CN107474189B - Slump-retaining clay inhibitor and preparation method thereof - Google Patents
Slump-retaining clay inhibitor and preparation method thereof Download PDFInfo
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- CN107474189B CN107474189B CN201710813622.XA CN201710813622A CN107474189B CN 107474189 B CN107474189 B CN 107474189B CN 201710813622 A CN201710813622 A CN 201710813622A CN 107474189 B CN107474189 B CN 107474189B
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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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
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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
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a slump-retaining clay inhibitor which is a product with solid content of 40% obtained by reacting a star initiator, a monomer, an oxidant, a reducing agent and a ligand through ARGET ATRP; the star initiator is a mixture of a monomer, an oxidant, a reducing agent and a ligand, wherein the molar ratio of the star initiator to the monomer to the reducing agent to the ligand is 1: 10-200: 0.01-0.1: 0.5-5: 0.01-0.5, and the monomer is a mixture of a cationic monomer and an amphoteric betaine monomer, wherein the molar ratio of the cationic monomer to the amphoteric betaine monomer is 30-95% and 5-70%. The invention also discloses a preparation method of the inhibitor, wherein the polymerization reaction can be carried out at room temperature, and the sensitivity to oxygen and the dosage of the catalyst are effectively reduced. The clay inhibitor is compounded with the industrial polycarboxylic acid water reducing agent, so that the adaptability of the water reducing agent to soil can be effectively improved, and higher construction requirements can be met.
Description
Technical Field
The invention relates to a clay inhibitor and a preparation method thereof, in particular to a slump loss resistant clay inhibitor and a preparation method thereof, belonging to the technical field of concrete admixtures in building materials.
Background
The polycarboxylate superplasticizer has the advantages of low mixing amount, high water reducing rate, good slump retaining performance, strong molecular structure adjustability, large high-performance potential and the like, and becomes a third-generation high-performance concrete water reducer. However, polycarboxylic acid water reducing agents also face a number of technical difficulties in practical use, of which the sensitivity to clay is most pronounced. In order to avoid the negative effect on concrete caused by high mud content of aggregate, the current commonly used solving measure is to wash the aggregate with high mud content or add a water reducing agent in an excessive amount. However, aggregate grading is damaged during washing, working procedures are increased, and construction period is affected; super-admixtures typically cause initial bleeding and segregation of the concrete and increase costs.
The clay in the sand and stone material is mainly montmorillonite soil and kaolin, has higher specific surface area and a layered structure, and is preferential to cement to adsorb a water reducing agent and free water, so that the problems of large slump loss, poor rheological property, reduced durability and strength and the like of concrete are caused. The surface of cement hydrated particles is mainly positively charged, while the surface of clay particles is negatively charged, so that the component containing cations is added into the polycarboxylic acid water reducing agent, and through electrostatic adsorption, the clay particles can be coated, so that a good anti-mud effect is achieved, and compared with a small-molecular cationic compound, the cationic polymer has unique advantages as a clay inhibitor.
The molecular configuration of the clay inhibitor itself is also of great concern for its effect on the effectiveness of the clay. The molecules of the star polymer contain a large number of short branched chains, the winding among the molecules is less, the acting force among the molecules is small, and the intrinsic viscosity of the star polymer is far smaller than that of linear molecules; the star polymer has a three-dimensional spherical structure, and molecules are not intertwined, so that the space volume is larger than that of a linear polymer with the same molecular weight, the steric hindrance effect is stronger, and the clay inhibitor with the star structure has higher adaptability and a dispersing effect.
The β -cyclodextrin (β -CD) has a slightly conical molecular structure, a large amount of hydroxyl exists outside a conical cavity to show hydrophilicity, the conical cavity is hydrophobic, the molecular weight is 1135, the spatial diameter is 0.8nm, the cavity depth is about 0.7-0.8 nm, and the cyclodextrin is taken as a functional group and is introduced into the clay inhibitor to generate a good effect.
At present, radical polymerization is mainly adopted for preparing the polycarboxylate water reducer and the clay inhibitor, the molecular weight distribution of the obtained polymer is wider, the active polymerization technology has the advantages of designable molecular structure, controllable molecular weight, narrow molecular weight distribution and the like, if the active polymerization technology is applied to the preparation of the polycarboxylate water reducer and the clay inhibitor, the active polymerization technology has important significance for constructing the polycarboxylate water reducer and the clay inhibitor with controllable molecular structures, and the active polymerization methods adopted in the field of the water reducer mainly comprise Atom Transfer Radical Polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT). Chinese patents CN106084157A, CN106146765A, CN106146859A, CN106519142A, CN106750046A, CN103482897A, CN102002134A and CN105669913A disclose that polycarboxylic acid water reducing agent is prepared by ATRP technology, Chinese patent CN106519121A discloses that reinforced mud-resisting agent is prepared by ATRP technology, and Chinese patents CN105712650A, CN105669912A, CN105153375A, CN106749958A and CN106496447A disclose that polycarboxylic acid water reducing agent is prepared by RAFT polymerization. However, the above living polymerization process is relatively severe in conditions, and is generally conducted in the absence of oxygen in a hermetic seal at relatively high temperatures. For ATRP, the catalyst is a low-valence transition metal compound, is easy to oxidize and deactivate, and is not beneficial to mass production, storage and transportation; the catalyst and the ligand have relatively large dosage, high toxicity and high cost; the post-treatment of the polymer is complicated and the recovery of the catalyst and ligand is difficult. These are the main factors limiting the large-scale industrial production of ATRP.
The ATRP technology (ARGET ATRP) with the function of regenerating the electron transfer catalyst which is developed recently solves the problems of the current industrial application of ATRP to a certain extent and has great industrial application value. The principle is that a certain amount of catalyst reducing agent is added in the ATRP reaction at the same time, so that divalent copper ions generated in the ATRP process can be reversibly reduced into monovalent copper ions, thereby improving the activity of the catalyst and effectively reducing the use amount of the catalyst and corresponding ligands. ARGET-ATRP has the following advantages: 1) the reaction conditions are relatively mild and can be carried out in the presence of a small amount of oxygen and free radicals; 2) no new initiating free radical or active species are generated in the reduction process of the reducing agent; 3) the catalyst is a stable high-valence transition metal compound, which is beneficial to mass production, storage and transportation; 4) the catalyst and ligand used in the system are relatively small in dosage (the dosage of the Cu catalyst can be reduced to several ppm), so that the post-polymerization treatment is simplified; 5) the used catalyst reducing agent has low toxicity (FDA certification) and is easy to obtain. The advantages are beneficial to further realizing industrial production, but no report of preparing the slump-retaining clay inhibitor by adopting ARGET ATRP technology is found in search.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a slump-retaining clay inhibitor and a preparation method thereof.
The slump-retaining clay inhibitor is a product with 40% of solid content obtained by reacting a star initiator, a monomer, an oxidant, a reducing agent and a ligand through atom transfer radical polymerization (ARGET ATRP) with an electron transfer catalyst regeneration function, and is characterized in that the star initiator is a mixture of a cationic monomer and an amphoteric betaine monomer, the molar ratio of the cationic monomer to the amphoteric betaine monomer is (30-95%) (5-70%), the star initiator is prepared by dissolving 11.35g (0.01mol) of 0.01mol of β -cyclodextrin in 60mL of anhydrous N, N-Dimethylformamide (DMF) in 100mL of a three-necked flask, adding 7.07g (0.07 mol) of triethylamine as an absorbent, stirring in an ice water bath atmosphere, adding 0.5 g of triethylamine in 0.07mol of triethylamine in 0.5 mL of an N, filtering in a water bath, precipitating in a water bath, reacting at room temperature for 2.24 h, adding ethanol in a nitrogen-containing neutral bromine, filtering, reacting at room temperature for a constant-pressure, adding bromine-removing water, filtering, reacting in a nitrogen-containing acetone-ethyl alcohol, adding a nitrogen-ethyl alcohol dropwise, reacting, adding a nitrogen-ethyl alcohol in a nitrogen-ethyl alcohol-16 h, filtering, and precipitating, reacting under a constant-pressure filtration, and filtering, wherein the ethyl alcohol is added in a constant-pressure, and the mixture of a constant-3 g of anhydrous DMF is obtained by adding bromine-3 g of β -16 h, and stirring, and adding bromine-16 h, and stirring, and the mixture of anhydrous DMF, andan initiator; the cationic monomer is methacryloyloxyethyl trimethyl ammonium chloride; the amphoteric betaine monomer is carboxyl betaine, sulfobetaine or phosphate betaine; the oxidant is CuBr2(cupric bromide) or CuCl2(copper chloride); the reducing agent is Vc (vitamin C); the ligand is PMDETA (pentamethyldiethylenetriamine) and Me6TREN (Tris [2- (dimethylamino) ethyl ester)]Amine) or bpy (bipyridine).
The preparation method of the slump-retaining clay inhibitor comprises the steps of halogenating cyclodextrin to obtain a star-shaped initiator, initiating copolymerization of a cationic monomer and an amphoteric betaine monomer by an atom transfer radical polymerization (ARGET ATRP) method with an electron transfer catalyst regeneration function at room temperature, and further processing the product to obtain a product with the solid content of 40%, namely the slump-retaining clay inhibitor; wherein the cationic monomer is methacryloyloxyethyl trimethyl ammonium chloride; the amphoteric betaine monomer is carboxyl betaine, sulfobetaine or phosphate betaine.
Further, the preferred preparation method of the slump-retaining clay inhibitor is as follows: dissolving a star-shaped initiator, a cationic monomer and an amphoteric betaine monomer in a liquid mixed by an organic solvent and deionized water according to a set molar ratio of 1-2: 0.1-1, sequentially adding an oxidant, a reducing agent and a ligand, and stirring at room temperature for reaction for 3-5 hours; then dialyzing in deionized water to remove residual monomers and other impurities, and regulating the solid content of the product to be 40% by a solution concentration mode to obtain the slump-retaining clay inhibitor; wherein the organic solvent is N, N-Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO).
The star initiator comprises a monomer, an oxidant, a reducing agent and a ligand, the molar ratio of the monomer to the reducing agent to the ligand is 1 (10-200): (0.01-0.1): 0.5-5): 0.01-0.5), wherein the monomer is a mixture of a cationic monomer and an amphoteric betaine monomer, and the molar ratio of the cationic monomer to the amphoteric betaine monomer is (30-95%): 5-70%. The most preferred embodiments are: the star initiator comprises a monomer, an oxidant, a reducing agent and a ligand, the molar ratio of the monomer to the reducing agent to the ligand is 1 (50-100) to (0.01-0.1) to (0.5-3) to (0.05-0.5), wherein the monomer is a mixture of a cationic monomer and an amphoteric betaine monomer, and the molar ratio of the cationic monomer to the amphoteric betaine monomer is 1: 1.
The invention takes cyclodextrin esterification products as an initiator, utilizes an active polymerization technology to prepare the slump-retaining clay inhibitor with a controllable molecular structure, and provides a new method for preparing the anti-mud agent. The slump-retaining clay inhibitor is compounded with the industrial polycarboxylic acid water reducing agent, so that the adaptability of the polycarboxylic acid water reducing agent to soil can be effectively improved, higher construction requirements can be met, and the slump-retaining clay inhibitor has a good application prospect.
The invention has the beneficial effects that:
1. ARGET ATRP adopted by the invention is an active polymerization technology, and the obtained clay inhibitor has the advantages of regular structure, controllable molecular weight, narrow molecular weight distribution and the like;
2. the invention adopts ARGET-ATRP technology, takes bivalent copper/ligand as catalyst, reduces part of bivalent copper into monovalent copper by reducing agent, thereby generating active species, but keeps the ratio of the monovalent copper to the bivalent copper higher, and still can keep acceptable polymerization rate. The advantages are that the dosage of catalyst and ligand is reduced, and the sensitivity of polymerization to oxygen is reduced.
3. The clay inhibitor prepared by the invention has a star topology structure, and can improve the self-dispersibility and the adsorption capacity to soil.
4. The clay inhibitor is formed by copolymerizing a cationic monomer and a zwitterionic monomer, wherein the coating effect of quaternary ammonium salt cations on clay particles forms a protective layer, so that the adsorption of the clay on the polycarboxylic acid water reducing agent can be effectively inhibited, and the dispersibility of concrete is improved; the molecular structure of the zwitterionic compound not only contains quaternary ammonium salt cations which are adsorbed with clay, but also has carboxyl, sulfonic group or phosphate group, and the anionic group can be adsorbed on the surface of cement particles to provide certain electrostatic repulsion and show certain water reducing and dispersing capacity.
5. Compared with micromolecules, β -cyclodextrin has larger steric hindrance, so that the mud-resisting agent taking β -cyclodextrin as a core is difficult to enter soil layers through the blocking effect, and meanwhile, the blocking effect is formed between the soil layers, the adsorption of the soil to the polycarboxylic acid water reducing agent is effectively inhibited, the adaptability of the water reducing agent to the soil is further improved, and the hydroxyl groups contained in β -cyclodextrin can enhance the slump retaining capability of the polycarboxylic acid water reducing agent and improve the water retention property and the cohesiveness of concrete.
Detailed Description
The present invention will be further understood from the following specific examples, which should not be construed as limiting the scope of the invention.
Example 1:
(1) preparation of Star initiators
β -cyclodextrin (11.35g, 0.01mol) is dissolved in 60mL of anhydrous N, N-Dimethylformamide (DMF), the obtained solution is added into a 100mL three-necked bottle, triethylamine (7.07g, 0.07mol) is added to serve as a proton absorbent, the obtained solution is stirred in an ice-water bath for 0.5h under a nitrogen atmosphere, 2-bromine isobutyryl bromide (16.1g, 0.07mol) is dissolved in 10mL of anhydrous DMF, then the obtained solution is added into a constant pressure dropping funnel, dropwise added into the three-necked bottle, after the dropwise addition is finished, the obtained solution reacts at room temperature for 24h under the nitrogen atmosphere, after the reaction is finished, the reaction solution is filtered to remove salt, and the filtrate is precipitated in anhydrous ethanol, filtered, washed with the anhydrous ethanol, and dried in vacuum at 50 ℃ overnight, so that the star initiator containing the terminal group bromine is obtained.
(2) Preparation of clay inhibitors
Dissolving the star initiator (0.01mol), methacryloxyethyl trimethyl ammonium chloride (0.5mol) and methacryloxyethyl sulfobetaine (0.5mol) obtained in the step (1) into a mixed solution of dimethyl sulfoxide and deionized water in a volume ratio of 2:1, and uniformly mixing and stirring. 0.0001mol of copper bromide, 0.005mol of Vc0.0005 mol and 0.0005mol of bipyridine are added in sequence, and the reaction is carried out for 3h at room temperature under mild stirring. The reaction product was placed in a dialysis bag and dialyzed against deionized water for 36 hours (water change every 12 hours). The remaining solution in the dialysis bag was concentrated to give a clay inhibitor with a solids content of 40%, named ACPM 1.
Example 2:
this example prepares an anti-sliming agent ACPM2 in the same manner as in example 1, except that the amount of methacryloyloxyethyltrimethyl ammonium chloride in step (2) was 1.0 mol.
Example 3:
this example prepares an anti-mud agent ACPM3 in the same manner as in example 1 except that the amount of methacryloyloxyethyl sulfobetaine in step (2) is 1 mol.
Example 4:
this example prepares an anti-mud agent ACPM4 in the same manner as in example 2, except that in step (2) the methacryloyloxyethyl carboxybetaine is replaced with an equimolar amount of methacryloyloxyethyl sulfobetaine.
Example 5:
this example prepares the anti-sliming agent ACPM5 in the same manner as in example 2, except that in step (2) the methacryloyloxyphosphoryl betaine is replaced with an equimolar amount of methacryloyloxyethyl sulfobetaine.
Example 6:
this example prepares an anti-mud agent ACPM6 in the same manner as in example 2 except that step (2) is reacted at room temperature for 4 hours with gentle stirring.
Example 7:
this example prepares an anti-mud agent ACPM7 in the same manner as in example 2 except that step (2) is reacted at room temperature for 5 hours with gentle stirring.
Example 8:
this example prepares an anti-mud agent ACPM8 in the same manner as in example 2 except that 0.0005mol of copper bromide, Vc0.025mol and 0.0025mol of bipyridine were added in this order in step (2).
Example 9:
this example prepares an anti-mud agent ACPM9 in the same manner as in example 2 except that in step (2) the catalyst was copper bromide 0.001mol, Vc0.05mol and bipyridine 0.005mol added in this order.
Comparative example 1
This comparative example manufactured anti-sliming ACP1 in the same manner as in example 1, except that the amount of methacryloyloxyethyl sulfobetaine added in step (2) was 0.
Comparative example 2
This comparative example manufactured anti-sliming ACP2 in the same manner as in example 2, except that the amount of methacryloyloxyethyl sulfobetaine added in step (2) was 0.
Testing the fluidity of the cement paste:
referring to GB8077-2000 'test method for homogeneity of concrete admixture', when the solid mixing amount of a commercial polycarboxylate superplasticizer is 0.13% of the mass of cement and the water-cement ratio is 0.29, the initial net slurry fluidity and the 60min net slurry fluidity are respectively 290mm and 295mm in a test.
When the solid content of a commercial polycarboxylic acid water reducer is 0.13 percent of the mass of the cement, the content of montmorillonite is 1 percent of the mass of the cement and the water-cement ratio is 0.29, the initial net slurry fluidity and the 60min net slurry fluidity are respectively tested to be 225mm and 150 mm.
When the solid content of a commercial polycarboxylate superplasticizer is 0.13 percent of the mass of cement, the dosage of an anti-mud agent accounts for 7 percent of the solid content of the polycarboxylate superplasticizer, the content of montmorillonite accounts for 1 percent of the mass of the cement, and the water-cement ratio is 0.29, the initial net slurry fluidity and the 60min fluidity are tested (table 1).
TABLE 1 test results of fluidity of cement paste in various conditions of examples
From the cement paste fluidity test results, it can be seen that: the existence of montmorillonite has great influence on the fluidity of cement paste: the fluidity of the ordinary cement paste mixed with the commercial polycarboxylic acid water reducing agent is initially 290mm and reaches 295mm after 60 min; the fluidity of the cement paste mixed with the commercial polycarboxylic acid water reducing agent and 1 percent of montmorillonite is only 225mm initially, and is reduced to 150mm after 60 min. The mud-resistant agent and the polycarboxylic acid water reducing agent are compounded, so that the initial fluidity is basically unchanged under the condition of containing 1% of montmorillonite, but the net slurry fluidity is improved after 60min, which shows that the mud-resistant agent and the commercially available polycarboxylic acid water reducing agent are compounded, the initial dispersing performance of the polycarboxylic acid water reducing agent is not adversely affected, and the dispersing performance is improved along with the time. The clay inhibitor is a polymer of a cationic monomer, the ammonium group with positive charges can be preferentially adsorbed on the surface of clay, a layer of coating layer is formed on the surface of the clay, the cyclodextrin macromolecular structure positioned on the outer side can play a role in steric hindrance, the polycarboxylate superplasticizer molecules are prevented from being close to clay particles, and then the polycarboxylate superplasticizer molecules are prevented from entering the interlayer of montmorillonite, so that the mud resistance effect is achieved.
The fluidity change of the cement paste containing montmorillonite when the anti-mud agent prepared by the comparative example and the comparative example is added into the cement paste is shown as follows: the inhibitory effect of the examples on clay is superior to the comparative examples, probably due to the synergistic effect of the cationic monomer with the different functional monomers in the zwitterionic monomer copolymer. The mud-resistant agent prepared by the invention is beneficial to improving the dispersibility and the retention performance of the cement paste, has good mud resistance and slump retaining effect, and can effectively inhibit the side effect of clay in cement concrete.
Claims (2)
1. A slump-retaining clay inhibitor is a product with 40% solid content obtained by reacting a star initiator, a monomer, an oxidant, a reducing agent and a ligand through atom transfer radical polymerization (ARGET ATRP) with an electron transfer catalyst regeneration function, wherein the star initiator is prepared by dissolving 11.35g, namely 0.01mol of β -cyclodextrin in 60mL of anhydrous N, N-Dimethylformamide (DMF) according to the following proportion, adding the mixture into a 100mL three-necked flask, then adding 7.07g, namely 0.07mol of triethylamine as a proton absorbent, stirring for 0.5h in an ice-water bath under nitrogen atmosphere, dissolving 16.1g, namely 0.07mol of 2-bromoisobutyryl bromide in 10mL of anhydrous DMF, then adding the obtained solution into a constant-pressure dropping funnel, dropwise adding the obtained solution into the three-necked flask, reacting for 24h under nitrogen atmosphere after dropwise adding, filtering and desalting a reaction solution after the reaction is finished, precipitating a filtrate in anhydrous ethanol, star-shaped washing with the anhydrous ethanol, washing under vacuum, drying at 50 ℃, and obtaining a Br-containing oxidant under vacuum and drying at 50 ℃ overnight2(cupric bromide) or CuCl2(copper chloride); the reducing agent is Vc (vitamin C); the ligand is PMDETA (pentamethyldiethylenetriamine) and Me6TREN (tris [2-(dimethylamino) ethyl group]Amine) or bpy (bipyridine);
the method is characterized in that:
the star initiator comprises a monomer, an oxidant, a reducing agent and a ligand, and the molar ratio of the monomer to the reducing agent to the ligand is 1 (50-100) to (0.01-0.1) to (0.5-3) to (0.05-0.5), wherein the monomer is a mixture of a cationic monomer and an amphoteric betaine monomer, and the molar ratio of the cationic monomer to the amphoteric betaine monomer is 1: 1; the cationic monomer is methacryloyloxyethyl trimethyl ammonium chloride; the amphoteric betaine monomer is carboxyl betaine, sulfobetaine or phosphate betaine.
2. The preparation method of the slump-retaining clay inhibitor as claimed in claim 1, wherein the cyclodextrin is halogenated to obtain a star-shaped initiator, the cationic monomer and the amphoteric betaine monomer are initiated to copolymerize by an atom transfer radical polymerization (ARGET ATRP) method with an electron transfer catalyst regeneration function at room temperature, and the product with the solid content of 40% is prepared after the product is further processed, namely the slump-retaining clay inhibitor; wherein the cationic monomer is methacryloyloxyethyl trimethyl ammonium chloride; the amphoteric betaine monomer is carboxyl betaine, sulfobetaine or phosphate betaine;
the method is characterized in that:
dissolving a star initiator, a cationic monomer and an amphoteric betaine monomer into a mixed liquid of dimethyl sulfoxide (DMSO) and deionized water according to a volume ratio of 1-2: 0.1-1 according to the molar ratio of the star initiator to the monomer to the oxidant to the reducing agent to the ligand of 1 (50-100) to (0.01-0.1) to (0.5-3) to (0.05-0.5), sequentially adding the oxidant, the reducing agent and the ligand, and stirring and reacting for 3-5 hours at room temperature; and dialyzing in deionized water to remove residual monomers and other impurities, and regulating the solid content of the product to be 40% by a solution concentration mode to obtain the slump-retaining clay inhibitor.
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| CN106046274A (en) * | 2016-08-17 | 2016-10-26 | 广州市建筑科学研究院有限公司 | Network-like polycarboxylate water reducer and preparation method thereof |
| CN106519121A (en) * | 2016-11-21 | 2017-03-22 | 山东交通学院 | Enhanced anti-mud agent and preparing method thereof |
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| CN106046274A (en) * | 2016-08-17 | 2016-10-26 | 广州市建筑科学研究院有限公司 | Network-like polycarboxylate water reducer and preparation method thereof |
| CN106519121A (en) * | 2016-11-21 | 2017-03-22 | 山东交通学院 | Enhanced anti-mud agent and preparing method thereof |
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