Solid sulfonic acid water reducing agent as well as preparation method and application thereof
Through the solid sulfonic acid reducing agent prepared by sulfide reactions under decompression distillation conditions, the existing water reducing agent's water accounted for a relatively high problem of transportation costs, realizing solidization and performance regulation, improving transportation efficiency And product performance.
Patent Information
- Application Number
- CN202411626364.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-14
- Publication Date
- 2025-01-24
AI Technical Summary
The high moisture content in existing water reducing agent products leads to high transportation costs and limits the profit and capacity development of production enterprises, especially in areas with relatively long transportation distances.
A solid sulfonate water reducing agent, which uses a large monomer of saturated polyether containing hydroxyl or amino groups and a polymer containing benzenezate groups under decompression distillation conditions to achieve efficient removal Moisture, forming a solid water reducing agent that does not require additional curing technology.
The solidization of the water reduction agent is realized, the transportation cost is reduced, and by adjusting the molecular weight of the polyether monomer, the adhesive effect or early strong effect of the water reduction can be adjusted to improve the product performance.
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Figure CN119350630A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of solid water reducing agents, and in particular relates to a solid sulfonic acid water reducing agent and a preparation method and application thereof. Background Art
[0002] In recent years, the scale of my country's construction industry has expanded rapidly, showing characteristics such as large scale and rapid development. The demand for concrete has further increased. At the same time, large-scale construction projects have expanded from the industrially intensive eastern coastal areas to the relatively backward central and western regions, and even to overseas regions such as Southeast Asia and Central Asia. Water reducers, as the main admixture of concrete, have also flourished, the market has expanded year by year, and the demand has continued to rise. Compared with industrially developed coastal cities, other relatively backward industrial areas have problems such as industrial mismatch and lack of chemical raw materials that seriously affect the production of water reducers, and finished water reducers have to be transported from distant areas.
[0003] Conventional polycarboxylic acid water-reducing agent products generally contain 40-50% water, and the rest is mostly water. In short-distance transportation, the proportion of transportation costs is relatively low; however, as the transportation distance increases, the transportation cost gradually increases, and its proportion also increases relatively, which compresses the profits of production companies and seriously restricts the enthusiasm of production companies and the development of underdeveloped production capacity areas. Therefore, reducing transportation costs has become the key to solving the problem. The 50-60% water content in water-reducing agent products has become the most critical factor affecting the transportation cost and the cost of water-reducing agent materials. Removing excess water has become the most effective measure to reduce transportation costs.
[0004] Domestic research on solid polycarboxylic acid-based high-efficiency water reducers is still in its infancy. There is no company with leading water reducer curing technology, and the few companies that develop solid water reducers do not have mature solid water reducer products. Therefore, the research and development of solid water reducers not only has a broad application market, but also has a certain profit margin.
[0005] At present, there are many research and development ideas for solid water reducers, and the main curing technologies used are spray drying, bulk polymerization and membrane filtration. However, no technology has yet dominated the mainstream, and various curing methods are still in the development stage, and each has its own difficulties.
[0006] The biggest feature of the spray drying method is the large amount of water removal and high energy consumption. The main reason for the high energy consumption is that this method requires the synthesis of a common water reducer solution first, and then spray drying at a solid content of 10-20%, with water accounting for 80% of the total mass of the raw material. Secondly, the performance of the solid water reducer produced by the spray drying method is lower than that of the raw material, which increases the cost of using the water reducer.
[0007] The advantage of bulk polymerization is that it can directly synthesize a water reducer with a solid content of 100% at high temperature without the need for extra water removal costs. The main disadvantages are as follows: First, bulk polymerization requires melting of polyether, the reaction temperature is high, and the double bonds of polyether are easily deactivated; second, the viscosity of the reaction materials is high, and acrylic acid and initiators are difficult to disperse evenly, resulting in local high temperature and violent polymerization, which may even damage the equipment in severe cases; third, heat exchange is difficult, and the heat of free radical polymerization is difficult to discharge. There is a huge difference between small-scale test, pilot test, and large-scale production.
[0008] The permeable membrane filtration method first uses a permeable membrane to filter part of the water, and then uses distillation to remove the remaining water. The advantage is that the filter membrane can be reused, and the filtered water does not need to be heated and vaporized, which reduces energy consumption. This method is relatively energy-saving and environmentally friendly, but it has two main disadvantages: first, the production line construction cost is high, the investment is greater, and the membrane needs to be replaced in batches in a timely manner after it is damaged; second, it is difficult to detect the membrane damage in time, resulting in material loss. Summary of the invention
[0009] In order to solve the above technical problems, the present invention provides a solid sulfonic acid water reducer and a preparation method and application thereof. The preparation method of the solid sulfonic acid water reducer is simple, and the performance of the synthetic water reducer can be adjusted by changing the molecular weight of the saturated polyether macromonomer containing hydroxyl groups or the saturated polyether macromonomer containing amino groups in the raw materials, so that the water reducer has excellent viscosity reduction effect or early strength effect.
[0010] The technical solution adopted by the present invention is as follows:
[0011] A solid sulfonic acid water reducer is obtained by sulfonating a saturated polyether macromonomer containing a hydroxyl group or a saturated polyether macromonomer containing an amino group and a polymer containing a benzenesulfonic acid group under reduced pressure distillation conditions.
[0012] The conditions of the reduced pressure distillation are: 0-5000 Pa, 120-180° C. reduced pressure distillation for 3-6 hours;
[0013] The mass ratio of the polymer containing benzenesulfonic acid groups to the saturated polyether macromonomer containing hydroxyl groups is 100:(150-400);
[0014] The mass ratio of the polymer containing benzenesulfonic acid groups to the saturated polyether macromonomer containing amino groups is 100:(150-400).
[0015] The saturated polyether macromonomer containing hydroxyl groups is at least one of polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether and methoxy polyethylene glycol monomethyl ether.
[0016] The saturated polyether macromonomer containing an amino group is at least one of amino polyethylene glycol monomethyl ether and amino polyethylene glycol monoethyl ether.
[0017] The polymer containing benzenesulfonic acid groups is at least one of benzenesulfonic acid polymer I and benzenesulfonic acid polymer II;
[0018] The structural formula of the benzenesulfonic acid polymer I is: Wherein R1 is one of -H, -CH3, CH3CH2-, C6H5-, and n is 20 to 50;
[0019] The structural formula of the benzenesulfonic acid polymer II is: Wherein, R2 is one of -CH2-, -CH2CH2-, -C6H4-, and m is 10-25.
[0020] The molecular weight of the saturated polyether macromonomer containing hydroxyl groups is 800-5000.
[0021] The molecular weight of the amino-containing saturated polyether macromonomer is 800-5000.
[0022] The molecular weight of the polymer containing benzenesulfonic acid groups is 5000-15000.
[0023] The present invention also provides a preparation method of the solid sulfonic acid water reducer, which comprises the following steps: mixing a saturated polyether macromonomer containing a hydroxyl group or a saturated polyether macromonomer containing an amino group with a polymer containing a benzenesulfonic acid group, heating until melting, and then performing reduced pressure distillation, maintaining the air pressure in the reactor at 0 to 5 kPa, the reaction temperature at 120 to 180° C., the reaction time at 3 to 6 hours, taking out the material while hot after the reaction, and slicing it after cooling.
[0024] The weight average molecular weight of the solid sulfonic acid water reducer prepared by the above preparation method is 30,000-80,000.
[0025] The invention also provides application of the solid sulfonic acid water reducing agent as a concrete additive.
[0026] The solid sulfonic acid water reducer provided by the present invention is obtained by sulfonation reaction of a saturated polyether macromonomer containing a hydroxyl group, or a saturated polyether macromonomer containing an amino group and a polymer containing a benzenesulfonic acid group under reduced pressure distillation conditions. The functions of the benzenesulfonic acid polymer are three: first, to provide the main chain structure of the water reducer and build the molecular framework of the water reducer; second, to provide sulfonic acid groups to improve the adsorption and dispersion capacity of the water reducer; third, to provide ionized hydrogen ions to replace the catalyst to increase the rate of the sulfonation reaction. Therefore, in the present invention, the reaction can be completed quickly without an additional catalyst. The functions of the saturated polyether macromonomer containing hydroxyl or amino groups are mainly two points: first, to provide hydroxyl / amino groups that are easily sulfonated, connect the main chain and the side chain, and build the molecular framework of the water reducer; second, to provide steric hindrance, enhance the dispersion ability of the water reducer, and improve the performance of the water reducer.
[0027] Compared with the prior art, the present invention has the following beneficial effects:
[0028] The solid sulfonic acid water reducing agent product prepared by the present invention is a solid water reducing agent, which does not require an additional curing process and does not cause performance loss. The performance of the synthetic water reducing agent can be adjusted by changing the molecular weight of the saturated polyether macromonomer containing hydroxyl or amino groups. When a small molecular weight polyether monomer with Mn < 1000 is used, the viscosity reduction effect of the water reducing agent can be enhanced; and when a large molecular weight polyether monomer with Mn > 3000 is used, the early strength effect of the water reducing agent can be enhanced.
[0029] The synthetic raw materials of the solid sulfonic acid described in the present invention are simple, and only include benzenesulfonic acid polymers that provide sulfonic acid groups and saturated polyether macromonomers that provide hydroxyl / amino groups. In the benzenesulfonic acid polymer, since the benzene ring structure is connected to the sulfonic acid group through a σ bond, it has an electron-withdrawing effect, which enhances the acidity of the sulfonic acid group and can make H + Leave, produce catalytic center, no need to add additional catalyst.
[0030] The synthesis process of the solid sulfonic acid water reducer in the present invention is simple. After the two materials are respectively connected to the reaction kettle, no manual operation is required. After the reaction is completed, the liquid water reducer can be injected into the slicer, which effectively reduces the labor cost and the difficulty of personnel operation. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 This is the GPC chart of the solid sulfonic acid water reducer prepared in Example 5. DETAILED DESCRIPTION
[0032] The present invention is described in detail below with reference to the embodiments.
[0033] The sources of the substances in the examples are as follows:
[0034] The structural formula of poly(di-p-hydroxybenzenesulfonyl methylene) is The synthesis method is as follows: 8.4g of p-hydroxybenzenesulfonic acid hydrate and 0.75g of formaldehyde are dissolved in a dimethyl sulfoxide solution containing 40mL of sulfuric acid, and then the mixture is transferred to a 200mL high-pressure polytetrafluoroethylene reactor, and reacted at 100°C. The reaction time is selected according to the different molecular weights of the desired products. Since formaldehyde is easily vaporized into gas and is fixed in the solution after the reaction, the reaction container needs to be sealed and the reaction time needs to be appropriately increased. The reaction time corresponding to the poly (di-p-hydroxybenzenesulfonic acid methylene) with a molecular weight of 5000 is about 1-2h, the reaction time corresponding to the poly (di-p-hydroxybenzenesulfonic acid methylene) with a molecular weight of 8000 is about 2-4h, and the reaction time corresponding to the poly (di-p-hydroxybenzenesulfonic acid methylene) with a molecular weight of 10000 is about 4-8h. After the reaction is completed, the volatile substances are removed by reduced pressure distillation, and the distillation product can be directly used in the synthesis of water reducers.
[0035] The structural formula of poly(1,1,3,3-tetrakis-(2-hydroxy-3-methyl-5-sulfonatophenyl)propyl) is The synthesis method is as follows: 16.8 g of p-hydroxybenzenesulfonic acid hydrate and 1.8 g of malondialdehyde are dissolved in a dimethyl sulfoxide solution containing 40 mL of sulfuric acid, and then the mixture is transferred to a 200 mL high-pressure polytetrafluoroethylene reactor for reaction at 120° C. The reaction time is selected according to the different molecular weights of the desired products, wherein the reaction time corresponding to the poly(1,1,3,3-tetra-(2-hydroxy-3-methyl-5-sulfonic acid phenyl) propyl) with a molecular weight of 5000 is about 1-3 hours, and the reaction time corresponding to the poly(1,1,3,3-tetra-(2-hydroxy-3-methyl-5-sulfonic acid phenyl) propyl) with a molecular weight of 15000 is about 3-8 hours. After the reaction is completed, the volatile substances are removed by reduced pressure distillation. The distillation product can be directly used in the synthesis of water reducers.
[0036] Aminopolyethylene glycol monomethyl ether: purchased from MacLean.
[0037] Polyethylene glycol monomethyl ether: purchased from Merck.
[0038] Aminopolyethylene glycol monomethyl ether: purchased from MacLean.
[0039] Methoxypolyethylene glycol monomethyl ether: purchased from Merck.
[0040] Example 1
[0041] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0042] Weigh 156.6 g of poly(di-p-hydroxybenzenesulfonyl methylene) with a molecular weight of 8000 and 600 g of aminopolyethylene glycol monomethyl ether with a molecular weight of 2000 and add them to a reactor, heat to 140°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 5 kPa, react for 4 hours, cool down and slice to obtain flaky solid sulfonic acid water reducer.
[0043] Example 2
[0044] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0045] Weigh 313.2 g of poly(di-p-hydroxybenzenesulfonyl methylene) with a molecular weight of 10,000 and 600 g of polyethylene glycol monomethyl ether with a molecular weight of 2,000 and add them to a reactor, heat to 140°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 5 kPa, react for 4 hours, cool down and slice to obtain a flaky solid sulfonic acid water reducer.
[0046] Example 3
[0047] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0048] Weigh 208.8 g of poly (1,1,3,3-tetrakis-(2-hydroxy-3-methyl-5-sulfonatophenyl)propyl) with a molecular weight of 5000 and 600 g of polyethylene glycol monomethyl ether with a molecular weight of 2000 and add them to a reactor, heat to 140°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 5 kPa, react for 4 hours, cool down and slice to obtain a flaky solid sulfonic acid water reducer.
[0049] Example 4
[0050] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0051] Weigh 261.0 g of poly (1,1,3,3-tetrakis-(2-hydroxy-3-methyl-5-sulfonatophenyl)propyl) with a molecular weight of 15000 and 600 g of aminopolyethylene glycol monomethyl ether with a molecular weight of 2000 and add them to a reactor, heat to 160°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 3 kPa, react for 4 hours, cool down and slice to obtain a flaky solid sulfonic acid water reducer.
[0052] Example 5
[0053] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0054] Weigh 174 g of poly(di-p-hydroxybenzenesulfonylethylene) with a molecular weight of 5000 and 600 g of polyethylene glycol monomethyl ether with a molecular weight of 3000 and add them to a reactor, heat to 160°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 3 kPa, react for 6 hours, cool down and slice, and obtain flaky solid sulfonic acid water reducer.
[0055] The GPC chart of the flaky solid sulfonic acid water reducer prepared in this example is as follows Figure 1 As shown in the figure, the peak at 31.203 min is the product peak, the peak area accounts for 97.3%, the number average molecular weight is 40,000, the weight average molecular weight is 74,000, and the PDI is 1.84.
[0056] Example 6
[0057] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0058] Weigh 156.6 g of poly (1,1,3,3-tetrakis-(2-hydroxy-3-methyl-5-sulfonatophenyl)propyl) with a molecular weight of 5000 and 600 g of polyethylene glycol monomethyl ether with a molecular weight of 3000 and add them to a reactor, heat to 180°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 3 kPa, react for 6 hours, cool down and slice to obtain a flaky solid sulfonic acid water reducer.
[0059] Example 7
[0060] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0061] Weigh 156.6 g of poly(di-p-hydroxybenzenesulfonyl methylene) with a molecular weight of 5000 and 400 g of aminopolyethylene glycol monomethyl ether with a molecular weight of 1000 and add them to a reactor, heat to 120°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 3 kPa, react for 3 hours, cool down and slice to obtain flaky solid sulfonic acid water reducer.
[0062] Example 8
[0063] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0064] Weigh 156.6 g of poly (1,1,3,3-tetrakis-(2-hydroxy-3-methyl-5-sulfonatophenyl)propyl) with a molecular weight of 5000 and 400 g of methoxy polyethylene glycol monomethyl ether with a molecular weight of 1000 and add them to a reactor, heat to 140°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 5 kPa, react for 3 hours, cool down and slice to obtain a flaky solid sulfonic acid water reducer.
[0065] Comparative Example 1
[0066] A method for preparing a solid sulfonic acid water reducing agent, comprising the following steps:
[0067] Weigh 156.6 g of poly (1,1,3,3-tetrakis-(2-hydroxy-3-methyl-5-sulfonatophenyl)propyl) with a molecular weight of 5000 and 400 g of methoxy polyethylene glycol monomethyl ether with a molecular weight of 15000 and add them into a reactor, heat to 100°C, start reduced pressure distillation after the materials melt, maintain the air pressure in the reactor at 10 kPa, react for 3 hours, cool down and slice to obtain a sheet sample.
[0068] Test Case
[0069] Concrete performance testing
[0070] According to GB / T8076-2008, the solid sulfonate water reducer prepared in Examples 1 to 8, the solid sulfonic acid water reducer prepared in Comparative Example 1 and the common water reducer on the market (Comparative Example 2) were compared. The performance of the polycarboxylate water reducer was tested at a solid content of 0.20%. The test results are shown in Table 1:
[0071] Table 1 Concrete test results
[0072]
[0073] As shown in Table 1, Examples 1-4 use a polyether with a molecular weight of 2000 as a branch chain, and the water reduction rate is the same as the performance of the market water reducer, and has no effect on the compressive strength; Examples 5-6 use a short main chain and a long branch chain molecular structure, which leads to a decrease in the water reduction rate of the water reducer and a prolonged collapse time, but greatly improves the strength of the concrete; Examples 7-8 use a short branch chain molecular structure, which greatly reduces the collapse time of the concrete and greatly improves the workability and viscosity of the concrete. The synthesis conditions of Comparative Example 1 do not meet the conditions required by the present invention, and it has no obvious water reduction effect, and when the dosage is the same as that of other water reducers, the concrete does not have workability and its performance cannot be detected.
[0074] The above-mentioned detailed description of a solid sulfonic acid water-reducing agent and its preparation method and application with reference to the embodiments is illustrative rather than restrictive, and several embodiments can be listed according to the limited scope. Therefore, changes and modifications without departing from the overall concept of the present invention should fall within the scope of protection of the present invention.
Claims
1. A solid sulfonic acid water reducing agent, characterized in that: The solid sulfonic acid water reducing agent is obtained by sulfonating a saturated polyether macromonomer containing a hydroxyl group or a saturated polyether macromonomer containing an amino group and a polymer containing a benzenesulfonic acid group under reduced pressure distillation conditions.
2. The solid sulfonic acid water reducing agent according to claim 1, characterized in that: The conditions of the reduced pressure distillation are: 0-5000 Pa, 120-180° C., reduced pressure distillation for 3-6 hours; the mass ratio of the polymer containing benzenesulfonic acid groups to the saturated polyether macromonomer containing hydroxyl groups is 100:(150-400); the mass ratio of the polymer containing benzenesulfonic acid groups to the saturated polyether macromonomer containing amino groups is 100: (150～400)。 3. The solid sulfonic acid water reducing agent according to claim 1, characterized in that: The saturated polyether macromonomer containing hydroxyl groups is at least one of polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether and methoxy polyethylene glycol monomethyl ether.
4. The solid sulfonic acid water reducing agent according to claim 1, characterized in that: The saturated polyether macromonomer containing an amino group is at least one of amino polyethylene glycol monomethyl ether and amino polyethylene glycol monoethyl ether.
5. The solid sulfonic acid water reducing agent according to claim 1, characterized in that: The polymer containing benzenesulfonic acid groups is at least one of benzenesulfonic acid polymer I and benzenesulfonic acid polymer II; The structural formula of the benzenesulfonic acid polymer I is: Wherein R1 is one of -H, -CH3, CH3CH2-, C6H5-, and n is 20 to 50; The structural formula of the benzenesulfonic acid polymer II is: Wherein, R2 is one of -CH2-, -CH2CH2-, -C6H4-, and m is 10-25.
6. The solid sulfonic acid water reducing agent according to claim 1 or 3, characterized in that: The molecular weight of the saturated polyether macromonomer containing hydroxyl groups is 800-5000.
7. The solid sulfonic acid water reducing agent according to claim 1 or 4, characterized in that: The molecular weight of the amino-containing saturated polyether macromonomer is 800-5000.
8. The solid sulfonic acid water reducing agent according to claim 1 or 5, characterized in that: The molecular weight of the polymer containing benzenesulfonic acid groups is 5000-15000.
9. The method for preparing the solid sulfonic acid water reducing agent according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: mixing a saturated polyether macromonomer containing a hydroxyl group or a saturated polyether macromonomer containing an amino group with a polymer containing a benzenesulfonic acid group, heating until melting, and then performing reduced pressure distillation, maintaining the air pressure in the reactor at 0 to 5 kPa, the reaction temperature at 120 to 180° C., and the reaction time at 3 to 6 hours, and after the reaction is completed, taking out the material while it is hot, and slicing it after cooling.
10. Use of the solid sulfonic acid water reducing agent according to any one of claims 1 to 8 as a concrete additive.