CN110746553A - Low-shrinkage viscosity-reduction type polycarboxylate superplasticizer and preparation method and application thereof - Google Patents
Low-shrinkage viscosity-reduction type polycarboxylate superplasticizer and preparation method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention belongs to the technical field of concrete admixtures, and particularly relates to a low-shrinkage viscosity-reduction type polycarboxylate superplasticizer as well as a preparation method and application thereof. The invention starts from the design of molecular structure, HPEG or TPEG with hydrophobic end and functional small monomer with functions of reducing shrinkage and reducing viscosity are selected, components of reducing shrinkage and reducing viscosity are introduced by utilizing free radical polymerization reaction to prepare the functional polycarboxylate superplasticizer, the polycarboxylate superplasticizer has the effects of reducing shrinkage and reducing viscosity on fresh concrete, and the production and the use of the polycarboxylate superplasticizer have great advantages (the viscosity reducing effect is that collapse, V leakage, T500 and expansion degree are all superior to those of the like products sold in the market, and the crack resistance of reducing shrinkage is that compared with the like products sold in the market, the crack area of a flat plate crack is reduced by 18-56%); the invention can adopt a normal-temperature reaction system, has simpler production process and method, saves energy consumption, has little environmental pollution and is beneficial to popularization and application in a larger range.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a low-shrinkage viscosity-reduction type polycarboxylate superplasticizer, and a preparation method and application thereof.
Background
With the rapid development of modern buildings and material industries, modern buildings tend to be high-rise, light-weight and large-span, and the application of high-grade concrete is an indispensable premise, and the high-grade concrete is increasingly applied to the national infrastructure due to the characteristics of high overall strength, light dead weight and the like. In order to enable the concrete to reach a high-strength high-grade, a large amount of cementing materials, reinforcing materials and a low water-cement ratio are often needed to realize the high-strength high-grade concrete, so that the problems of high viscosity and low flow rate of fresh concrete are caused, a series of construction problems such as concrete stirring, transportation and pumping are further caused, particularly the problem of high viscosity of ultrahigh-strength concrete is serious in China, the construction difficulty is high, and engineering accidents are frequent. At present, the viscosity reduction method of high-strength concrete mainly adopts the steps of increasing the mixing amount of a water reducing agent, preparing high-quality superfine powder and optimizing the particle grading. The viscosity of the concrete is reduced by adopting a method of increasing the mixing amount of the water reducing agent, so that on one hand, the cost is increased, on the other hand, the excessive retardation of the slurry is caused, and the formwork removal period is prolonged; although a lot of researches on reducing the viscosity of concrete are carried out on the ultrafine powder and the optimized particle gradation, the method has certain limitations, the flowability of the fresh concrete mainly depends on the strong adsorption and dispersion effects of the high-efficiency water reducing agent, and the actual problem cannot be fundamentally solved by optimizing the particle gradation.
The method for reducing the concrete shrinkage mainly adopts the methods of doping fiber, shrinkage reducing agent, expanding agent and the like. However, these methods have limitations, for example, too little amount of the expanding agent is added to fail to achieve the desired effect, and too much amount of the expanding agent is added to cause excessive expansion and cracks to appear or to make existing cracks larger; the fiber has a certain shrinkage reducing effect, the cost is not high, but the compatibility with concrete is not good; some shrinkage reducing agent products in the market have good shrinkage reducing effect, but the mixing amount is large and the unit price is high, so that the cost of concrete is greatly increased, and therefore, the research and development of the low-shrinkage viscosity-reduction type polycarboxylate superplasticizer has great practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a low-shrinkage viscosity-reduction type polycarboxylate superplasticizer as well as a preparation method and application thereof, which are mainly applied to special buildings such as bridge concrete, reservoir dams and the like.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a low-shrinkage viscosity-reduction type polycarboxylate superplasticizer comprises a scheme A and a scheme B,
the scheme A is an ammonium persulfate initiating system, and specifically comprises the following steps:
(1) maleic Anhydride (MA) and diethylene glycol monobutyl ether are reacted to prepare a shrinkage-reducing functional monomer;
(2) adding a functional monomer into deionized water, heating and stirring until the functional monomer is completely dissolved to obtain a functional monomer solution, wherein the functional monomer is TPEG (isopentenol polyoxyethylene ether) or HPEG (methallyl alcohol polyoxyethylene ether);
(3) adding the shrinkage reducing functional monomer obtained in the step (1) into the functional monomer solution obtained in the step (2);
(4) preparing solution A and solution B: adding thioglycollic acid into deionized water to obtain a solution A; mixing acrylic acid and diethylene glycol dimethacrylate to obtain a solution B;
(5) adding initiator ammonium persulfate into the mixed solution obtained in the step (3), controlling a certain reaction temperature, simultaneously dropwise adding the solution A and the solution B, continuing to perform heat preservation reaction for a period of time after dropwise adding is finished, then cooling to room temperature, adjusting the pH value to 7-8, and uniformly stirring to obtain a polycarboxylic acid water reducer product;
scheme B is H2O2The Vc initiation system comprises the following steps:
(1) maleic Anhydride (MA) and diethylene glycol monobutyl ether are reacted to prepare a shrinkage-reducing functional monomer;
(2) adding a functional monomer into deionized water, heating and stirring until the functional monomer is completely dissolved to obtain a functional monomer solution, wherein the functional monomer is TPEG (isopentenol polyoxyethylene ether) or HPEG (methallyl alcohol polyoxyethylene ether);
(3) adding the shrinkage reducing functional monomer obtained in the step (1) into the functional monomer solution obtained in the step (2);
(4) preparing solution A and solution B: adding thioglycolic acid and Vc (ascorbic acid) into deionized water to obtain a solution A; mixing acrylic acid and diethylene glycol dimethacrylate to obtain a solution B;
(5) cooling the mixed solution obtained in the step (3) to room temperature, and adding an initiator H2O2Controlling a certain reaction temperature, simultaneously dropwise adding the solution A and the solution B, continuously keeping the reaction for a period of time after the dropwise adding is finished, then cooling the temperature to room temperature, adjusting the pH value to 7-8, and uniformly stirring to obtain the polycarboxylate superplasticizer product.
In the above scheme a and scheme B, the reaction process of the shrinkage reducing functional monomer is as follows: and (3) placing Maleic Anhydride (MA) and diethylene glycol monobutyl ether at 80-100 ℃ to react for 3 hours under the action of a catalyst, and carrying out reduced pressure distillation and cooling to obtain the shrinkage reducing functional monomer.
In the scheme A and the scheme B, the heating and stirring temperature in the step (2) is 50-70 ℃.
In the scheme, the reaction temperature in the step (5) in the scheme A is controlled to be 50-70 ℃, and the reaction temperature in the step (5) in the scheme B is controlled to be 25-30 ℃.
In the scheme A and the scheme B, the dropping time of the solution A and the solution B which are simultaneously dropped in the step (5) is controlled to be 2.5-4 h, and the reaction is continuously kept for 1-2 h after the dropping is finished.
In the neutralization scheme B of the scheme A, the mass ratio of the maleic anhydride, the functional monomer, the diethylene glycol monobutyl ether, the diethylene glycol dimethacrylate and the acrylic acid is 0.5-0.8: 1: 0.6-1.0: 0.5-1.0: 3-3.5.
In the scheme A and the scheme B, the relative molecular mass of the functional monomer is 2200-2600.
In the above scheme A, the addition amount of the thioglycolic acid is 1 to 3 percent (molar ratio) based on the functional monomer; the addition amount of the initiator ammonium persulfate is 2-5% (molar ratio).
In the above scheme B, based on the functional monomer, the added amount of thioglycolic acid is 1% to 3% (molar ratio), the added amount of Vc (ascorbic acid) is 4% to 6% (molar ratio), and the initiator H is2O2The amount of (c) is 0.15 to 0.30 (molar ratio).
The TPEG and HPEG molecular structures are shown as follows, wherein the value range of n is 48-57, and the relative molecular mass is 2200-2600:
the structure of the shrinkage reducing functional monomer is as follows:
the structural formula of the small monomer diethylene glycol dimethacrylate with the viscosity reduction function is shown as the following formula:
the synthetic route of the low-shrinkage and viscosity-reduction type polycarboxylate superplasticizer synthesized by taking TPEG as a raw material is shown as the following formula:
the synthetic route of the low-shrinkage and viscosity-reduction type polycarboxylate superplasticizer synthesized by taking HPEG as a raw material is shown as the following formula:
the invention has the beneficial effects that: the invention starts from the design of molecular structure, selects HPEG or TPEG with hydrophobic end and monomer with functions of reducing shrinkage and reducing viscosity, utilizes free radical polymerization reaction to introduce components of reducing shrinkage and reducing viscosity, and controls the polymerization degree by controlling the parameters of the reaction process, thus preparing a novel functional polycarboxylic acid water reducer, wherein the functional polycarboxylic acid water reducer has the effects of reducing shrinkage and reducing viscosity on fresh concrete, and the production and use of the water reducer have great advantages (the viscosity reduction effect is that collapse, V leakage, T500 and expansion are superior to the similar products sold in the market, and the crack resistance of the reducing shrinkage is that the crack area of a flat plate crack is reduced by 18-56 percent compared with the similar products sold in the market); the invention can adopt a normal-temperature reaction system, has simpler production process and method, saves energy consumption, has little environmental pollution and is beneficial to popularization and application in a larger range.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A low-shrinkage viscosity-reduction polycarboxylate superplasticizer is prepared by an ammonium persulfate initiation system, and comprises the following components in parts by weight:
(1) adding 1.2 parts of maleic anhydride, 2.0 parts of diethylene glycol monobutyl ether and 0.2 part of catalyst (p-toluenesulfonic acid) into a three-neck flask provided with a thermometer, a mechanical stirrer and a reflux condenser, heating to 100 ℃ in an oil bath, heating, stirring, reacting for 3 hours, carrying out reduced pressure distillation, and cooling to obtain a shrinkage-reducing functional monomer;
(2) adding 37.6 parts of functional monomer TPEG (relative molecular mass 2400) and 44.5 parts of deionized water into a three-neck flask provided with a thermometer, a mechanical stirrer and a reflux condenser, heating to 60 ℃ in a water bath, and stirring for 10min until the TPEG and the deionized water are completely dissolved;
(3) adding 3.2 parts of the shrinkage-reducing functional monomer obtained in the step (1) into 82.1 parts of the functional monomer solution obtained in the step (2);
(4) preparing solution A and solution B: adding 0.04 part of thioglycollic acid into 7.3 parts of deionized water to obtain a solution A; mixing 3.9 parts of acrylic acid and 3.0 parts of diethylene glycol dimethacrylate to obtain a solution B;
(5) adding 0.1 part of initiator ammonium persulfate into the mixed solution obtained in the step (3), controlling the reaction temperature to be 60 ℃, simultaneously dropwise adding the solution A and the solution B into the mixed solution, heating, refluxing and stirring the mixture, simultaneously dropwise adding the solution A and the solution B for 3 hours, and continuously carrying out heat preservation reaction for 1 hour after the dropwise adding is finished; and finally, cooling the reaction temperature to room temperature, adjusting the pH value to 7-8 by using a 30% NaOH solution, and uniformly stirring to obtain a polycarboxylate superplasticizer product PCA-1.
Example 2
A low-shrinkage viscosity-reduction polycarboxylate superplasticizer is prepared by an ammonium persulfate initiation system, and comprises the following components in parts by weight:
(1) adding 1.2 parts of maleic anhydride, 2.0 parts of diethylene glycol monobutyl ether and 0.2 part of catalyst (p-toluenesulfonic acid) into a three-neck flask provided with a thermometer, a mechanical stirrer and a reflux condenser, heating in an oil bath to 100 ℃, heating, stirring, reacting for 3 hours, distilling under reduced pressure, and cooling to obtain a shrinkage-reducing functional monomer;
(2) adding 37.6 parts of functional monomer HPEG (relative molecular mass 2400) and 44.5 parts of deionized water into a three-neck flask provided with a thermometer, a mechanical stirrer and a reflux condenser, heating to 60 ℃ in a water bath, and stirring for 10min until the functional monomer HPEG and the deionized water are completely dissolved;
(3) adding 3.2 parts of the shrinkage-reducing functional monomer obtained in the step (1) into 82.1 parts of the functional monomer solution obtained in the step (2);
(4) preparing solution A and solution B: adding 0.04 part of thioglycollic acid into 7.3 parts of deionized water to obtain a solution A; mixing 3.9 parts of acrylic acid and 3.0 parts of diethylene glycol dimethacrylate to obtain a solution B;
(5) adding 0.1 part of initiator ammonium persulfate into the mixed solution obtained in the step (3), controlling the reaction temperature to be 60 ℃, simultaneously dropwise adding the solution A and the solution B into the mixed solution, heating, refluxing and stirring the mixture, simultaneously dropwise adding the solution A and the solution B for 3 hours, and continuously carrying out heat preservation reaction for 1 hour after the dropwise adding is finished; and finally, cooling the reaction temperature to room temperature, adjusting the pH value to 7-8 by using a 30% NaOH solution, and uniformly stirring to obtain a polycarboxylate superplasticizer product PCA-2.
Example 3
A low-shrinkage viscosity-reduction polycarboxylate superplasticizer which is prepared by reacting H2O2The Vc initiation system is prepared as follows:
(1) adding 1.2 parts of maleic anhydride, 2.0 parts of diethylene glycol monobutyl ether and 0.2 part of catalyst (p-toluenesulfonic acid) into a three-neck flask provided with a thermometer, a mechanical stirrer and a reflux condenser, heating in an oil bath to 100 ℃, heating, stirring, reacting for 3 hours, distilling under reduced pressure, and cooling to obtain a shrinkage-reducing functional monomer;
(2) adding 37.6 parts of functional monomer TPEG (relative molecular mass 2400) and 44.5 parts of deionized water into a three-neck flask provided with a thermometer, a mechanical stirrer and a reflux condenser, heating to 60 ℃ in a water bath, and stirring for 10min until the TPEG and the deionized water are completely dissolved;
(3) adding 3.2 parts of the shrinkage-reducing functional monomer obtained in the step (1) into 82.1 parts of the functional monomer solution obtained in the step (2);
(4) preparing solution A and solution B: adding 0.04 part of thioglycolic acid and 0.16 part of Vc (ascorbic acid) into 7.3 parts of deionized water to obtain a solution A; mixing 3.9 parts of acrylic acid and 3.0 parts of diethylene glycol dimethacrylate to obtain a solution B;
(5) cooling the mixed solution obtained in the step (3) to room temperature, and adding 0.2 part of initiator H2O2Controlling the reaction temperature to be 25 ℃, simultaneously dripping the solution A and the solution B into the mixture, heating, refluxing and stirring the mixture, simultaneously dripping the solution A and the solution B for 3 hours, and continuously reacting for 1 hour after the dripping is finished; and finally, cooling the reaction temperature to room temperature, adjusting the pH value to 7-8 by using a 30% NaOH solution, and uniformly stirring to obtain a polycarboxylate superplasticizer product PCA-3.
Example 4
A low-shrinkage viscosity-reduction polycarboxylate superplasticizer which is prepared by reacting H2O2The Vc initiation system is prepared as follows:
(1) adding 1.2 parts of maleic anhydride, 2.0 parts of diethylene glycol monobutyl ether and 0.2 part of catalyst (p-toluenesulfonic acid) into a three-neck flask provided with a thermometer, a mechanical stirrer and a reflux condenser, heating in an oil bath to 100 ℃, heating, stirring, reacting for 3 hours, distilling under reduced pressure, and cooling to obtain a shrinkage-reducing functional monomer;
(2) adding 37.6 parts of functional monomer HPEG (relative molecular mass 2400) and 44.5 parts of deionized water into a three-neck flask provided with a thermometer, a mechanical stirrer and a reflux condenser, heating to 60 ℃ in a water bath, and stirring for 10min until the functional monomer HPEG and the deionized water are completely dissolved;
(3) adding 3.2 parts of the shrinkage-reducing functional monomer obtained in the step (1) into 82.1 parts of the functional monomer solution obtained in the step (2);
(4) preparing solution A and solution B: adding 0.04 part of thioglycolic acid and 0.16 part of Vc (ascorbic acid) into 7.3 parts of deionized water to obtain a solution A; mixing 3.9 parts of acrylic acid and 3.0 parts of diethylene glycol dimethacrylate to obtain a solution B;
(5) cooling the mixed solution obtained in the step (3) to room temperature, and adding 0.2 part of initiator H2O2Controlling the reaction temperature to be 25 ℃, simultaneously dripping the solution A and the solution B into the mixture, heating, refluxing and stirring the mixture, keeping the time for dripping the solution A and the solution B for 3 hours, and continuously reacting for 1 hour after the dripping is finished; and finally, cooling the reaction temperature to room temperature, adjusting the pH value to 7-8 by using a 30% NaOH solution, and uniformly stirring to obtain a polycarboxylate superplasticizer product PCA-4.
Comparative example 1
The use of a commercially available polycarboxylate water reducer of the same type (type Subot-404) is a comparative example of the present patent.
Application example 1
In order to detect the cement adaptability of the functional polycarboxylate water reducer prepared by two initiation systems and two macromonomers, the three cements are selected as reference cement, Tianshan cement and Qingsong cement respectively, the cement paste fluidity test is carried out according to the national standard GB/T8077 plus 2012 'concrete additive homogeneity test method', the mixing amount of the water reducer is 0.25% (taking the weight of the cement after solid folding as the reference), and the test results are shown in Table 1.
TABLE 1 neat paste fluidity and loss over time contrast (mm) for different water reducers
As can be seen from the results in Table 1, under two initiation systems, the dispersibility and the dispersion retention of the polycarboxylic acid water reducer prepared from two macromonomers are basically the same as those of a similar product (Subot 404 type water reducer) sold in the market, the cement dispersing performance is not influenced by the introduction of the functional monomer, and the synthesized polycarboxylic acid water reducer has better cement adaptability as can be seen from the net slurry fluidity results of 3 types of cement.
Application example 2
The 4 polycarboxylate water reducers obtained by the invention are doped into cement mortar, the water reducing effect of the functional polycarboxylate water reducers and the similar products (Subo 404 type water reducers) sold in the market on cement mortar is contrastively researched according to the national standard GB/T2419-2005 cement mortar fluidity test standard, the doping amount of the water reducers is 0.30% (based on the weight of cement after fracture), and the test results are shown in Table 2.
TABLE 2 test results of water reducing rate of cement mortar with different water reducing agents
As can be seen from Table 2, for the same type of products (Subot 404 type water reducing agent) sold in the market, the water reducing rate of the mortar is 21.9%, and the water reducing rate of the mortar prepared by the functional water reducing agent prepared by the two macromonomers is 21.3-24.4%, so that the functional water reducing agent has good water reducing effect on cement mortar.
Application example 3
The compressive strength and the flexural strength of the cement mortar are evaluated according to the national standard GB/T17697 and 1999 'cement mortar strength test method', the flexural strength and the compressive strength of the functional water reducer prepared by two macromonomers for cement mortar test pieces at different curing ages are evaluated, the used cement is 42.5, the doping amount of the water reducer is 0.30% (based on the weight of the cement after fracture setting), and the test results are shown in Table 3.
TABLE 3 Cement mortar compression and rupture Strength test results (MPa)
As can be seen from Table 3, the cement mortar of the functional water reducer prepared by using two macromonomers has obvious enhancement effect compared with the blank in early and later strength, and the effect is similar to that of a similar product (Subot 404 type water reducer) sold in the market. Compared with blank mortar, the early compressive strength of the cement mortar doped with the functional water reducer is improved by 20.3-23.3 MPa, the standard-age compressive strength is improved by 6.5-12 MPa, and the flexural strength is also improved. The functional water reducing agent prepared by the invention has good promotion effect on the compression resistance and the fracture resistance of the cement mortar.
Application example 4
The concrete water-reducing rate of the functional water-reducing agent is evaluated according to national standard GB/T8076 and 2008 'concrete admixture', the water-reducing rate of the 4 water-reducing agents prepared by two macromonomers for concrete is 0.30 percent (based on the weight of the gelled material after being folded and fixed), and the test results are shown in Table 4.
TABLE 4 test results of water reducing rate of concrete with different water reducing agents
As can be seen from Table 4, the water reduction of the concrete mix was 17.3% for the same commercial product (Subot 404 type water reducer). The water reducing rate of the concrete mixture of the functional water reducing agent prepared by two macromonomers is 18.0-19.3%, the water reducing agent has good water reducing effect on the concrete mixture, and the water reducing rate of the functional water reducing agent meets the requirements of standards on the water reducing rate of a high-efficiency water reducing agent.
Application example 5
A commercially available similar product (Subot 404 type water reducing agent) is used as a comparison sample, a C50 self-compacting concrete trial preparation is used as an investigation object, and the adjustment condition of 4 functional polycarboxylic acid water reducing agents on the viscosity of C50 self-compacting concrete is contrastively tested. The viscosity reduction performance of the C50 self-compacting concrete is examined by testing the slump loss, the V leakage, the T500, the expansion degree and the like of the self-compacting concrete. The concrete slump loss, V funnel determination, the expansion degree and T500 tests are carried out according to the relevant requirements of JGJ/T283-2012 'technical specification for self-compacting concrete application', and the test results are shown in Table 5.
TABLE 5 Performance testing of functional polycarboxylate superplasticizer concrete
As shown in Table 5, compared with the concrete prepared from the similar product (Subot 404 type water reducing agent) sold in the market, the concrete prepared from the functional water reducing agent has better effects on slump test, expansion test, slump loss test, T500 test and V leakage test than the comparative sample. Fully shows that the introduction of the functional polycarboxylate superplasticizer has obvious improvement effect on the fluidity and the viscosity of the C50 self-compacting concrete.
Application example 6
A commercially available similar product (Subot 404 type water reducing agent) is taken as a comparison sample, a C50 self-compacting concrete trial is taken as an investigation object, and the reduction and cracking resistance of the 4 functional polycarboxylic acid water reducing agents to the C50 self-compacting concrete are contrastively tested. According to GB/T50082-2009 test method for long-term performance and durability of ordinary concrete, a flat plate edge constraint method is selected to evaluate the cracking of the concrete, and the test results are shown in Table 6.
TABLE 6 concrete cracking Performance parameters prepared with different Water reducing Agents
Note: a is the average crack area of the crack; b, the cracking number of the cracks in unit area; c total area of cracking per unit area
As shown in Table 6, compared with the concrete prepared from the same type of commercial product (Subot 404 type water reducing agent), the concrete prepared from the functional water reducing agent has better maximum crack width and total crack area per unit area than the comparative sample in the flat crack test. The introduction of the functional polycarboxylate superplasticizer has obvious improvement effect on reducing the shrinkage and cracking of concrete.
Application example 7
The compressive strength ratio of the hardened concrete is tested according to national standard GB/T8076-.
TABLE 7 compressive strength ratio test results of concrete prepared from different water reducing agents at different ages
As can be seen from Table 7, the functional water reducing agent prepared by two macromonomers of the invention is superior to the concrete compressive strength prepared by the similar products (Subot 404 type water reducing agent) on the market in both early strength and later strength except PCA-4; wherein the 3d compressive strength is improved by 3.5-6.3 MPa, and the 28d compressive strength is improved by 7.2-14.6 MPa. The functional water reducer prepared by the invention has a good promotion effect on improving the compressive strength of concrete.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a low-shrinkage viscosity-reduction type polycarboxylate superplasticizer is characterized by comprising a scheme A and a scheme B,
the scheme A is an ammonium persulfate initiating system, and specifically comprises the following steps:
(1) maleic Anhydride (MA) and diethylene glycol monobutyl ether are reacted to prepare a shrinkage-reducing functional monomer;
(2) adding a functional monomer into deionized water, heating and stirring until the functional monomer is completely dissolved to obtain a functional monomer solution
The monomer is TPEG (isopentenol polyoxyethylene ether) or HPEG (methyl allyl alcohol polyoxyethylene ether);
(3) adding the shrinkage reducing functional monomer obtained in the step (1) into the functional monomer solution obtained in the step (2);
(4) preparing solution A and solution B: adding thioglycollic acid into deionized water to obtain a solution A; mixing acrylic acid and diethylene glycol dimethacrylate to obtain a solution B;
(5) adding initiator ammonium persulfate into the mixed solution obtained in the step (3), controlling a certain reaction temperature, simultaneously dropwise adding the solution A and the solution B, continuing to perform heat preservation reaction for a period of time after dropwise adding is finished, then cooling to room temperature, adjusting the pH value to 7-8, and uniformly stirring to obtain a polycarboxylic acid water reducer product;
scheme B is H2O2The Vc initiation system comprises the following steps:
(1) maleic Anhydride (MA) and diethylene glycol monobutyl ether are reacted to prepare a shrinkage-reducing functional monomer;
(2) adding a functional monomer into deionized water, heating and stirring until the functional monomer is completely dissolved to obtain a functional monomer solution, wherein the functional monomer is TPEG (isopentenol polyoxyethylene ether) or HPEG (methallyl alcohol polyoxyethylene ether);
(3) adding the shrinkage reducing functional monomer obtained in the step (1) into the functional monomer solution obtained in the step (2);
(4) preparing solution A and solution B: adding thioglycolic acid and Vc (ascorbic acid) into deionized water to obtain a solution A;
mixing acrylic acid and diethylene glycol dimethacrylate to obtain a solution B;
(5) cooling the mixed solution obtained in the step (3) to room temperature, and adding an initiator H2O2Controlling a certain reaction temperature, simultaneously dropwise adding the solution A and the solution B, continuously keeping the reaction for a period of time after the dropwise adding is finished, then cooling the temperature to room temperature, adjusting the pH value to 7-8, and uniformly stirring to obtain the polycarboxylate superplasticizer product.
2. The method of claim 1, wherein the reaction process of reducing the functional monomer in scheme a and scheme B is as follows: and (3) placing Maleic Anhydride (MA) and diethylene glycol monobutyl ether at 80-100 ℃ to react for 3 hours under the action of a catalyst, and carrying out reduced pressure distillation and cooling to obtain the shrinkage reducing functional monomer.
3. The preparation method of claim 1, wherein in the scheme A and the scheme B, the heating and stirring temperature in the step (2) is 50-70 ℃.
4. The method of claim 1, wherein the reaction temperature in step (5) in scheme A is controlled to be 50-70 ℃, and the reaction temperature in step (5) in scheme B is controlled to be 25-30 ℃.
5. The preparation method according to claim 1, wherein in the scheme A and the scheme B, the dropping time of the solution A and the solution B in the step (5) is controlled to be 2.5-4 h.
6. The method according to claim 1, wherein in the neutralization step B, the mass ratio of the maleic anhydride, the functional monomer, the diethylene glycol monobutyl ether, the diethylene glycol dimethacrylate and the acrylic acid is 0.5-0.8: 1: 0.6-1.0: 0.5-1.0: 3-3.5.
7. The method according to claim 1, wherein the relative molecular mass of the functional monomer in the neutralization scheme B in the scheme A is 2200 to 2600.
8. The method of claim 1, wherein in scheme a: taking a functional monomer as a reference, wherein the addition amount of the thioglycolic acid is 1-3% (molar ratio); the addition amount of the initiator ammonium persulfate is 2-5% (molar ratio); in scheme B: based on functional monomers, the addition amount of thioglycolic acid is 1-3% (mol ratio), the addition amount of ascorbic acid is 4-6% (mol ratio), and the initiator H2O2The amount of (c) is 0.15 to 0.30 (molar ratio).
9. The low-shrinkage viscosity-reduction polycarboxylate superplasticizer prepared by the preparation method of any one of claims 1 to 8.
10. The application of the low-shrinkage viscosity-reduction type polycarboxylate superplasticizer disclosed by claim 9 in the field of concrete.
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