuously initiating atom transfer radical polymerization by using the polymerization product I prepared in the step (2) as a macromolecular initiator: adding a polymerization product I, a monomer B, a ligand and a solvent, stirring and dissolving, completing the three-time freezing-vacuumizing-thawing process under the protection of nitrogen, adding a catalyst, uniformly stirring, repeating the three-time freezing-vacuumizing-thawing process, and placing in an oil bath at 85 ℃ for stirring for 18 hours after thawing; after the reaction is finished, separating, and drying under vacuum to obtain a polymerization product II, wherein the polymerization product II is an AB type diblock copolymer with a four-arm structure; (4) hydrolysis reaction: and (3) dissolving the polymerization product II prepared in the step (3) in an acid solution, stirring for 10 hours at room temperature, after the reaction is finished, carrying out rotary evaporation and concentration on the reaction solution, precipitating the product in absolute methanol to obtain the white precipitate, and drying the white precipitate under a vacuum condition to obtain the polycarboxylate water reducer with the four-arm structure. Compared with the traditional comb-shaped polycarboxylate superplasticizer, the problems that the polycarboxylate superplasticizer is sensitive to soil in concrete and performance is reduced due to the existence of the soil can be solved to a certain extent, and the comb-shaped polycarboxylate superplasticizer is particularly suitable for concrete with higher mud content.
In summary, the novel polycarboxylate water reducer is always a research hot point, whether the design is structural or the polymerization method is adopted, and the pursuit of water reduction efficiency is never changed for the control of the process flow.
Disclosure of Invention
The invention unexpectedly discovers that the hydrophobic polycarboxylate water reducer prepared from the ether macromonomer, the ester macromonomer, (methyl) acrylic acid, the small molecular nitrogen-containing monomer M1 and the small molecular sulfur-containing monomer M2 can simultaneously improve slump and expansibility when used in concrete.
Therefore, the application firstly provides a hydrophobic polycarboxylate water reducer which is prepared from an ether macromonomer, an ester macromonomer, (methyl) acrylic acid, a small molecule nitrogen-containing monomer M1 and a small molecule sulfur-containing monomer M2.
The invention provides a preparation method of a comb-shaped polycarboxylate superplasticizer, which comprises the following specific steps: (1) Placing the ether macromonomer and the ester macromonomer in a reaction container, and heating and stirring uniformly; (2) Dropwise adding (methyl) acrylic acid, an initiator and a small molecular nitrogen-containing monomer M1 and a small molecular sulfur-containing monomer M2 into a reaction container, and heating for reaction; (3) After the solution in the step (2) is kept warm, alkali liquor is added to adjust the pH value to 6-8, preferably 7, and the solution is cooled to room temperature. The ether macromonomer is one or more of methyl allyl polyoxyethylene ether, isopentenyl alcohol polyoxyethylene ether and modified isopentenyl alcohol polyoxyethylene ether; the ester macromonomer is one or two of polyethylene glycol monomethyl ether methacrylate (MPEGMA) and polyethylene glycol monomethyl ether maleate.
The small molecule nitrogen-containing monomer M1 is one or more of N-vinylformamide, N-vinylacetamide, N-vinylpropionamide, N-methylolacrylamide and N-methylacrylamide, preferably N-methylolacrylamide. The small molecular sulfur-containing monomer M2 is one or more of sodium methacrylate and 2-acrylamide-2-methylpropanesulfonic acid.
The molar ratio of the ether macromonomer, the ester macromonomer, (meth) acrylic acid, the small molecule nitrogen-containing monomer M1 and the small molecule sulfur-containing monomer M2 is 1:0.8-1.2:2-5:1.5-3.5:3-5, preferably 1:1:3:2:3. The initiator is 1-3wt% of the total monomer, and the initiator is ammonium persulfate, potassium persulfate, sodium persulfate and the like.
And the molecular weight of the ether macromonomer is 500-1000.
The alkali liquor is NaOH solution, KOH solution, ethylenediamine or triethanolamine.
Preferably, the (meth) acrylic acid, the small molecule nitrogen-containing monomer M1 and the small molecule sulfur-containing monomer M2 are added dropwise for 3 to 4 hours, and the initiator is added dropwise for 3.5 to 4.5 hours, more preferably, the monomer is added dropwise over the initiator.
Optionally, a chain transfer agent selected from thioglycolic acid and mercaptopropionic acid is added in the step (2).
Preferably, the temperature of the step (1) is raised to 40-50 ℃, and the temperature of the step (2) is raised to 70-80 ℃.
Preferably, the reaction time of step (2) is 1-2 hours, and the incubation time of step (3) is 1-2 hours.
Preferably, after the reaction is completed, water is added to dilute the reaction product.
The water reducer has excellent slump/expansion degree.
Detailed Description
Example 1
(1) Placing an ether macromonomer TPEG and an ester macromonomer MPEGA in a reaction container, heating to 40 ℃ and uniformly stirring; (2) Dropwise adding acrylic acid, an initiator potassium persulfate and a small molecular nitrogen-containing monomer M1, a small molecular sulfur-containing monomer M2 into a reaction container, and heating to 70 ℃ for reaction for 1.5h, wherein the dropwise adding time of the monomer is 3h, the dropwise adding time of the initiator is 3.5h, and the monomer is completely dropwise added before the initiator; (3) And (3) after the solution in the step (2) is kept for 1h, adding KOH solution to adjust the pH value to 7, and cooling to room temperature. M1 is N-vinylformamide. M2 is sodium methallyl sulfonate. The molar ratio of the ether macromonomer, the ester macromonomer, the acrylic acid, the micromolecular nitrogen-containing monomer M1 and the micromolecular sulfur-containing monomer M2 is 1:1:3:2:3.
Example 2
M1 is N-methylolacrylamide, otherwise as in example 1.
Example 3
The molar ratio of the ether macromonomer, the ester macromonomer, the acrylic acid, the small molecule nitrogen-containing monomer M1 and the small molecule sulfur-containing monomer M2 is 1:1:2:2:3, and the same as in example 1.
Example 4
The molar ratio of the ether macromonomer, the ester macromonomer, the acrylic acid, the small molecule nitrogen-containing monomer M1 and the small molecule sulfur-containing monomer M2 is 1:1:3:1.5:3, and the same as in example 1 is used.
Example 5
The molar ratio of the ether macromonomer, the ester macromonomer, the acrylic acid, the small molecule nitrogen-containing monomer M1 and the small molecule sulfur-containing monomer M2 is 1:1:3:3.5:3, and the same as in example 1 is used.
Comparative example 1
The ether macromonomers were used in their entirety, and the procedure of example 1 was followed.
Comparative example 2
All of the ester macromers were used, as in example 1.
Comparative example 3
M1 was replaced by M2, i.e., only M2 monomer was used, otherwise as in example 1.
Comparative example 4
M2 was replaced by M1, i.e., only M1 monomer was used, otherwise as in example 1.
Comparative example 5
M1 was replaced with acrylamide, and the procedure of example 1 was followed.
The expansion and slump exhibited by each of the examples and comparative examples in the concrete system were determined as shown in Table 1. The test uses GB/T50080-2016.
TABLE 1 concrete flowability performance results
Claims (9)
1. A preparation method of a comb-shaped polycarboxylate superplasticizer comprises the following specific steps:
(1) Placing the ether macromonomer and the ester macromonomer in a reaction container, and heating and stirring uniformly;
(2) Dropwise adding (methyl) acrylic acid, an initiator and a small molecular nitrogen-containing monomer M1 and a small molecular sulfur-containing monomer M2 into a reaction container, and heating for reaction;
(3) After the solution in the step (2) is kept warm, adding alkali liquor to adjust the pH value to 6-8, and cooling to room temperature;
the ether macromonomer is one or more of methyl allyl polyoxyethylene ether, isopentenyl alcohol polyoxyethylene ether and modified isopentenyl alcohol polyoxyethylene ether; the ester macromonomer is one or two of polyethylene glycol monomethyl ether methacrylate (MPEGMA) and di-polyethylene glycol monomethyl ether maleate;
the small molecule nitrogen-containing monomer M1 is one or more of N-vinylformamide, N-vinylacetamide, N-vinylpropionamide and N-methylol acrylamide;
the small molecular sulfur-containing monomer M2 is one or more of sodium methacrylate and 2-acrylamide-2-methylpropanesulfonic acid;
the molar ratio of the ether macromonomer, the ester macromonomer, (methyl) acrylic acid, the micromolecular nitrogen-containing monomer M1 and the micromolecular sulfur-containing monomer M2 is 1:0.8-1.2:2-5:1.5-3.5:3-5.
2. The method of claim 1, wherein: the initiator is 1-3wt% of the total monomer, the initiator is ammonium persulfate, potassium persulfate or sodium persulfate, and the alkali solution is NaOH solution, KOH solution, ethylenediamine or triethanolamine.
3. The method of claim 1, wherein: and the molecular weight of the ether macromonomer is 500-1000.
4. The method of claim 1, wherein: the dropping time of the (methyl) acrylic acid, the small molecule nitrogen-containing monomer M1 and the small molecule sulfur-containing monomer M2 is 3-4h, and the dropping time of the initiator is 3.5-4.5h.
5. The method of claim 1, wherein: and (3) adding a chain transfer agent selected from thioglycollic acid and mercaptopropionic acid in the step (2).
6. The method of claim 1, wherein: the temperature of the step (1) is raised to 40-50 ℃, and the temperature of the step (2) is raised to 70-80 ℃.
7. The method of claim 1, wherein: the reaction time of the step (2) is 1-2h, and the heat preservation time of the step (3) is 1-2h.
8. The method of claim 1, wherein: after the reaction, water was added to the reaction product for dilution.
9. A comb polycarboxylate superplasticizer prepared according to any one of claims 1-8.
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| CN111777350A (en) * | 2020-05-28 | 2020-10-16 | 滕宏军 | High-performance polycarboxylate superplasticizer |
| CN112708072B (en) * | 2020-12-22 | 2021-11-23 | 科之杰新材料集团有限公司 | Anti-corrosion ether polycarboxylic acid water reducing agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708973A (en) * | 2009-11-04 | 2010-05-19 | 山东华伟银凯建材有限公司 | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same |
| CN102503226A (en) * | 2011-10-19 | 2012-06-20 | 中建商品混凝土有限公司 | High slump retaining type polycarboxylic acid water reducing agent with sustained-release effect and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708973A (en) * | 2009-11-04 | 2010-05-19 | 山东华伟银凯建材有限公司 | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same |
| CN102503226A (en) * | 2011-10-19 | 2012-06-20 | 中建商品混凝土有限公司 | High slump retaining type polycarboxylic acid water reducing agent with sustained-release effect and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 马来酸型聚羧酸减水剂的合成研究;韩利华等;《混凝土》;20090427(第04期);第2.1节 * |
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