CN115572095A - Rheological agent and preparation method and application thereof - Google Patents
Rheological agent and preparation method and application thereof Download PDFInfo
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- CN115572095A CN115572095A CN202211062151.0A CN202211062151A CN115572095A CN 115572095 A CN115572095 A CN 115572095A CN 202211062151 A CN202211062151 A CN 202211062151A CN 115572095 A CN115572095 A CN 115572095A
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
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Abstract
The invention belongs to the technical field of functional polymer materials, and particularly relates to a rheological agent, and a preparation method and application thereof. The preparation method of the rheological agent provided by the invention takes unsaturated polyether phosphate monomers as raw materials, the unsaturated polyether phosphate monomers are modified to form a similar basic phosphate end sealing structure, and then the rheological agent is synthesized by the modified monomers, amide compounds, acrylic acid and polyester monomers. The rheological agent prepared by the method can be preferentially adsorbed on the surface of cement particles, simultaneously effectively reduces the Zeta potential of the cement particles, and hinders the further adsorption of the rheological agent on the cement particles, so that the clay tolerance of the rheological agent is improved, and meanwhile, the alkali-like phosphate structure enables the rheological agent to have the antibacterial and mildewproof effects. Finally, when the rheological agent is synthesized, the amide compound is used for replacing a small acrylic acid monomer commonly used in a synthesis process in the industry in a certain proportion, so that the early hydration reaction speed in a concrete system can be accelerated when the rheological agent is applied, and the early strength performance of the rheological agent is further endowed.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a rheological agent, and a preparation method and application thereof.
Background
The polycarboxylic acid rheological agent has the characteristics of low doping amount, high water reducing rate, good adaptability, green and environment-friendly production process and the like when in use, becomes one of indispensable chemical admixtures for concrete materials, and meanwhile, has stronger designability of molecular structure, and also gets wide attention of high-performance concrete material research workers.
In recent years, with the adjustment of relevant policies of national housing industrialization, green development concepts are gradually proposed, sustainable development strategies are deepened day by day, and the application of the concrete industry is gradually shifted from premixed concrete to the building industrialization represented by concrete prefabricated parts. Compared with ready-mixed concrete, the concrete prefabricated part requires good workability of the concrete and also needs to have better early strength performance. The conventional methods for improving the early strength performance of the prefabricated part comprise methods of increasing the cement mixing amount, using higher-grade cement, reducing the water-cement ratio in a proper amount and the like, but the practical application effects of the methods are not ideal, the medium-later volume stability and the durability of the concrete are more or less affected, and the economic applicability is poor.
Meanwhile, in both research and development tests and production applications, it is found that the polycarboxylic acid rheological agent is influenced by clay introduced by aggregate in a concrete prefabricated part system to different degrees (including the aspects of system viscosity, fluidity, strength and the like) when used, and further reduces the overall working performance. In addition, in order to meet different working condition requirements, functional components are added in a certain proportion in the production process of the concrete prefabricated part, wherein organic matters are not lacked, the organic matters provide necessary nutrient substrates for the propagation of microorganisms such as mold and the like, and particularly, the microorganisms on the part are rapidly propagated when the concrete prefabricated part is produced, transported and used in a high-temperature and humid environment in summer, so that the part is smelly, flatulence and even cracked, the material use performance is reduced, and potential safety hazards are brought to product use.
In conclusion, the development of the rheological agent with early strength, anti-adhesion, antibacterial and anti-mildew properties can better meet the development needs of the concrete prefabricated part material related industries.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the rheological agent in the prior art has no antibacterial and mildewproof performance, and has early strength, adhesion resistance to be further improved and the like, and provides the rheological agent, and the preparation method and the application thereof.
Therefore, the invention provides the following technical scheme:
the invention provides a preparation method of a rheological agent, which comprises the following steps:
s1, mixing an unsaturated polyether phosphate monomer, a supersaturation regulator and ammonia water, adding an acidic calcium salt solution containing a calcium ion slow release agent under a protective atmosphere, carrying out hydrothermal reaction, and dehydrating to obtain a modified monomer;
s2, mixing the obtained modified monomer, the amide compound and the acrylic acid compound with water to obtain a material A;
s3, dissolving sodium formaldehyde sulfoxylate and mercaptopropionic acid in water to obtain a material B;
and S4, mixing the polyester monomer with water, adding a catalyst, dropwise adding the material A and the material B, reacting, and adjusting the pH value to obtain the rheological agent.
Optionally, the unsaturated polyether type phosphate monomer is obtained by end capping unsaturated polyether with phosphoric acid;
and/or, the preparation of the unsaturated polyether phosphate comprises the following steps: mixing unsaturated polyether and phosphoric acid, reacting at 60-70 deg.C for 3-5h, and adding phosphorus pentoxide in several times during the reaction;
and/or the unsaturated polyether is one or more of (methyl) allyl polyglycol ether, isobutylene polyglycol ether, isopentenyl polyglycol ether, hydroxyethyl vinyl polyglycol ether and 4-hydroxybutyl vinyl polyglycol ether;
and/or the catalyst is ammonium persulfate or hydrogen peroxide;
and/or the unsaturated polyether has a number average molecular weight of 400-600;
and/or the amount of the phosphoric acid accounts for 8-12% of the mass of the unsaturated polyether;
and/or the mass concentration of the phosphoric acid is more than 85 percent;
and/or the dosage of the phosphorus pentoxide accounts for 10-15% of the mass of the unsaturated polyether;
and/or adding the phosphorus pentoxide in 3-6 times during the reaction.
Optionally, the hydrothermal reaction temperature in the step S1 is 160-180 ℃, and the reaction time is 20-24h;
and/or unsaturated polyether phosphate monomer, wherein the molar ratio of ammonia water to calcium salt is 3: 3.5-4.5: 5 to 7;
wherein, the mole number of the unsaturated polyether phosphate ester monomer is calculated by the average molecular weight.
And/or the amount of the supersaturation degree regulator accounts for 2-6 per mill of the mass of the unsaturated polyether phosphate monomer;
and/or the dosage of the calcium ion slow release agent accounts for 4-10 per mill of the mass of the unsaturated polyether phosphate monomer;
and/or the supersaturation degree regulator is one or more of formamide, acetamide, propionamide and butyramide;
and/or the calcium ion slow release agent is one or more of sodium citrate, potassium citrate, sodium carbonate and potassium carbonate;
and/or, the acrylic monomer is acrylic acid or methacrylic acid.
Alternatively, the amide-based compound: modifying monomers: polyester monomers: the molar ratio of acrylic monomers is 1.9-2.1; preferably 2;
and/or the using amount of the sodium formaldehyde sulfoxylate is 0.1 to 0.2 percent of the mass of the polyester monomers;
and/or the using amount of the mercaptopropionic acid is 0.25 to 0.5 percent of the mass of the polyester monomer;
and/or the using amount of the ammonium persulfate is 1.5 to 3.0 percent of the mass of the polyester monomer.
Optionally, the time for dripping the material A and the material B in the step S4 is 2-4h;
and/or the reaction temperature in the step S4 is 40-60 ℃, and the total time of dripping the material A and the material B and reacting is 3-6h;
and controlling the material A to be dripped before the material B.
And/or, in step S4, adjusting the pH to 6.5-7.
Optionally, the amide compound is one or more of hydroxyethyl acrylamide, hydroxymethyl acrylamide, acrylamide and crotonamide;
and/or the polyester monomer is one or more of methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol isopropenyl acid ester and methoxy polyethylene glycol acrylate;
and/or the number average molecular weight of the polyester monomer is 3500-5000.
Optionally, in the step S1, the dehydration temperature is 80-100 ℃, and the dehydration time is 30-60min;
the acidic calcium salt solution containing the calcium ion slow release agent is obtained by dissolving the calcium ion slow release agent and calcium salt in nitric acid.
Optionally, the steps S2 to S4 have no special requirement for the amount of water, and the water mainly acts to dissolve or disperse the raw materials, so that the solid content of the product finally meets the requirement.
The invention also provides the rheological agent prepared by the preparation method.
Optionally, the solids content of the rheological agent is 45-55%.
The invention also provides an application of the rheological agent in concrete or concrete prefabricated parts. .
Typically, and without limitation, the rheology agent provided by the present invention may comprise the steps of:
(1) preparing unsaturated polyether phosphate ester monomers: weighing a proper amount of unsaturated polyether, adding the unsaturated polyether into a four-neck round-bottom flask, heating the unsaturated polyether in a water bath at 60 ℃, and connecting a temperature monitoring device, a mechanical stirring device and a nitrogen protection device. Weighing appropriate amount of H 3 PO 4 Adding into a four-mouth bottle, stirring, and weighing appropriate amount of P 2 O 5 Adding the mixture into a reaction bottle for multiple times, controlling the reaction temperature to be 60-70 ℃, reacting for 3-5h, and dehydrating to obtain a yellow-brown unsaturated polyether phosphate intermediate.
According to the invention, the unsaturated polyether is blocked by phosphoric acid innovatively, the anti-adhesion performance of the unsaturated polyether is improved, and the adaptability of the polycarboxylic acid superplasticizer is increased laterally.
(2) Preparation of modified monomer: adding the intermediate obtained in the step (1) into a pressure reaction kettle, and sealingThe kettle is replaced for 3 to 4 times under nitrogen atmosphere, and then a proper amount of supersaturation degree regulator and NH are added 3 ·H 2 And (O). Then Ca (NO) 3 ) 2 Dissolving 4H2O and calcium ion sustained release agent in 2mol/L HNO 3 Preparing a calcium salt mixed solution from the solution, slowly dropwise adding the calcium salt mixed solution into a reaction kettle, starting stirring to perform hydrothermal reaction, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30min, and then dehydrating and filtering to obtain a modified monomer.
According to the invention, the supersaturation regulator and the calcium ion slow-release agent are added in the synthesis of the modified monomer, so that the reaction unicity is improved to a greater extent, the generation of byproducts is reduced, and meanwhile, by introducing the basic phosphate-like structure, the new antibacterial and mildew-proof effects of the rheological agent are given after the further synthesis at the later stage.
(3) Synthesis of rheological agent: deionized water and polyester monomers are added into a four-neck round-bottom flask one by one and stirred to be dissolved. Preparation of material A: a certain amount of modified monomer, amide compound and acrylic acid are dissolved in deionized water. Preparation of material B: a certain amount of formaldehyde sodium sulfoxylate and mercaptopropionic acid are put into deionized water and stirred for dissolution. Adding a certain amount of ammonium persulfate into a round-bottom flask, stirring for 3-7 min, and then slowly dropwise adding a A, B material. A. The dripping time of the material B is 2-4h, and the reaction temperature is maintained for 1-2 h after the dripping is finished; after the reaction is completed, naturally cooling, and then dripping sodium hydroxide solution (30%) into the flask to adjust the pH value to 6.5-7, so as to obtain the rheological agent.
The rheological agent is synthesized by adopting the monomer after mildew-proof modification, the amide compound, the acrylic acid and the polyester monomer, and on the premise of ensuring the basic performance of the common rheological agent, the early hydration reaction speed in a concrete system can be accelerated by introducing the amide compound (hydroxyethyl acrylamide and the like) during application.
The above step (1)H) 3 PO 4 The amount of the P is 8 to 12 percent, preferably 8 to 10 percent of the mass of the unsaturated polyether monomer 2 O 5 The amount of (B) is 10 to 15%, preferably 10 to 12% by mass of the unsaturated polyether.
The dehydration time in the step (1) is 30-40 min, and the dehydration temperature is 95-105 ℃.
The addition amount of the supersaturation degree regulator in the step (2) is 2-6 per mill of the mass of the intermediate, preferably 2-4 per mill.
The addition amount of the calcium ion sustained release agent in the step (2) is 4-10 per mill, preferably 6-9 per mill of the mass of the intermediate.
The intermediate and NH in the step (2) 3 ·H 2 O、Ca(NO 3 ) 2 ·4H 2 The molar ratio of O is 3: 3.5-4.5: 5 to 7 of HNO 3 Solution with Ca (NO) 3 ) 2 ·4H 2 The mass ratio of O is 1:1.
the temperature of the hydrothermal reaction in the step (2) is 160-180 ℃, the reaction time is 22-24 h, preferably 170-180 ℃, and the reaction time is 22-24 h.
In the step (2), the dehydration temperature is 80-100 ℃, the dehydration time is 30-60min, preferably the dehydration temperature is 80-90 ℃, and the dehydration time is 30-45 min.
The molecular weight of the polyester-based monomer in the step (3) is 3500 to 5000, preferably 3600 to 4200.
The technical scheme of the invention has the following advantages:
the preparation method of the rheological agent provided by the invention takes unsaturated polyether phosphate monomers as raw materials, the unsaturated polyether phosphate monomers are modified to form an alkali-like phosphate end-sealing structure, and then the rheological agent is synthesized by the modified monomers, amide compounds, acrylic acid and polyester monomers. According to the invention, unsaturated polyether phosphate monomers are used as raw materials, and an alkali-like phosphate end-sealing structure is formed through modification, so that the rheological agent with the structure can be preferentially adsorbed on the surface of cement particles, the Zeta potential of the cement particles is effectively reduced, and the further adsorption of the rheological agent on the cement particles is hindered, thereby improving the clay tolerance of the rheological agent, reducing the apparent viscosity of a paste, improving the fluidity, and simultaneously, the alkali-like phosphate structure enables the alkali-like phosphate end-sealing structure to have antibacterial and mildewproof effects. Finally, when the rheological agent is synthesized, the amide compound is used for replacing a small acrylic acid monomer commonly used in a synthesis process in the industry in a certain proportion, so that the early hydration reaction speed in a concrete system can be accelerated when the rheological agent is applied, and the early strength performance of the rheological agent is further endowed.
The preparation method of the rheological agent provided by the invention has the advantages of simple and convenient operation, reasonable process, good reaction unicity, less reaction residue and strong product performance, and can play a great promoting role in the application of the rheological agent in concrete prefabricated parts.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
Example 1
The embodiment provides a rheological agent, and a specific preparation method thereof comprises the following steps:
(1) preparing unsaturated polyether type phosphate ester monomers: 600g of methallyl alcohol polyoxyethylene ether 500 is added into a four-neck flask, the flask is placed into a water bath kettle, a temperature monitoring device, a mechanical stirring device and a nitrogen protection device are installed, the temperature of the water bath kettle is set to be 60 ℃, and the methallyl alcohol polyoxyethylene ether 500 is melted. Weighing 60g H 3 PO 4 Adding into a four-neck flask, stirring, and weighing 64g P 2 O 5 Adding the mixture into a four-neck flask for three times, controlling the reaction temperature to be 65 ℃ for reaction for 3h, then heating to 100 ℃, vacuumizing and dehydrating for 30min, then cooling to 60 ℃, and discharging to obtain the yellowish-brown unsaturated polyether phosphate monomer with the average molecular weight of 580.
(2) Preparation of modified monomer: 600g of the monomer obtained in the step (1) is added into a reaction kettle, the kettle is sealed and replaced for 3 times under nitrogen atmosphere, and then 1.2g of acetamide and 48g of NH are added 3 ·H 2 And O. Then 488gCa (NO) 3 ) 2 ·4H 2 O and 3.6g of sodium carbonate are dissolved in 488g of 2mol/L HNO 3 Preparing a calcium salt mixed solution from the solution, adding the calcium salt mixed solution into a reaction kettle at a speed of 15g/min by using a constant flow pump, starting stirring, controlling the temperature to be 175 ℃ for reaction for 24 hours, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30 minutes, then controlling the temperature to be 90 ℃ for dehydration for 45 minutes, then cooling to 80 ℃, filtering and discharging to obtain the anti-adhesion mildew-proof modified monomer with the average molecular weight of 633.
(3) Synthesis of rheological agent: 200g of deionized water and 300g of methoxypolyethylene glycol methacrylate 3600 are added into a four-neck round-bottom flask and stirred to be dissolved. Preparation of material A: 39.6g of the anti-adhesion and anti-mildew modified monomer obtained in the step (2), 4.83g of hydroxyethyl acrylamide and 6g of acrylic acid are dissolved in 30g of deionized water. Preparation of material B: 0.3g of sodium formaldehyde sulfoxylate and 0.75g of mercaptopropionic acid were dissolved in 80g of deionized water with stirring. 4.5g of ammonium persulfate is added into a round-bottom flask, stirred for 5min, and then slowly added with A, B by a constant flow pump. The dripping time of the material A is controlled to be 2h30min, the dripping time of the material B is controlled to be 2h40min, the reaction temperature is maintained for curing for 60min after the dripping is finished (the temperature of the system is increased generally between 40 and 60 ℃ in the process of dripping the material A and the material B, if the temperature reduction amplitude of the system is large in the curing process, the system is heated and preserved, and if the temperature is maintained above 40 ℃ all the time, additional heating is not needed); after the reaction is completed, naturally cooling to below 40 ℃, and then dripping 12g of sodium hydroxide solution (30%) and 41g of deionized water into the flask to adjust the pH value to 6.5-7, so as to obtain the rheological agent with the theoretical solid content (the total dosage of the deionized water in the step is determined according to the theoretical solid content, and the same applies below) of 50%.
Example 2
The embodiment provides a rheological agent, and a specific preparation method thereof comprises the following steps:
(1) preparation of unsaturated polyether phosphate: adding 600g of allyl polyglycol ether 400 into a four-neck flask, placing the flask into a water bath, installing a temperature monitoring device, a mechanical stirring device and a nitrogen protection device, setting the temperature of the water bath to be 60 ℃, and melting the allyl polyglycol ether 400. Weighing 60gH 3 PO 4 Adding into a four-neck flask, and stirringAfter being uniform, 72g P is weighed 2 O 5 Adding the mixture into a four-neck flask for three times, controlling the reaction temperature to be 60 ℃ for reaction for 3h, then heating to 105 ℃, vacuumizing and dehydrating for 30min, then cooling to 60 ℃, and discharging to obtain the yellowish-brown unsaturated polyether phosphate monomer with the average molecular weight of 480.
(2) Preparation of anti-sticking and mildew-proof modified monomer: adding 500g of the monomer obtained in the step (1) into a reaction kettle, sealing the kettle, replacing for 3 times under nitrogen atmosphere, and then adding 1.5g of formamide and 45g of NH 3 ·H 2 And O. Then 492gCa (NO) 3 ) 2 ·4H 2 Dissolving O and 3.5g of sodium carbonate in 492g of 2mol/L HNO 3 Preparing a calcium salt mixed solution from the solution, adding the calcium salt mixed solution into a reaction kettle at a speed of 15g/min by using a constant flow pump, starting stirring, controlling the temperature to be 170 ℃ for reacting for 23 hours, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30 minutes, controlling the temperature to be 100 ℃ for dehydrating for 45 minutes, cooling to 80 ℃, filtering and discharging to obtain the anti-adhesion mildew-proof modified monomer with the average molecular weight of 533.
(3) Synthesis of rheological agent: 200g of deionized water and 300g of methoxy polyethylene glycol isopentene acid ester 4000 are added into a four-mouth round-bottom flask and stirred to be dissolved. Preparation of material A: 30g of the anti-adhesion and anti-mildew modified monomer obtained in the step (2), 3.8g of hydroxymethyl acrylamide and 5.4g of acrylic acid are dissolved in 30g of deionized water. Preparation of material B: 0.4g of sodium formaldehyde sulfoxylate and 0.9g of mercaptopropionic acid were dissolved in 80g of deionized water with stirring. 6g of ammonium persulfate is added into a round-bottom flask, stirred for 5min, and then slowly added with A, B by a constant flow pump. The dripping time of the material A is controlled to be 2h30min, the dripping time of the material B is controlled to be 2h40min, and the reaction temperature is maintained for curing for 60min after the dripping is finished; after the reaction is completed, the mixture is naturally cooled to below 40 ℃, and then 10.8g of sodium hydroxide solution (30%) and 35g of deionized water are dripped into the flask to adjust the pH value to 6.5-7, so that the rheological agent with the theoretical solid content of 50% is obtained.
Example 3
The embodiment provides a rheological agent, and a specific preparation method thereof comprises the following steps:
(1) preparing unsaturated polyether type phosphate ester monomers: 600g of isopentenyl polyglycol ether 500 is added into a four-neck flask and putAnd (3) putting the mixture into a water bath kettle, installing a temperature monitoring device, a mechanical stirring device and a nitrogen protection device, setting the temperature of the water bath kettle to be 60 ℃, and melting the isopentenyl polyglycol ether 500. Weigh 61.6gH 3 PO 4 Adding into a four-neck flask, stirring, and weighing 62gP 2 O 5 Adding the mixture into a four-neck flask for three times, controlling the reaction temperature to be 70 ℃ for reaction for 3h, then heating to 95 ℃, vacuumizing for dehydration for 35min, then cooling to 60 ℃, discharging, and obtaining the yellowish-brown unsaturated polyether phosphate monomer with the average molecular weight of 580 to.
(2) Preparation of anti-sticking and mildew-proof modified monomer: adding 600g of the monomer obtained in the step (1) into a reaction kettle, sealing the kettle for 3 times in nitrogen atmosphere, and then adding 1.8g of propionamide and 50g of NH 3 ·H 2 And O. Then 550gCa (NO) 3 ) 2 ·4H 2 O and 3.6g potassium carbonate are dissolved in 550g 2mol/L HNO 3 Preparing a calcium salt mixed solution from the solution, adding the calcium salt mixed solution into a reaction kettle at a speed of 15g/min by using a constant flow pump, starting stirring, controlling the temperature to be 170 ℃ for reaction for 22h, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30min, then controlling the temperature to be 80 ℃ for dehydration for 50min, then cooling to 80 ℃, filtering and discharging to obtain the anti-adhesion mildew-proof modified monomer with the average molecular weight of 633.
(3) Synthesis of rheological agent: 200g of deionized water and 300g of methoxypolyethylene glycol acrylate 3600 are added into a four-neck round-bottom flask and stirred to be dissolved. Preparation of material A: 39.6g of the anti-adhesion and anti-mildew modified monomer obtained in the step (2), 3g of acrylamide and 6g of acrylic acid are dissolved in 30g of deionized water. Preparation of material B: 0.3g of sodium formaldehyde sulfoxylate and 0.75g of mercaptopropionic acid were dissolved in 80g of deionized water with stirring. 4.5g of ammonium persulfate is added into a round-bottom flask, stirred for 5min, and then slowly added with A, B by a constant flow pump. The dripping time of the material A is controlled to be 2h30min, the dripping time of the material B is controlled to be 2h40min, and the reaction temperature is maintained for curing for 60min after the dripping is finished; after the reaction is completed, naturally cooling to below 40 ℃, and then dropping 12g of sodium hydroxide solution (30%) and 40g of deionized water into the flask to adjust the pH to 6.5-7, thereby obtaining the rheological agent with the theoretical solid content of 50%.
Example 4
The embodiment provides a rheological agent, and a specific preparation method thereof comprises the following steps:
(1) preparing unsaturated polyether type phosphate ester monomers: adding 600g of hydroxyethyl vinyl polyglycol ether 600 into a four-neck flask, putting the flask into a water bath kettle, installing a temperature monitoring device, a mechanical stirring device and a nitrogen protection device, setting the temperature of the water bath kettle to be 60 ℃, and melting the hydroxyethyl vinyl polyglycol ether 600. Weighing 48gH 3 PO 4 Adding into a four-neck flask, stirring, and weighing 60gP 2 O 5 Adding the mixture into a four-neck flask for three times, controlling the reaction temperature to be 68 ℃ for reaction for 3.5h, then heating to 98 ℃, vacuumizing and dehydrating for 40min, then cooling to 60 ℃, and discharging to obtain the yellowish-brown unsaturated polyether phosphate monomer with the average molecular weight of 680.
(2) Preparation of anti-sticking and anti-mildew modified monomer: adding 700g of the monomer obtained in the step (1) into a reaction kettle, sealing the kettle for 3 times in nitrogen atmosphere, and then adding 2.1g of butyramide and 46g of NH 3 ·H 2 And O. Then 486gCa (NO) 3 ) 2 ·4H 2 O and 5.6g sodium citrate are dissolved in 486g 2mol/L HNO 3 Preparing a calcium salt mixed solution from the solution, adding the calcium salt mixed solution into a reaction kettle at a speed of 15g/min by using a constant flow pump, starting stirring, controlling the temperature to 172 ℃ for reaction for 24 hours, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30 minutes, then controlling the temperature to 95 ℃ for dehydration for 45 minutes, then cooling to 80 ℃, filtering and discharging to obtain the anti-adhesion mildew-proof modified monomer with the average molecular weight of 733.
(3) Synthesis of rheological agent: into a four-necked round-bottomed flask were added 200g of deionized water and 300g of methoxypolyethylene glycol methacrylate 4000 and dissolved by stirring. Preparation of material A: 41.23g of the anti-adhesion and anti-mildew modified monomer obtained in the step (2), 3.2g of butenamide and 5.4g of acrylic acid were dissolved in 30g of deionized water. Preparation of material B: 0.6g of sodium formaldehyde sulfoxylate and 1.5g of mercaptopropionic acid were dissolved in 80g of deionized water with stirring. 9g of ammonium persulfate is added into a round-bottom flask, stirred for 5min, and then slowly added with A, B by a constant flow pump. The dripping time of the material A is controlled to be 2h30min, the dripping time of the material B is controlled to be 2h40min, and after the dripping is finished, the reaction temperature is maintained for curing for 60min; after the reaction is completed, the mixture is naturally cooled to below 40 ℃, and then 10.8g of sodium hydroxide solution (30%) and 46g of deionized water are dripped into the flask to adjust the pH value to 6.5-7, so that the rheological agent with the theoretical solid content of 50% is obtained.
Example 5
The embodiment provides a rheological agent, and a specific preparation method thereof comprises the following steps:
(1) preparing unsaturated polyether type phosphate ester monomers: adding 600g of 4-hydroxybutyl vinyl polyglycol ether 500 into a four-neck flask, placing the flask into a water bath, installing a temperature monitoring device, a mechanical stirring device and a nitrogen protection device, setting the temperature of the water bath to 60 ℃, and melting the 4-hydroxybutyl vinyl polyglycol ether 500. Weighing 60gH 3 PO 4 Adding into a four-neck flask, stirring, and weighing 64gP 2 O 5 Adding the mixture into a four-neck flask for three times, controlling the reaction temperature to be 68 ℃ for 5 hours, then heating to 102 ℃, vacuumizing and dehydrating for 40 minutes, then cooling to 60 ℃, and discharging to obtain the yellowish-brown unsaturated polyether phosphate monomer with the average molecular weight of 580.
(2) Preparation of anti-sticking and anti-mildew modified monomer: 600g of the monomer obtained in the step (1) is added into a reaction kettle, the kettle is sealed and replaced for 3 times under nitrogen atmosphere, and then 2.4g of butyramide and 48g of NH are added 3 ·H 2 And O. Then 480gCa (NO) 3 ) 2 ·4H 2 Dissolving O and 4.2g potassium citrate in 480g 2mol/L HNO 3 Preparing a calcium salt mixed solution from the solution, adding the calcium salt mixed solution into a reaction kettle at a speed of 15g/min by using a constant flow pump, starting stirring, controlling the temperature to 178 ℃ for reaction for 24 hours, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30 minutes, then controlling the temperature to 88 ℃ for dehydration for 45 minutes, then cooling to 80 ℃, filtering and discharging to obtain the anti-adhesion mildew-proof modified monomer with the average molecular weight of 633.
(3) Synthesis of rheological agent: 200g of deionized water and 300g of methoxypolyethylene glycol methacrylate 4000 were added to a four-necked round-bottomed flask and dissolved with stirring. Preparation of material A: 35.6g of the anti-adhesion and anti-mildew modified monomer obtained in the step (2), 4.3g of hydroxyethyl acrylamide and 5.4g of acrylic acid are dissolved in 30g of deionized water. Preparing a material B: 0.5g of sodium formaldehyde sulfoxylate and 1.5g of mercaptopropionic acid were dissolved in 80g of deionized water with stirring. 8g of ammonium persulfate is added into a round-bottom flask, stirred for 5min, and then slowly added with A, B by a constant flow pump. The dripping time of the material A is controlled to be 2h30min, the dripping time of the material B is controlled to be 2h40min, and the reaction temperature is maintained for curing for 60min after the dripping is finished; after the reaction is completed, the mixture is naturally cooled to below 40 ℃, and then 10.8g of sodium hydroxide solution (30%) and 41g of deionized water are dropped into the flask to adjust the pH value to 6.5-7, so as to obtain the rheological agent with the theoretical solid content of 50%.
Comparative example 1
A rheological agent mother liquor of PS-102 designation from advanced chemical (Fushun) materials, inc. was used.
Comparative example 2
The difference compared to example 1 is that step (1) is not included and the reaction of step (2) is carried out directly with the unsaturated polyether.
Comparative example 3
The difference compared with example 2 is that the same amount of water is used instead of NH in step (2) 3 ·H 2 O and Ca (NO) 3 ) 2 ·4H 2 O。
Comparative example 4
The difference compared to example 3 is that an equal mass of acrylic acid is used instead of acrylamide in step (3) in example 3.
Examples of the experiments
The rheological agents prepared in the above examples and comparative examples were tested for net slurry fluidity by referring to the GB 8077 "test method for homogeneity of concrete admixture", wherein the folded solid content of the rheological agent is 0.1%. Meanwhile, the strength of the examples and the comparative examples is tested by referring to GB/T50081 Standard test method for physical and mechanical properties of concrete.
The concrete formulation used in the experimental examples was: and (3) reference cement: 360kg, sand: 790kg; stone: 1060kg, water: 175kg, rheology agent: 2kg. The apparent viscosity of the neat paste was measured using a rotational viscometer.
The rheological agents prepared in the above examples and comparative examples are tested for antibacterial rate by referring to HG/T3950-2007 Standard "antibacterial paint". The specific test method comprises the following steps:
1. preparation of a sample: respectively adding 87g of water and 300g of reference cement into 1g of the samples in the embodiments and the comparative examples, uniformly stirring, and pouring into a mold to prepare a cylindrical cement block with the diameter of 10 cm and the thickness of 1 cm; placing the cement blocks into triangular flasks respectively, and then placing the triangular flasks into an autoclave for sterilization for 15 minutes. And a blank control was prepared.
2. Preparing test bacterial liquid: transferring fresh Escherichia coli slant thallus Porphyrae into a triangular flask containing nutrient broth culture medium (prepared by taking 18g of NB particles in Bobo biological nutrient broth in Qingdao, adding 1000ml of distilled water, heating, stirring, dissolving, and autoclaving at 121 deg.C for 15 min), culturing at 37 deg.C + -1 deg.C for 16 hr, and adjusting the concentration of the above bacteria solution to 1.0 × 10 by tenfold dilution method 5 -1.1*10 5 Test bacterial solution cfu/ml.
3. And (3) detection: adding 250ml of test bacterial liquid into a triangular flask for placing a sample and a blank sample bottle respectively to ensure that the cement block is fully contacted with the test bacterial liquid, and then placing the triangular flask into a constant-temperature incubator at 37 +/-1 ℃ for culturing for 24 hours; pouring the bacterial liquid in 1ml triangular flask into a sterile plate, adding 41.5g of 10VRBA (adopting crystal violet neutral red bile salt agar (VRBA)) granules, heating to dissolve and boiling in 1000ml distilled water for no more than 2 min, cooling to 45 +/-0.5 deg.C to obtain the final product, carefully rotating the plate to fully mix the sample liquid with VRBA, solidifying, adding 3ml VRBA to cover the surface layer of the plate, turning over the plate, culturing at 36 +/-1 deg.C for 24 hr, observing the number of bacterial colonies by naked eye or microscope, multiplying by dilution times to obtain the bacterial colony concentration,% antibacterial rate = (C) 0 -C 24 )/C 0 *100％，C 0 Colony concentration representing 0 contact time, C 24 The colony concentration after 24 hours of contact is indicated. The test results are shown in the following table:
TABLE 1
As can be seen from the test results in the table, the apparent viscosity of the neat paste of the comparative examples 1 and 2 is much higher than that of the examples, which shows that the introduction of the phosphoric acid group on the monomer can actually reduce the apparent viscosity of the neat paste and improve the fluidity and the antibacterial effect of the neat paste; the antibacterial rate of the comparative examples 1 and 3 is lower than that of the examples, which shows that the modification step can enable the rheological agent to have the antibacterial and mildewproof functions; the compressive strength of comparative examples 1 and 4 is lower than that of examples, which shows that the selection of amide compounds and the like can play a role in early strength.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of a rheological agent is characterized by comprising the following steps:
s1, mixing an unsaturated polyether phosphate monomer, a supersaturation regulator and ammonia water, adding an acidic calcium salt solution containing a calcium ion slow release agent under a protective atmosphere, carrying out hydrothermal reaction, and dehydrating to obtain a modified monomer;
s2, mixing the obtained modified monomer, the amide compound and the acrylic acid compound with water to obtain a material A;
s3, dissolving sodium formaldehyde sulfoxylate and mercaptopropionic acid in water to obtain a material B;
and S4, mixing the polyester monomer with water, adding a catalyst, dropwise adding the material A and the material B, reacting, and adjusting the pH value to obtain the rheological agent.
2. The preparation method of the rheological agent according to claim 1, wherein the unsaturated polyether phosphate ester monomer is obtained by end capping of unsaturated polyether through phosphoric acid;
optionally, the preparation of the unsaturated polyether phosphate comprises the following steps: mixing unsaturated polyether and phosphoric acid, reacting at 60-70 deg.C for 3-5h, and adding phosphorus pentoxide in several times during the reaction;
optionally, the unsaturated polyether is one or more of (methyl) allyl polyglycol ether, isobutylene polyglycol ether, isopentenyl polyglycol ether, hydroxyethyl vinyl polyglycol ether, 4-hydroxybutyl vinyl polyglycol ether;
optionally, the unsaturated polyether has a number average molecular weight of 400 to 600;
and/or the catalyst is ammonium persulfate or hydrogen peroxide;
and/or the amount of the phosphoric acid accounts for 8-12% of the mass of the unsaturated polyether;
and/or the mass concentration of the phosphoric acid is more than 85 percent;
and/or the dosage of the phosphorus pentoxide accounts for 10-15% of the mass of the unsaturated polyether;
and/or adding the phosphorus pentoxide in 3-6 times during the reaction.
3. The method for preparing the rheological agent according to claim 1, wherein the hydrothermal reaction temperature in step S1 is 160-180 ℃ and the reaction time is 20-24h;
and/or unsaturated polyether phosphate monomer, wherein the molar ratio of ammonia water to calcium salt is 3: 3.5-4.5: 5 to 7;
and/or the amount of the supersaturation degree regulator accounts for 2-6 per mill of the mass of the unsaturated polyether phosphate monomer;
and/or the dosage of the calcium ion slow release agent accounts for 4-10 per mill of the mass of the unsaturated polyether phosphate monomer;
and/or the supersaturation degree regulator is one or more of formamide, acetamide, propionamide and butyramide;
and/or the calcium ion slow release agent is one or more of sodium citrate, potassium citrate, sodium carbonate and potassium carbonate;
and/or the acidic calcium salt solution containing the calcium ion slow release agent is obtained by mixing the calcium ion slow release agent, acid liquor and calcium salt, wherein the mass ratio of the acid liquor to the calcium salt is 1: (0.9-1.1);
and/or the concentration of the acid liquor is 2.0-2.1mol/L;
and/or, the acrylic monomer is acrylic acid or methacrylic acid.
4. A process for the preparation of a rheological agent according to any one of claims 1 to 3, characterized in that the amide compound: modifying monomers: polyester monomers: the molar ratio of acrylic monomers is 1.9-2.1; preferably 2;
and/or the using amount of the sodium formaldehyde sulfoxylate is 0.1 to 0.2 percent of the mass of the polyester monomers;
and/or the using amount of the mercaptopropionic acid is 0.25 to 0.5 percent of the mass of the polyester monomer;
and/or the using amount of the ammonium persulfate is 1.5 to 3.0 percent of the mass of the polyester monomer.
5. The method for preparing the rheological agent according to claim 4, wherein the time for dripping the material A and the material B in the step S4 is 2-4h;
and/or the reaction temperature in the step S4 is 40-60 ℃, and the total time of dripping the material A and the material B and reacting is 3-6h;
and/or, in step S4, adjusting the pH to 6.5-7.
6. The preparation method of the rheological agent according to claim 4, wherein the amide compound is one or more of hydroxyethyl acrylamide, hydroxymethyl acrylamide, acrylamide and crotonamide;
and/or the polyester monomer is one or more of methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol isopropenyl acid ester and methoxy polyethylene glycol acrylate;
and/or the number average molecular weight of the polyester monomer is 3500-5000.
7. The method for preparing a rheological agent according to any one of claims 1 to 6, wherein the dehydration temperature in step S1 is 80 to 100 ℃ and the dehydration time is 30 to 60min;
the acidic calcium salt solution containing the calcium ion slow release agent is obtained by dissolving the calcium ion slow release agent and calcium salt in nitric acid.
8. A rheological agent prepared by the preparation method of any one of claims 1 to 7.
9. The rheology agent according to claim 8, characterized in that the solids content of the rheology agent is 45-55wt%.
10. Use of a rheology agent according to claim 8 or 9 in concrete or precast concrete components.
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| CN111234201A (en) * | 2020-03-12 | 2020-06-05 | 厦门路桥翔通建材科技有限公司 | Slump-retaining water reducer containing polyether phosphate monomer and preparation method thereof |
| CN111961147A (en) * | 2020-07-16 | 2020-11-20 | 佳化化学（茂名）有限公司 | Polycarboxylate superplasticizer powder containing phosphate ester and preparation method thereof |
| CN113248647A (en) * | 2020-12-30 | 2021-08-13 | 马永峰 | Preparation method of concrete rheological agent |
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| US6388023B1 (en) * | 1997-10-10 | 2002-05-14 | Cook Composites And Polymers Co. | End-capped unsaturated polyetherester, unsaturated polyester and vinyl monomer |
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