CN115572095B - Rheological agent and preparation method and application thereof - Google Patents
Rheological agent and preparation method and application thereof Download PDFInfo
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- CN115572095B CN115572095B CN202211062151.0A CN202211062151A CN115572095B CN 115572095 B CN115572095 B CN 115572095B CN 202211062151 A CN202211062151 A CN 202211062151A CN 115572095 B CN115572095 B CN 115572095B
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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, 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, forms a similar basic phosphate end-capped structure through modification, and synthesizes the rheological agent by adopting 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, meanwhile, the Zeta potential of the cement particles is effectively reduced, the further adsorption of the rheological agent on the cement particles is prevented, the clay tolerance of the rheological agent is improved, and meanwhile, the basic phosphate-like structure has the antibacterial and mildew-proof effects. Finally, when the rheological agent is synthesized, the amide compound is used for replacing the small acrylic acid monomer commonly used in the 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, a preparation method and application thereof.
Background
The polycarboxylic acid rheological agent is one of indispensable chemical additives for concrete materials due to the characteristics of low mixing amount, high water reducing rate, good adaptability, green and environment-friendly production process and the like when in use, and meanwhile, the polycarboxylic acid rheological agent is widely paid attention to high-performance concrete material researchers due to the strong designability of molecular structures.
In recent years, along with the adjustment of national residence industrialization related policies, the green development concept is gradually proposed, the sustainable development strategy is gradually in deep, and the application of the concrete industry is gradually changed from ready-mixed concrete to the building industrialization direction represented by concrete prefabricated parts. Compared with ready-mixed concrete, the concrete prefabricated part is required to have good workability and early strength. The conventional method for improving the early strength performance of the prefabricated part comprises the methods of improving the cement mixing amount, using higher-grade cement, properly reducing the water-cement ratio and the like, but the practical application effects of the methods are not ideal, the volume stability and the durability of the concrete in the middle and later stages are more or less adversely affected, and the economic applicability is poor.
Meanwhile, when the polycarboxylic acid rheological agent is used in research and development tests or production applications, people find that the polycarboxylic acid rheological agent is affected by clay introduced by aggregate in a concrete prefabricated part system (including aspects of system viscosity, fluidity, strength and the like) to different degrees, so that the overall working performance is reduced. In addition, in order to meet the demands of different working conditions, functional components with a certain proportion are added in the production process of the concrete prefabricated part, and organic matters are not lack, so that necessary nutrient matrixes are provided for the propagation of microorganisms such as mould, and particularly microorganisms on the part are rapidly propagated when the prefabricated part is produced, transported and used in a high-temperature and humid environment in summer, so that the part is smelly, swelled and even cracked, the material usability is reduced, and potential safety hazards are brought to the use of products.
In conclusion, the rheological agent with early strength, anti-adhesion, antibacterial and mildew-proof properties is developed, and the rheological agent can better meet the development needs of the related industries of concrete precast member materials.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the rheological agent in the prior art has no antibacterial and mildew-proof properties, and the early strength and the anti-sticking properties are required to be further improved, and the like, thereby providing 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 with a supersaturation degree 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, an amide compound and an acrylic compound with water to obtain a material A;
s3, dissolving sodium formaldehyde sulfoxylate and mercaptopropionic acid in water to obtain a material B;
s4, mixing polyester monomers with water, adding a catalyst, dropwise adding the material A and the material B, reacting, and adjusting pH to obtain the rheological agent.
Optionally, the unsaturated polyether phosphate monomer is obtained by capping unsaturated polyether with phosphoric acid;
and/or, the preparation of the unsaturated polyether phosphate comprises the following steps: mixing unsaturated polyether with phosphoric acid, reacting for 3-5h at 60-70 ℃, and adding phosphorus pentoxide in the reaction process;
and/or the unsaturated polyether is one or more of (methyl) allyl polyethylene glycol ether, isobutylene polyethylene glycol ether, isopentenyl polyethylene glycol ether, hydroxyethyl vinyl polyethylene glycol ether and 4-hydroxybutyl vinyl polyethylene glycol ether;
and/or the catalyst is ammonium persulfate or hydrogen peroxide;
and/or the unsaturated polyether has a number average molecular weight of 400 to 600;
and/or the phosphoric acid accounts for 8-12% of the mass of the unsaturated polyether;
and/or the mass concentration of phosphoric acid is above 85%;
and/or the dosage of phosphorus pentoxide accounts for 10-15% of the mass of the unsaturated polyether;
and/or phosphorus pentoxide is added for 3-6 times in the reaction process.
Optionally, the hydrothermal reaction temperature in the step S1 is 160-180 ℃ and the reaction time is 20-24 hours;
and/or, unsaturated polyether type phosphate monomer, the molar ratio of ammonia water to calcium salt is 3:3.5 to 4.5:5 to 7;
wherein the mole number of the unsaturated polyether phosphate monomer is calculated by the average molecular weight.
And/or the dosage of the supersaturation degree regulator accounts for 2 to 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.
Optionally, the amide compound: modifying monomer: polyester monomer: the molar ratio of the acrylic monomers is 1.9-2.1:2.9-3.1:3.9-4.1:3.9-4.1; preferably 2:3:4:4;
and/or the dosage of the sodium formaldehyde sulfoxylate is 0.1-0.2% of the mass of the polyester monomer;
and/or the dosage of the mercaptopropionic acid is 0.25-0.5% of the mass of the polyester monomer;
and/or the ammonium persulfate dosage is 1.5-3.0% of the mass of the polyester monomer.
Optionally, in the step S4, the time for dropwise adding the material A and the material B is 2-4 hours;
and/or the reaction temperature in the step S4 is 40-60 ℃, and the total reaction time of the dropwise adding material A and the material B is 3-6 hours;
and controlling the material A to be added before the material B.
And/or, in the step S4, the pH is adjusted to 6.5-7.
Optionally, the amide compound is one or more of hydroxyethyl acrylamide, hydroxymethyl acrylamide, acrylamide and butenamide;
and/or the polyester monomer is one or more of methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol isopentenyl 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 prepared by dissolving the calcium ion slow-release agent and calcium salt in nitric acid.
Optionally, the water consumption in the steps S2-S4 is not particularly required, and the water mainly dissolves or disperses the raw materials, so that the solid content of the product finally meets the requirement.
The invention also provides a rheological agent prepared by the preparation method.
Optionally, the rheology agent has a solids content of 45-55%.
The invention also provides application of the rheological agent in concrete or concrete prefabricated parts. .
Typically, but not by way of limitation, the rheology agent provided by the present invention may comprise the steps of:
(1) and (3) preparing an unsaturated polyether type phosphate monomer: weighing a proper amount of unsaturated polyether, adding into a four-necked round-bottomed flask, heating in a water bath at 60 ℃, and then connecting with a temperature monitoring device, a mechanical stirring device and a nitrogen protection device. Weighing a proper amount of H 3 PO 4 Adding into 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 ℃ for reaction for 3-5 hours, and obtaining the yellow-brown unsaturated polyether phosphate intermediate after dehydration.
The invention creatively adopts phosphoric acid to end-cap the unsaturated polyether, improves the anti-adhesive property of the unsaturated polyether, and increases the adaptability of the polycarboxylic acid superplasticizer on the side surface.
(2) Preparation of modified monomer: adding the intermediate obtained in the step (1) into a pressure reaction kettle, sealing the kettle, replacing for 3-4 times under nitrogen atmosphere, and then adding a proper amount of supersaturation regulator and NH 3 ·H 2 O. After that Ca (NO) 3 ) 2 4H2O and calcium ion sustained release agent are dissolved in HNO of 2mol/L 3 The solution is prepared into a calcium salt mixed solution, then the calcium salt mixed solution is slowly and dropwise added into a reaction kettle, stirring is started to carry out hydrothermal reaction, 100g of deionized water is added into the reaction kettle to be stirred for 30min after the reaction is finished, and then the modified monomer is obtained through dehydration and filtration.
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 singleness is improved to a greater extent, the generation of byproducts is reduced, and meanwhile, the novel antibacterial and mildew-proof effects of the rheological agent are provided after the later-stage further synthesis by introducing the basic phosphate-like structure.
(3) Synthesis of rheological agent: deionized water and polyester monomers are added into a four-neck round bottom flask one by one and stirred for dissolution. And (3) preparing a material A: and (3) dissolving a certain amount of modified monomers, amide compounds and acrylic acid in deionized water. And (3) preparing a material B: and (3) taking a certain amount of sodium formaldehyde sulfoxylate and mercaptopropionic acid, and placing the sodium formaldehyde sulfoxylate and mercaptopropionic acid into deionized water for stirring and dissolving. After a certain amount of ammonium persulfate is added into the round-bottom flask and stirred for 3-7 min, the dropwise addition of A, B material is started slowly. A. The dripping time of the material B is 2-4 hours, and the reaction temperature is maintained for 1-2 hours after the dripping is finished; after the reaction is completed, naturally cooling, then dripping sodium hydroxide solution (30%) into the flask, and regulating the pH value to 6.5-7 to obtain the rheological agent.
The invention synthesizes the rheological agent by adopting the mildew-proof modified monomer, the amide compound, the acrylic acid and the polyester monomer, and can accelerate the early hydration reaction speed in a concrete system when in application by introducing the amide compound (hydroxyethyl acrylamide and the like) under the premise of ensuring the basic performance of the common rheological agent.
Step (1)H) above 3 PO 4 The dosage is 8 to 12 percent, preferably 8 to 10 percent, of the mass of the unsaturated polyether monomer, and P 2 O 5 The amount of (C) is 10 to 15% by mass, preferably 10 to 12% by mass, based on 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 to 6 per mill, preferably 2 to 4 per mill of the mass of the intermediate.
The calcium ion slow release agent in the step (2) is added in an amount of 4-10 per mill, preferably 6-9 per mill of the mass of the intermediate.
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 to 4.5:5 to 7, HNO 3 Solution and 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 the reaction temperature is 170-180 ℃, and the reaction time is 22-24 h.
The dehydration temperature in the step (2) is 80-100 ℃, the dehydration time is 30-60min, preferably 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, forms a similar basic phosphate end-capped structure through modification, and synthesizes the rheological agent by adopting the modified monomers, amide compounds, acrylic acid and polyester monomers. According to the invention, the unsaturated polyether phosphate monomer is used as a raw material, and the modification is carried out to form the similar basic phosphate end-capped structure, so that the rheological agent with the structure can be preferentially adsorbed on the surface of cement particles, and meanwhile, the Zeta potential of the cement particles is effectively reduced, the further adsorption of the rheological agent on the cement particles is prevented, thereby improving the clay tolerance of the rheological agent, reducing the apparent viscosity of clear slurry, improving the fluidity, and simultaneously, the similar basic phosphate structure has the antibacterial and mildew-proof effects. Finally, when the rheological agent is synthesized, the amide compound is used for replacing the small acrylic acid monomer commonly used in the 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 operation, reasonable process, good reaction singleness, less reaction residue and strong product performance, and can play a great role in promoting the application of the rheological agent in the precast concrete components.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a rheological agent, which is prepared by the following steps:
(1) preparation of unsaturated polyether phosphate monomer: 600g of methallyl alcohol polyoxyethylene ether 500 is added into a four-neck flask, the flask is put into a water bath, a temperature monitoring device, a mechanical stirring device and a nitrogen protection device are arranged, the temperature of the water bath is set to be 60 ℃, and the methallyl alcohol polyoxyethylene ether 500 is melted. Weigh 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 65 ℃ for reaction for 3 hours, heating to 100 ℃, vacuumizing and dehydrating for 30 minutes, cooling to 60 ℃ and discharging to obtain the yellow-brown unsaturated polyether type 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 for replacement for 3 times under nitrogen atmosphere, and 1.2g of acetamide and 48gNH are added 3 ·H 2 O. Will later 488gCa (NO 3 ) 2 ·4H 2 O and 3.6g sodium carbonate dissolved in 488g 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 175 ℃ for reaction for 24 hours, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30 minutes, controlling the temperature to 90 ℃ for dehydration for 45 minutes, 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-necked round bottom flask and stirred for dissolution. And (3) preparing a material A: 39.6g of the anti-sticking and mildew-proof modified monomer obtained in the step (2), 4.83g of hydroxyethyl acrylamide and 6g of acrylic acid are taken and dissolved in 30g of deionized water. And (3) preparing a material B: 0.3g of sodium formaldehyde sulfoxylate and 0.75g of mercaptopropionic acid were placed in 80g of deionized water and dissolved with stirring. After adding 4.5g of ammonium persulfate to the round-bottom flask and stirring for 5min, A, B was slowly added dropwise with a constant flow pump. The material A is dripped for 2h30min, the material B is dripped for 2h40min, and the reaction temperature is maintained for curing for 60min after the dripping is finished (the temperature of the system is generally raised between 40 and 60 ℃ in the process of dripping the material A and the material B, if the temperature of the system is relatively large in the curing process, the system is heated and kept, and if the temperature is always maintained above 40 ℃, additional heating is not needed); after the reaction is completed, naturally cooling to below 40 ℃, then dropwise adding 12g of sodium hydroxide solution (30%) and 41g of deionized water into the flask, and adjusting the pH to 6.5-7 to obtain the rheological agent with the theoretical solid content (the total consumption of the deionized water in the steps is determined according to the theoretical solid content, and the same applies below) of 50%.
Example 2
The embodiment provides a rheological agent, which is prepared by the following steps:
(1) preparation of unsaturated polyether phosphate: 600g of allyl polyethylene glycol ether 400 is added into a four-neck flask, the flask is placed into a water bath, a temperature monitoring device, a mechanical stirring device and a nitrogen protection device are arranged, the temperature of the water bath is set to be 60 ℃, and the allyl polyethylene glycol ether 400 is melted. Weigh 60gH 3 PO 4 Adding into a four-neck flask, stirring, and weighing 72g P 2 O 5 Adding the mixture into a four-neck flask for three times, controlling the reaction temperature to be 60 ℃ for reaction for 3 hours, heating to 105 ℃, vacuumizing and dehydrating for 30 minutes, cooling to 60 ℃ and discharging to obtain the yellow-brown unsaturated polyether type phosphate monomer with the average molecular weight of 480.
(2) Preparation of anti-sticking and mildew-proof modified monomer: 500g of the monomer obtained in the step (1) is added into a reaction kettle, the kettle is sealed for replacement for 3 times under nitrogen atmosphere, and then 1.5g of formamide and 45gNH are added 3 ·H 2 O. Later 492gCa (NO) 3 ) 2 ·4H 2 O and 3.5g sodium carbonate dissolved 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 reaction for 23h, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30min, controlling the temperature to be 100 ℃ for dehydration for 45min, cooling to 80 ℃, and filteringAnd discharging to obtain the anti-sticking and mildew-proof modified monomer with the average molecular weight of 533.
(3) Synthesis of rheological agent: 200g of deionized water and 300g of methoxypolyethylene glycol isopentenyl acid ester 4000 are added into a four-necked round bottom flask and stirred for dissolution. And (3) preparing a material A: 30g of the anti-sticking and mildew-proof modified monomer obtained in the step (2), 3.8g of methylol acrylamide and 5.4g of acrylic acid are taken and dissolved in 30g of deionized water. And (3) preparing a material B: 0.4g of sodium formaldehyde sulfoxylate and 0.9g of mercaptopropionic acid are placed in 80g of deionized water and stirred for dissolution. 6g of ammonium persulfate was added to the round-bottom flask and stirred for 5min, and then A, B was slowly added dropwise with a constant flow pump. The material A is dripped for 2h30min, the material B is dripped for 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 ℃, then dropwise adding 10.8g of sodium hydroxide solution (30%) and 35g of deionized water into the flask, and adjusting the pH to 6.5-7 to obtain the rheological agent with the theoretical solid content of 50%.
Example 3
The embodiment provides a rheological agent, which is prepared by the following steps:
(1) preparation of unsaturated polyether phosphate monomer: 600g of isopentenyl polyethylene glycol ether 500 was added to a four-necked flask, placed in a water bath, and a temperature monitoring, mechanical stirring and nitrogen protection device was installed, and the temperature of the water bath was set to 60℃to melt the isopentenyl polyethylene glycol ether 500. Weigh 61.6gH 3 PO 4 Adding into a four-necked flask, uniformly 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 3 hours, heating to 95 ℃, vacuumizing and dehydrating for 35 minutes, cooling to 60 ℃ and discharging to obtain unsaturated polyether phosphate monomers with average molecular weights of 580 to yellow-brown.
(2) Preparation of anti-sticking and mildew-proof modified monomer: 600g of the monomer obtained in the step (1) is added into a reaction kettle, the kettle is sealed for replacement for 3 times under nitrogen atmosphere, and then 1.8g of propionamide and 50gNH g of propionamide are added 3 ·H 2 O. Will then 550gCa (NO) 3 ) 2 ·4H 2 O and 3.6g of potassium carbonate are dissolved in 550g of 2mol/L HNO 3 Preparing a calcium salt mixed solution from the solution, and then using constant current to the calcium salt mixed solutionAdding the mixture into a reaction kettle at a speed of 15g/min, starting stirring, controlling the temperature to 170 ℃ for reaction for 22h, adding 100g of deionized water into the reaction kettle after the reaction is finished, stirring for 30min, controlling the temperature to 80 ℃ for dehydration for 50min, cooling to 80 ℃, filtering and discharging to obtain the anti-sticking and 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-necked round bottom flask and stirred for dissolution. And (3) preparing a material A: 39.6g of the anti-sticking and mildew-proof modified monomer obtained in the step (2), 3g of acrylamide and 6g of acrylic acid are taken and dissolved in 30g of deionized water. And (3) preparing a material B: 0.3g of sodium formaldehyde sulfoxylate and 0.75g of mercaptopropionic acid were placed in 80g of deionized water and dissolved with stirring. After adding 4.5g of ammonium persulfate to the round-bottom flask and stirring for 5min, A, B was slowly added dropwise with a constant flow pump. The material A is dripped for 2h30min, the material B is dripped for 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 ℃, then dropwise adding 12g of sodium hydroxide solution (30%) and 40g of deionized water into a flask, and adjusting the pH to 6.5-7 to obtain the rheological agent with the theoretical solid content of 50%.
Example 4
The embodiment provides a rheological agent, which is prepared by the following steps:
(1) preparation of unsaturated polyether phosphate monomer: 600g of hydroxyethyl vinyl polyethylene glycol ether 600 is added into a four-necked flask, the flask is placed into a water bath, a temperature monitoring device, a mechanical stirring device and a nitrogen protection device are arranged, the temperature of the water bath is set to be 60 ℃, and the hydroxyethyl vinyl polyethylene glycol ether 600 is melted. Weigh 48gH 3 PO 4 Adding into a four-necked flask, uniformly stirring, and weighing 60gP 2 O 5 Adding the mixture into a four-neck flask for three times, controlling the reaction temperature to 68 ℃ for reaction for 3.5 hours, then heating to 98 ℃, vacuumizing and dehydrating for 40 minutes, then cooling to 60 ℃ and discharging to obtain the yellowish-brown unsaturated polyether type phosphate monomer with the average molecular weight of 680.
(2) Preparation of anti-sticking and mildew-proof modified monomer: 700g of the monomer obtained in the step (1) is added into a reaction kettle, the kettle is sealed, the replacement is carried out for 3 times under the nitrogen atmosphere, and then 2 is added.1g of butyramide and 46gNH 3 ·H 2 O. Will then 486gCa (NO) 3 ) 2 ·4H 2 O and 5.6g sodium citrate dissolved in 4810 g 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, controlling the temperature to 95 ℃ for dehydration for 45 minutes, 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: 200g of deionized water and 300g of methoxypolyethylene glycol methacrylate 4000 were added to a four-necked round bottom flask and dissolved with stirring. And (3) preparing a material A: 41.23g of the anti-sticking and mildew-proof modified monomer obtained in the step (2), 3.2g of butenamide and 5.4g of acrylic acid are taken and dissolved in 30g of deionized water. And (3) preparing a material B: 0.6g of sodium formaldehyde sulfoxylate and 1.5g of mercaptopropionic acid are placed in 80g of deionized water and stirred for dissolution. 9g of ammonium persulfate was added to the round-bottomed flask and stirred for 5 minutes, and then A, B was slowly added dropwise with a constant flow pump. The material A is dripped for 2h30min, the material B is dripped for 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 ℃, then dropwise adding 10.8g of sodium hydroxide solution (30%) and 46g of deionized water into the flask, and adjusting the pH to 6.5-7 to obtain the rheological agent with the theoretical solid content of 50%.
Example 5
The embodiment provides a rheological agent, which is prepared by the following steps:
(1) preparation of unsaturated polyether phosphate monomer: 600g of 4-hydroxybutyl vinyl polyethylene glycol ether 500 was added to a four-necked flask, placed in a water bath, equipped with temperature monitoring, mechanical stirring and nitrogen protection device, and the water bath temperature was set to 60℃to melt 4-hydroxybutyl vinyl polyethylene glycol ether 500. Weigh 60gH 3 PO 4 Adding into a four-necked flask, uniformly stirring, and weighing 64gP 2 O 5 Adding into a four-neck flask for three times, controlling the reaction temperature to 68 ℃ for reaction for 5 hours, then heating to 102 ℃, vacuumizing and dehydrating for 40 minutes, then cooling to 60 ℃ and discharging to obtain average scoreYellow brown unsaturated polyether phosphate monomer with molecular weight of 580.
(2) Preparation of anti-sticking and mildew-proof modified monomer: 600g of the monomer obtained in the step (1) is added into a reaction kettle, the kettle is sealed for replacement for 3 times under nitrogen atmosphere, and 2.4g of butyramide and 48gNH are added 3 ·H 2 O. Will later 480gCa (NO) 3 ) 2 ·4H 2 O and 4.2g of potassium citrate dissolved in 480g of HNO 2mol/L 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, controlling the temperature to 88 ℃ for dehydration for 45 minutes, 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 bottom flask and dissolved with stirring. And (3) preparing a material A: 35.6g of the anti-sticking and mildew-proof modified monomer obtained in the step (2), 4.3g of hydroxyethyl acrylamide and 5.4g of acrylic acid are taken and dissolved in 30g of deionized water. And (3) preparing a material B: 0.5g of sodium formaldehyde sulfoxylate and 1.5g of mercaptopropionic acid are placed in 80g of deionized water and stirred for dissolution. 8g of ammonium persulfate was added to the round-bottom flask and stirred for 5min, and then A, B was slowly added dropwise with a constant flow pump. The material A is dripped for 2h30min, the material B is dripped for 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 ℃, then dropwise adding 10.8g of sodium hydroxide solution (30%) and 41g of deionized water into the flask, and adjusting the pH to 6.5-7 to obtain the rheological agent with the theoretical solid content of 50%.
Comparative example 1
A rheology mother liquor with the brand PS-102 produced by the chemical (Fushun) new material Co., ltd was used.
Comparative example 2
In comparison with example 1, the reaction of step (2) was carried out directly with an unsaturated polyether, except that step (1) was not included.
Comparative example 3
In comparison with example 2, the difference is that an equal amount of water is usedReplacing 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 the acrylamide in step (3) in example 3 is replaced with an equal mass of acrylic acid.
Experimental example
The rheology agents prepared in the above examples and comparative examples were tested for net-slurry fluidity with reference to GB 8077 Standard for concrete admixture homogeneity test method, wherein the rheology agent fold-solid incorporation was 0.1%. The strength of the above examples and comparative examples was also tested with reference to GB/T50081 Standard for physical and mechanical Properties test method of concrete.
The concrete formula adopted in the experimental example is as follows: reference cement: 360kg of sand: 790kg; stone: 1060kg of water: 175kg, rheology agent: 2kg. The apparent viscosity of the neat paste was tested using a rotational viscometer.
The rheology agents prepared in the above examples and comparative examples were tested for antimicrobial efficacy with reference to HG/T3950-2007 "antimicrobial coatings" standard. The specific test method comprises the following steps:
1. preparation of the samples: taking 1g of the samples of the examples and the comparative examples, respectively adding 87g of water and 300g of reference cement, 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; the cement blocks are respectively put into triangular bottles, and then put into an autoclave for sterilization for 15 minutes. And a blank control was prepared.
2. Preparing a test bacterial liquid: transferring fresh coliform slant fungus to a triangular flask containing nutrient broth (prepared by taking 18g of Qingdao sea Bo biological nutrient broth NB particles, adding 1000ml of distilled water, heating, stirring for dissolving, and sterilizing at 121deg.C for 15 min), culturing at 37deg.C+ -1deg.C for 16 hr, and adjusting the concentration of the fungus solution to 1.0X10 by ten times dilution 5 -1.1*10 5 cfu/ml of test bacterial liquid.
3. And (3) detection: 250ml of test bacterial liquid is respectively added into a triangle bottle for placing a sample and a blank sample bottle, so that the cement blocks are fully contacted with the test bacterial liquidThen placing the triangular flask in a constant temperature incubator at 37+/-1 ℃ for culturing for 24 hours; pouring the bacterial liquid in a 1ml triangular flask into a sterile plate, adding 41.5g of 10VRBA (crystal violet red bile salt agar (VRBA) particles adopting Qingdao sea Bo) into the sterile plate, heating and dissolving the particles and 1000ml of distilled water, boiling the particles for no more than 2 minutes, cooling the particles to 45+/-0.5 ℃, carefully rotating the plate to fully mix the sample liquid with the VRBA, solidifying the sample liquid, adding 3ml of VRBA to cover the surface layer of the plate, turning the plate, placing the plate at 36+/-1 ℃ for culturing for 24 hours, observing the colony number by naked eyes or a microscope, multiplying the colony number by dilution factor, and obtaining the bacterial colony concentration and the antibacterial rate% = (C) 0 -C 24 )/C 0 *100％，C 0 Colony concentration indicating 0 contact time, C 24 The colony concentration after 24 hours of contact is shown. 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 clear pulp of the comparative examples 1 and 2 is far higher than that of the examples, which shows that the apparent viscosity of the clear pulp can be reduced and the fluidity and antibacterial effect of the clear pulp can be improved by introducing phosphate groups into the monomers; the antimicrobial ratio of comparative examples 1, 3 is lower than that of examples, indicating that the modification step can provide the rheology agent with antimicrobial and mildew-proof functions; the compressive strength of comparative examples 1 and 4 is lower than that of examples, which indicates that the selection of the amide compound and the like can play a role in early strength.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A method of preparing a rheological agent, comprising the steps of:
s1, mixing an unsaturated polyether phosphate monomer with a supersaturation degree 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, an amide compound and an acrylic compound with water to obtain a material A;
s3, dissolving sodium formaldehyde sulfoxylate and mercaptopropionic acid in water to obtain a material B;
s4, mixing polyester monomers with water, adding a catalyst, dropwise adding a material A and a material B, reacting, and adjusting pH to obtain the rheological agent;
wherein the supersaturation degree regulator is one or more of formamide, acetamide, propionamide and butyramide;
the calcium ion slow release agent is one or more of sodium citrate, potassium citrate, sodium carbonate and potassium carbonate;
the acidic calcium salt solution containing the calcium ion slow-release agent is obtained by mixing a calcium ion slow-release agent, an acid solution and a calcium salt, wherein the calcium salt is calcium nitrate, and the acid solution is nitric acid;
the catalyst is ammonium persulfate or hydrogen peroxide;
the amide compound: modifying monomer: polyester monomer: the molar ratio of the acrylic monomers is 1.9-2.1:2.9-3.1:3.9-4.1:3.9-4.1;
the hydrothermal reaction temperature is 160-180 ℃ and the reaction time is 20-24h.
2. The method of preparing a rheology agent according to claim 1, characterized in that said unsaturated polyether phosphate monomer is obtained from unsaturated polyether by phosphoric acid capping;
the preparation of the unsaturated polyether phosphate comprises the following steps: mixing unsaturated polyether with phosphoric acid, reacting for 3-5h at 60-70 ℃, and adding phosphorus pentoxide in the reaction process;
the unsaturated polyether is one or more of (methyl) allyl polyethylene glycol ether, isobutylene polyethylene glycol ether, isopentenyl polyethylene glycol ether, hydroxyethyl vinyl polyethylene glycol ether and 4-hydroxybutyl vinyl polyethylene glycol ether;
the number average molecular weight of the unsaturated polyether is 400-600;
and/or the phosphoric acid accounts for 8-12% of the mass of the unsaturated polyether;
and/or the mass concentration of phosphoric acid is above 85%;
and/or the dosage of phosphorus pentoxide accounts for 10-15% of the mass of the unsaturated polyether;
and/or phosphorus pentoxide is added for 3-6 times in the reaction process.
3. The method of preparing a rheological agent according to claim 1, wherein in step S1, the molar ratio of the unsaturated polyether phosphate monomer, ammonia water and calcium salt is 3:3.5 to 4.5: 5-7;
and/or the dosage of the supersaturation degree regulator accounts for 2 to 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 mass ratio of the acid liquor to the calcium salt is 1: (0.9-1.1);
and/or the concentration of the acid solution is 2.0-2.1mol/L;
and/or the acrylic monomer is acrylic acid or methacrylic acid.
4. A method of preparing a rheology agent according to any of claims 1 to 3 characterised in that said amide compound: modifying monomer: polyester monomer: the molar ratio of the acrylic monomers is 2:3:4:4;
and/or the dosage of the sodium formaldehyde sulfoxylate is 0.1-0.2% of the mass of the polyester monomer;
and/or the dosage of mercaptopropionic acid is 0.25% -0.5% of the mass of the polyester monomer;
and/or the ammonium persulfate dosage is 1.5% -3.0% of the mass of the polyester monomer.
5. The method of preparing a rheological agent according to claim 4, wherein the time for dropping the materials a and B in step S4 is 2-4 hours;
and/or the reaction temperature in the step S4 is 40-60 ℃, and the total reaction time of the dropwise adding material A and the material B is 3-6 hours;
and/or, in the step S4, the pH is adjusted to 6.5-7.
6. The method for preparing a rheological agent according to claim 4, wherein the amide compound is one or more of hydroxyethylacrylamide, methylolacrylamide, acrylamide and butenamide;
and/or the polyester monomer is one or more of methoxy polyethylene glycol methacrylate, methoxy polyethylene glycol isopentenyl acid ester and methoxy polyethylene glycol acrylate;
and/or the number average molecular weight of the polyester monomer is 3500-5000.
7. The method of preparing a rheology agent according to any of claims 1 to 3 or 5 to 6, characterized in that 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 prepared by dissolving the calcium ion slow-release agent and calcium salt in nitric acid.
8. A rheology agent prepared by the preparation method of any one of claims 1 to 7.
9. The rheology agent of claim 8, wherein 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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| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN107501479A (en) * | 2017-08-16 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer |
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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 |
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| CN113248647A (en) * | 2020-12-30 | 2021-08-13 | 马永峰 | Preparation method of concrete rheological agent |
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