CN111087552A - Synthetic method of polycarboxylic acid water reducer with high water reducing rate and mud resistance - Google Patents
Synthetic method of polycarboxylic acid water reducer with high water reducing rate and mud resistance Download PDFInfo
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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
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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
Abstract
The invention relates to a synthesis method of a polycarboxylic acid water reducer with high water reducing rate and mud resistance, which comprises the following steps: (1) weighing an initiator reduction component, a chain transfer agent and deionized water, and uniformly mixing to prepare a solution A; (2) weighing unsaturated acid monomers, anti-mud functional monomers and deionized water, and uniformly mixing to prepare a solution B; (3) under the condition of water bath, adding unsaturated polyether macromonomer and deionized water into a reaction vessel, and stirring and mixing; (4) adding an initiator oxidation component into the reaction container in the step (3), and then simultaneously dropwise adding the solution A and the solution B to start polymerization; (5) after the dropwise addition is finished, stirring is continued, the temperature is kept for a certain time, and the target product can be obtained after cooling to the normal temperature. Compared with the prior art, the polycarboxylic acid water reducer synthesized by the invention has the advantages of small mixing amount, high water reduction rate, no need of compounding with the water reducer with high water reduction rate, good mud resistance effect, strong adaptability to cement, simple synthesis process, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of concrete water reducers, and relates to a synthesis method of a polycarboxylic acid water reducer with high water reduction rate and mud resistance, in particular to a synthesis method for preparing the polycarboxylic acid water reducer with high water reduction rate and mud resistance by using isobutylene polyoxyethylene ether (HPEG2400), an unsaturated acid monomer, a mud resistance functional monomer, a chain transfer agent, an initiator and deionized water and adopting a free radical copolymerization method.
Background
In recent years, with the increasingly extensive infrastructure of China, the demand of people on building materials is continuously increased, but due to the limited material resources such as sandstone, high-quality materials which can be used for engineering become less and less, and a large amount of sandstone materials with poor quality and high mud content enter the market. Compared with traditional series water reducing agents such as naphthalene water reducing agents, aliphatic water reducing agents and the like, the polycarboxylic acid water reducing agent is particularly sensitive to the mud content of concrete gravel materials, and mainly shows that when the mud content of the concrete gravel materials is high, the dispersing capacity of the polycarboxylic acid water reducing agent is seriously reduced, the slump retaining effect is poor, and the workability of concrete mixtures is reduced, the strength of hardened concrete is reduced and the like. Therefore, the problem that the polycarboxylic acid water reducer is sensitive to the mud content of the concrete sandstone material becomes the focus of research of current researchers.
At present, measures such as a water-washing aggregate method, a super-water reducing agent mixing method, a compound anti-mud agent and the like are usually adopted in engineering to relieve the engineering problem of concrete caused by high mud content of a concrete raw material. However, these measures inevitably increase the manufacturing cost per cubic meter of concrete and even cause other engineering problems, such as: the washing of the aggregate can damage the gradation of the aggregate, which is not beneficial to the design of the mix proportion; the super-doped water reducing agent can cause high gas content and overlong setting time of concrete; besides increasing the manufacturing cost of concrete, the compound anti-mud agent also needs to consider the compatibility problem of the anti-mud agent and other additives.
Chinese patent CN104558434A discloses a preparation method of a silicon-containing polycarboxylate water reducer, which is characterized in that an organic silicon structure is introduced into a common polycarboxylate water reducer structure, a double bond-containing organic silicon monomer with large-size molecules is prepared through hydrolysis reaction, and the prepared organic silicon monomer is used for synthesizing the polycarboxylate water reducer, so that the molecular size of the polycarboxylate water reducer is increased, the polycarboxylate water reducer is difficult to enter an intercalation structure of soil, and the effects of resisting the soil and reducing the consumption of the water reducer are achieved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for synthesizing a polycarboxylic acid water reducer with high water reducing rate and mud resistance, so as to reduce the sensitivity of the polycarboxylic acid water reducer to the mud content of a concrete material sandstone material, realize the application and popularization of the polycarboxylic acid water reducer in concrete engineering with higher mud content, simultaneously, the water reducer has the characteristics of low doping amount, no harmful impurities such as chloride ions and the like, and the synthesis process is simple, energy-saving and environment-friendly.
The purpose of the invention can be realized by the following technical scheme:
a synthetic method of a polycarboxylic acid water reducer with high water reducing rate and mud resistance comprises the following steps:
(1) weighing an initiator reduction component, a chain transfer agent and deionized water, and uniformly mixing to prepare a solution A;
(2) weighing unsaturated acid monomers, anti-mud functional monomers and deionized water, and uniformly mixing to prepare a solution B;
(3) adding unsaturated polyether macromonomer and deionized water into a four-neck flask of a reaction vessel, wherein the four-neck flask of the reaction vessel is fixed on an iron support, the bottom of the four-neck flask is immersed in a water bath kettle, a cantilever type stirrer is connected above the four-neck flask, and the stirrer is started to dissolve the unsaturated polyether macromonomer in the deionized water;
(4) adding an initiator oxidation component into the reaction container in the step (3) at one time, then adding the solution A and the solution B into the reaction container in the step (3) at a constant speed within a certain time to start polymerization reaction, wherein the control of the process time is controlled by an automatic dropping instrument or a peristaltic pump and other instruments, and the whole polymerization reaction is continuously carried out under the conditions of water bath temperature and stirring;
(5) and (4) after the solution A and the solution B are dropwise added in the step (4), continuously stirring and preserving heat for a certain time, cooling the synthesized product to normal temperature, and neutralizing the prepared polycarboxylate superplasticizer mother liquor by adopting 35% NaOH aqueous solution until the pH value is 6-7 to obtain the target superplasticizer product.
Further, in the step (3), the unsaturated polyether macromonomer is isobutylene polyoxyethylene ether (HPEG), and the number average molecular weight of the unsaturated polyether macromonomer is preferably 2400.
Further, the unsaturated acid monomer is acrylic acid.
Further, the anti-mud functional monomer is end-capped amide phosphate; preferably, the blocked amide phosphate is a blocked amide phosphate produced by wurtzits environmental protection technology ltd, xu.
Preferably, the initiator reduction component is ascorbic acid.
Preferably, the oxidizing component of the initiator is hydrogen peroxide or persulfate; further preferably, the initiator oxidizing component is hydrogen peroxide.
Preferably, the chain transfer agent is thioglycolic acid or mercaptopropionic acid; further preferably, the chain transfer agent is thioglycolic acid.
Preferably, the molar ratio of unsaturated polyether macromonomer to unsaturated acid monomer is 1: (4.2-4.8).
Preferably, the mixing amount of the anti-mud type functional monomer is 1-1.5% of the total weight of the unsaturated polyether macromonomer, the unsaturated acid monomer and the anti-mud type functional monomer by calculation and weighing by an internal mixing method.
Preferably, the initiator reduction component accounts for 0.1-0.2% of the total weight of all the monomers, the initiator oxidation component accounts for 0.5-1.5% of the total weight of all the monomers, and the chain transfer agent accounts for 0.3-0.4% of the total weight of all the monomers; further preferably, the initiator reducing component is 0.15% of the total weight of all monomers, the initiator oxidizing component is 1% of the total weight of all monomers, and the chain transfer agent is 0.35% of the total weight of all monomers.
Preferably, the temperature of the water bath is 40-50 ℃, and the duration of the polymerization reaction is 3.5-4 h; further preferably, the water bath temperature is 45 ℃.
Preferably, the dropping speeds of the solution A and the solution B respectively satisfy the following conditions: the finishing time of the solution A is 3-4 h, the finishing time of the solution B is 2.5-3.5 h, after finishing the dripping, a certain amount of deionized water is supplemented to ensure that the solid content of the prepared polycarboxylic acid water reducer is 40-41%, and the stirring and the heat preservation are continued for 15min-1 h; further preferably, the time for completing the dropwise addition of the solution A is 3.5 hours, the time for completing the dropwise addition of the solution B is 3 hours, and the temperature is kept for 0.5 hour after the dropwise addition is completed.
The synthesized polycarboxylic acid water reducer with high water reducing rate and mud resistance has a molecular structure of a linear comb-shaped structure, and is prepared by copolymerizing unsaturated polyether macromonomers, unsaturated acid monomers and mud resistance functional monomers through unsaturated bond carbon-carbon double bonds. The main chain of the polycarboxylic acid water reducer mainly comprises an unsaturated acid monomer and a mud-resistant functional monomer water reducer, wherein the two groups respectively provide carboxyl, phosphate group and other adsorption groups in the cement hydration process, so that water reducer molecules can be adsorbed and anchored in cement particles, and the cement particles are charged with the same charge to generate electrostatic repulsion so as to disperse, wherein the negative charge carried by the phosphate group is more than the carboxyl, so that enough water reducer molecules for dispersing the cement particles can be contained in the slurry, and the shortage of the polycarboxylic acid water reducer for dispersing the cement slurry due to the adsorption of clay is avoided, so that the mud resistance of the polycarboxylic acid water reducer is greatly improved; the side chain mainly consists of polyether macromonomer and plays a role in dispersing cement particles mainly through steric hindrance. In the preparation process, the molar ratio of the polyether macromonomer to the unsaturated acid monomer and the mixing amount of the anti-mud monomer are mainly determined by a synthesis process and a water reducer performance characterization experiment, and the water reducer synthesized in the mixing amount range has the best water reducing performance and mud resistance.
In the preparation process, the chain transfer agent, the initiator oxidation component and the initiator reduction component are respectively used for controlling the chain length of the polymer, initiating the unsaturated monomer to generate the polymerization reaction and terminating the polymerization reaction, although the three components have small mixing amount, the influence on the molecular synthesis structure of the water reducer and the control on the reaction process are very important, the mixing amount of the three components is mainly determined by a synthesis process and a water reducer performance characterization experiment, and the water reducing performance and the mud resistance of the water reducer synthesized in the mixing amount range are optimal.
The polycarboxylic acid water reducer with high water reducing rate and mud resistance is prepared by introducing functional groups capable of reducing clay adsorption from the basis of the molecular structure design of the polycarboxylic acid water reducer and the mud resistance mechanism of the mud resistance type functional monomer, and has important significance for promoting the application and development of the polycarboxylic acid water reducer in the premixed concrete industry, realizing high performance of concrete and promoting sustainable development of the building material industry.
Compared with the prior art, the invention has the following advantages.
(1) Compared with the common polycarboxylic acid water reducer, the product has the advantages of low mixing amount, high water reducing rate, high water reducing capacity and excellent mud resistance, so that the product is not required to be compounded with the water reducer with high water reducing rate or the mud resistance agent in the using process, and is convenient to use;
(2) compared with the common polycarboxylic acid water reducing agent, the product of the invention can still enable the cement paste to have higher fluidity under the condition of higher mud content, and show excellent mud resistance effect;
(3) the polycarboxylic acid water reducing agent synthesized by the method does not use substances harmful to human bodies, such as formaldehyde, and the like in the synthesis process, and the process is green and environment-friendly; the synthesized product does not contain chloride ions and has no corrosion hazard to reinforcing steel bars in concrete;
(4) the synthetic method of the polycarboxylic acid water reducing agent is simple, compared with the general polycarboxylic acid water reducing agent synthetic process, the synthetic temperature is lower, the energy consumption is less, the normal pressure production is adopted, the requirement on equipment is low, the operation is convenient, and the industrial production is convenient.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, the starting materials or processing techniques are all those conventionally used in the art.
Example 1
A polycarboxylic acid water reducer with high water reducing rate and mud resistance is synthesized into 500 parts by weight of mother liquor, and the concrete operation steps are as follows: fixing a four-mouth flask on an iron support, immersing the bottom end of the four-mouth flask in a constant-temperature water bath, adjusting the water bath temperature to 45 ℃, keeping the whole polymerization reaction process to be carried out under the temperature condition, placing a thermometer, a stirrer, a constant-pressure funnel and a wood plug inserted with a conduit for connecting A liquid and B liquid on the four-mouth flask, and adjusting the height of the four-mouth flask to ensure that the stirrer can normally work. The molar ratio of the polyether macromonomer HPEG-2400 to the unsaturated acid monomer AA is about 1: 4.2, the blocked amide phosphate was 1.25% of the total weight of all monomers. 175.40 parts by weight of HPEG-2400 and 100 parts by weight of deionized water were added to a four-necked flask, and the stirrer was started and rotated at a constant high speed by adjusting the rotation speed of the stirrer. Weighing 0.3 part by weight of VC, 0.7 part by weight of thioglycolic acid and 100 parts by weight of deionized water to prepare solution A, uniformly stirring, weighing 22.10 parts by weight of AA, 2.5 parts by weight of end-capped amide phosphate and 50 parts by weight of deionized water to prepare solution B, uniformly stirring, and adding 2.0 parts by weight of H into a four-neck flask into which 175.40 parts by weight of HPEG-2400 and 100 parts by weight of deionized water are added at one time2O2And then setting relevant parameters of an automatic dropping instrument and starting reaction equipment to enable the solution A and the solution B to be added into a four-neck flask according to the dropping rate of 3.5h of the solution A/3 h of the solution B to start polymerization, supplementing a certain amount of deionized water to the obtained solution of 500 parts by weight after the dropping is finished, enabling the solid content of the prepared water reducer to be 40.6%, continuing stirring and keeping the temperature for 30min to finish the polymerization. After cooling to normal temperature, the obtained water reducing agent mother liquor was neutralized with 35% NaOH aqueous solution to pH 6-7, thereby obtaining the polycarboxylic acid having both high water reducing rate and mud resistance of example 1An acid water reducing agent.
Example 2
A polycarboxylic acid water reducer with high water reducing rate and mud resistance is synthesized into 500 parts by weight of mother liquor, and the concrete operation steps are as follows: fixing a four-mouth flask on an iron support, immersing the bottom end of the four-mouth flask in a constant-temperature water bath, adjusting the water bath temperature to 45 ℃, ensuring that the whole polymerization reaction process is carried out under the temperature condition, placing a thermometer, a stirrer, a constant-pressure funnel and a wood plug inserted with a conduit for connecting A liquid and B liquid on the four-mouth flask, and adjusting the height of the four-mouth flask to ensure that the stirrer can normally work. The molar ratio of the polyether macromonomer HPEG-2400 to the unsaturated acid monomer AA is 1: 4.5, the blocked amide phosphate was 1.25% of the total weight of all monomers. 174.00 parts by weight of HPEG-2400 and 100 parts by weight of deionized water were added to a four-necked flask, and the stirrer was started and rotated at a constant high speed by adjusting the rotation speed of the stirrer. Weighing 0.3 part by weight of VC, 0.7 part by weight of thioglycolic acid and 100 parts by weight of deionized water to prepare solution A, uniformly stirring, weighing 23.50 parts by weight of AA, 2.5 parts by weight of end-capped amide phosphate and 50 parts by weight of deionized water to prepare solution B, uniformly stirring, and adding 2.0 parts by weight of H into a four-neck flask into which 174.00 parts by weight of HPEG-2400 and 100 parts by weight of deionized water are added at one time2O2And then setting relevant parameters of an automatic dropping instrument and starting reaction equipment to enable the solution A and the solution B to be added into a four-neck flask according to the dropping rate of 3.5h of the solution A/3 h of the solution B to start polymerization, supplementing a certain amount of deionized water to the obtained solution of 500 parts by weight after the dropping is finished, enabling the solid content of the prepared water reducer to be 40.6%, continuing stirring and keeping the temperature for 30min to finish the polymerization. After cooling to normal temperature, the obtained water reducing agent mother liquor was neutralized with 35% NaOH aqueous solution to pH 6-7, thereby obtaining the polycarboxylic acid water reducing agent of example 2 having both high water reducing rate and mud resistance.
Example 3
A polycarboxylic acid water reducer with high water reducing rate and mud resistance is synthesized into 500 parts by weight of mother liquor, and the concrete operation steps are as follows: fixing a four-mouth flask on an iron support, immersing the bottom end of the four-mouth flask in a constant-temperature water bath, adjusting the temperature of the water bath to 45 ℃ to ensure the whole polymerization reactionThe process is carried out under the temperature condition, a thermometer, a stirrer, a constant pressure funnel and a wooden plug inserted with a conduit for connecting the liquid A and the liquid B are arranged on the four-mouth flask, and the height of the four-mouth flask is adjusted to ensure that the stirrer can work normally. The molar ratio of the polyether macromonomer HPEG-2400 to the unsaturated acid monomer AA is 1: 4.8, the blocked amide phosphate was 1.25% of the total weight of all monomers. 172.64 parts by weight of HPEG-2400 and 100 parts by weight of deionized water were added to a four-necked flask, and the stirrer was started and rotated at a constant high speed by adjusting the rotation speed of the stirrer. Weighing 0.3 part by weight of VC, 0.7 part by weight of thioglycolic acid and 100 parts by weight of deionized water to prepare solution A, uniformly stirring, weighing 24.86 parts by weight of AA, 2.5 parts by weight of end-capped amide phosphate and 50 parts by weight of deionized water to prepare solution B, uniformly stirring, and adding 2.0 parts by weight of H into a four-neck flask into which 172.64 parts by weight of HPEG-2400 and 100 parts by weight of deionized water are added at one time2O2And then setting relevant parameters of an automatic dropping instrument and starting reaction equipment to enable the solution A and the solution B to be added into a four-neck flask according to the dropping rate of 3.5h of the solution A/3 h of the solution B to start polymerization, supplementing a certain amount of deionized water to the obtained solution of 500 parts by weight after the dropping is finished, enabling the solid content of the prepared water reducer to be 40.6%, continuing stirring and keeping the temperature for 30min to finish the polymerization. After cooling to normal temperature, the obtained mother liquor of the water reducing agent is neutralized by 35% NaOH aqueous solution to pH 6-7, thereby obtaining the polycarboxylic acid water reducing agent of the embodiment 3 with high water reducing rate and mud resistance.
Example 4
A polycarboxylic acid water reducer with high water reducing rate and mud resistance is synthesized into 500 parts by weight of mother liquor, and the concrete operation steps are as follows: fixing a four-mouth flask on an iron support, immersing the bottom end of the four-mouth flask in a constant-temperature water bath, adjusting the water bath temperature to 45 ℃, ensuring that the whole polymerization reaction process is carried out under the temperature condition, placing a thermometer, a stirrer, a constant-pressure funnel and a wood plug inserted with a conduit for connecting A liquid and B liquid on the four-mouth flask, and adjusting the height of the four-mouth flask to ensure that the stirrer can normally work. The molar ratio of the polyether macromonomer HPEG-2400 to the unsaturated acid monomer AA is 1: 4.5, the blocked amide phosphate is 1.5% of the total weight of all monomers. At the fourth place173.57 parts by weight of HPEG-2400 and 100 parts by weight of deionized water were added to the flask and the stirrer was started and was rotated at a constant high speed by adjusting the rotational speed of the stirrer. Weighing 0.3 part by weight of VC, 0.7 part by weight of thioglycolic acid and 100 parts by weight of deionized water to prepare solution A, uniformly stirring, weighing 23.65 parts by weight of AA, 3 parts by weight of end-capped amide phosphate and 50 parts by weight of deionized water to prepare solution B, uniformly stirring, and adding 2.0 parts by weight of H into a four-neck flask into which 173.57 parts by weight of HPEG-2400 and 100 parts by weight of deionized water are added at one time2O2And then setting relevant parameters of an automatic dropping instrument and starting reaction equipment to enable the solution A and the solution B to be added into a four-neck flask according to the dropping rate of 3.5h of the solution A/3 h of the solution B to start polymerization, supplementing a certain amount of deionized water to the obtained solution of 500 parts by weight after the dropping is finished, enabling the solid content of the prepared water reducer to be 40.6%, continuing stirring and keeping the temperature for 30min to finish the polymerization. After cooling to normal temperature, the pH value of the mother liquor of the water reducing agent obtained by neutralizing with 35% NaOH aqueous solution is 6-7, thereby obtaining the polycarboxylic acid water reducing agent of the embodiment 4 with high water reducing rate and mud resistance.
The samples obtained in the above four examples were subjected to a net slurry fluidity test according to GBT 8077-2012 "test method for concrete admixture", honest cement p.o 42.5 cement was used as the cement, the water-cement ratio was 0.29, and the folding solid content of the polycarboxylic acid water-reducing agent was 0.16%. Selecting sodium bentonite provided by great industry and trade company of Ensheng, province, Sichuan province, removing particles with size of 0.075mm, oven drying at 105 + -5 deg.C to constant weight, cooling to room temperature, and adding in an internal mixing manner. The fluidity test results of the cement paste are shown in Table 1, wherein blank 1 is the fluidity of the cement paste without the admixture of the water reducing agent, and blank 2 is the fluidity of the cement paste with the admixture of the common polycarboxylic acid water reducing agent without the anti-mud function (the breaking admixture amount of the water reducing agent is consistent with that of each example).
Table 1 results of performance testing of examples
As can be seen from Table 1, the initial fluidity of the cement paste obtained by adding the samples of the four examples is greatly changed compared with that of the blank group 1, which shows that the synthesized polycarboxylic acid water reducer has higher water reducing rate, and the fluidity of the cement paste obtained by adding the samples of the four examples is not greatly lost along with the increase of the bentonite addition amount compared with that of the blank group 2, which shows that the polycarboxylic acid water reducer synthesized by the invention has excellent mud resistance.
In the above embodiments, the addition amounts of the raw materials such as the unsaturated polyether macromonomer, the unsaturated acid monomer, the anti-mud functional monomer, the initiator reducing component, and the like, and the process conditions such as the reaction time, the reagent titration time, the temperature, and the like can be arbitrarily selected and adjusted within the range defined in the above description.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A synthetic method of a polycarboxylic acid water reducer with high water reducing rate and mud resistance is characterized by comprising the following steps:
(1) weighing an initiator reduction component, a chain transfer agent and deionized water, and uniformly mixing to prepare a solution A;
(2) weighing unsaturated acid monomers, anti-mud functional monomers and deionized water, and uniformly mixing to prepare a solution B;
(3) adding unsaturated polyether macromonomer and deionized water into a four-neck flask serving as a reaction container, wherein the four-neck flask of the reaction container is fixed on an iron support, the bottom of the four-neck flask is immersed in a water bath kettle, a cantilever type stirrer is connected above the four-neck flask, and the cantilever type stirrer is started to dissolve the unsaturated polyether macromonomer in the deionized water;
(4) adding an initiator oxidation component into the reaction container in the step (3) at one time, adding the solution A and the solution B into the four-neck flask in the step (3) at a constant speed within a certain time to start a polymerization reaction, and continuously carrying out the whole polymerization reaction under the conditions of water bath temperature and stirring;
(5) and (4) after the solution A and the solution B are dropwise added in the step (4), continuously stirring and preserving heat for a certain time, cooling the synthesized product to normal temperature, and neutralizing the prepared polycarboxylic acid water reducer mother liquor by adopting 35% of NaOH aqueous solution until the pH value is 6-7 to obtain the target product.
2. The method for synthesizing the polycarboxylic acid water reducer having both high water reduction rate and mud resistance according to claim 1, wherein in the step (3), the unsaturated polyether macromonomer is isobutylene polyoxyethylene ether and has a number average molecular weight of 2400.
3. The method for synthesizing the polycarboxylic acid water reducer having both high water reduction rate and mud resistance according to claim 1, wherein the unsaturated acid monomer is acrylic acid.
4. The method for synthesizing the polycarboxylic acid water reducer with high water reduction rate and mud resistance according to claim 1, wherein the mud resistance type functional monomer is blocked amide phosphate.
5. The method for synthesizing the polycarboxylic acid water reducer having both high water reduction rate and anti-mud property according to claim 1, wherein the initiator reducing component is ascorbic acid.
6. The synthesis method of the polycarboxylic acid water reducer with both high water reduction rate and mud resistance according to claim 1, characterized in that the initiator oxidizing component is hydrogen peroxide or persulfate.
7. The method for synthesizing the polycarboxylic acid water reducer having both high water reduction rate and mud resistance according to claim 1, wherein the chain transfer agent is thioglycolic acid or mercaptopropionic acid.
8. The method for synthesizing the polycarboxylic acid water reducer with high water reduction rate and mud resistance according to claim 1, wherein the molar ratio of the unsaturated polyether macromonomer to the unsaturated acid monomer is 1: (4.2-4.8);
the anti-mud type functional monomer is calculated and weighed by an internal doping method, and the doping amount of the anti-mud type functional monomer is 1 to 1.5 percent of the total weight of the unsaturated polyether macromonomer, the unsaturated acid monomer and the anti-mud type functional monomer;
calculated and weighed by an external doping method, the initiator reduction component accounts for 0.1-0.2 percent of the total weight of all monomers, the initiator oxidation component accounts for 0.5-1.5 percent of the total weight of all monomers, and the chain transfer agent accounts for 0.3-0.4 percent of the total weight of all monomers.
9. The synthesis method of the polycarboxylic acid water reducer with both high water reducing rate and mud resistance according to claim 1, characterized in that the temperature of the water bath is 40-50 ℃, and the duration of the polymerization reaction is 3.5-4 h.
10. The method for synthesizing the polycarboxylic acid water reducer with both high water reduction rate and mud resistance according to claim 1, wherein the dropping speeds of the solution A and the solution B respectively satisfy: the finishing time of the solution A is 3-4 h, the finishing time of the solution B is 2.5-3.5 h, and the solution A is kept warm for 15min-1h after finishing the dripping.
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| CN112062910A (en) * | 2020-09-09 | 2020-12-11 | 安徽海螺新材料科技有限公司 | Micro-crosslinking anti-mud polycarboxylate superplasticizer and preparation method thereof |
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