A sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF) and its preparation method and application

Abstract

This invention discloses a sulfonated modified phenol-acetone-formaldehyde copolymer (PSAF), its preparation method, and its applications. The preparation method uses sodium sulfite, phenol, and formaldehyde as raw materials, and prepares a sulfonated phenol-formaldehyde condensate (SPF) through sulfonation and polycondensation reactions under alkaline conditions. Simultaneously, using sodium sulfite, acetone, and formaldehyde as raw materials, an acetone-formaldehyde sulfonated copolymer (SAF-3) is synthesized through a stepwise polycondensation reaction under alkaline conditions. Finally, SPF and SAF-3 are subjected to a blending grafting reaction at 95°C, and the product is discharged at room temperature to obtain the target product, PSAF. This invention, by optimizing the formaldehyde dosage and SPF addition ratio, can precisely control the molecular structure and properties of the product. The preparation process is mild, controllable, and uses readily available raw materials. The obtained PSAF exhibits excellent water solubility, dispersibility, and interfacial activity, and can be widely used in coal-water slurry dispersants, oilfield chemicals, water treatment agents, and other fields, showing promising prospects for industrial application.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, and specifically relates to a sulfonated modified phenolic-acetone-formaldehyde copolymer PSAF, its preparation method, and its application. Background Technology

[0002] As a highly efficient and clean coal-based fluid fuel, the dispersion stability of coal-water slurry is a core indicator determining its storage, transportation, and combustion performance. Dispersants are key additives in the preparation of coal-water slurry, directly affecting its fluidity, stability, and maximum slurry concentration. Coal-water slurry dispersants are mainly classified into four categories: naphthalene-based, melamine-based, aliphatic-based, and phenolic-based. Among them, aliphatic sulfonated condensates (such as sulfonated acetone-formaldehyde condensate SAF) are widely used in coal-water slurry preparation due to their readily available raw materials, low cost, and excellent temperature resistance. Chinese invention patent CN202110841103.0 discloses a modified narrow-distribution coal-water slurry dispersant, prepared by batch-drop reaction using sulfonating agents, formaldehyde, and acetone as raw materials. Although it can improve molecular weight distribution, single aliphatic dispersants still have drawbacks such as low dispersion efficiency, poor adaptability to coals that are difficult to slurry, and easy stratification during long-term storage, limiting their application in high-quality coal-water slurries. Phenolic dispersants (such as sulfonated phenol-formaldehyde condensate SPF) have the characteristics of adjustable molecular structure, strong adsorption performance, and good dispersion stability. Chinese invention patent CN201910785313.5 discloses a supramolecular sulfonated phenolic condensate, which improves the friction resistance of the dispersant by introducing urea monomer. Chinese invention patent CN202311703569.X uses p-hydroxybenzoic acid-aniline condensate to modify sulfonated phenolic resin to reduce foam generation. However, such phenolic dispersants generally have the problem of high production cost, and the effect of improving fluidity is limited when used alone, making it difficult to balance dispersibility and economy.

[0003] To address the performance limitations of single dispersants, the industry often employs optimization methods such as compounding different types of dispersants or chemical modification. Chinese invention patent CN202110518279.2 discloses a method for preparing sulfonate phenolic resin, which uses the polymerization reaction of 4-hydroxybenzenesulfonic acid and formaldehyde to prepare the resin. While this method optimizes the sulfonation effect, it fails to achieve effective integration with aliphatic condensate polymers. Other patents have attempted to compound phenolic and aliphatic dispersants, but these compound systems suffer from poor compatibility between components, weak synergistic effects, and complex process control, failing to fundamentally improve the overall performance of the dispersant. Therefore, developing a modified aliphatic coal-water slurry additive that combines aliphatic sulfonated condensate polymers with phenolic sulfonated condensate polymers through chemical grafting modification, achieving complementary performance advantages, and possessing a simple preparation process, controllable cost, and wide applicability, has become a pressing technical problem in the field of coal-water slurry dispersants. Summary of the Invention

[0004] Based on the shortcomings of the prior art, this invention provides a sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF), its preparation method, and its application. The method, through precise control of the reaction process and raw material ratio, prepares a modified dispersant with excellent comprehensive performance, meeting the requirements for the preparation of high-quality coal-water slurry.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention uses sodium sulfite, phenol, acetone, formaldehyde, etc. as raw materials. By precisely controlling the raw material ratio and process parameters (pH, temperature, reaction time), sulfonated acetone formaldehyde condensate (SAF-3) and sulfonated phenol formaldehyde condensate (SPF) are first prepared. Then, the two are combined through a chemical grafting reaction to prepare a modified aliphatic coal-water slurry additive that combines the low cost of aliphatic additives with the high dispersibility of phenolic additives.

[0006] A method for preparing sulfonated modified phenolic-acetone-formaldehyde copolymer PSAF includes the following steps: S1. Add sodium sulfite and phenol to a reaction vessel containing deionized water, and adjust the pH to alkaline with NaOH. S2. After stirring to dissolve and heating, formaldehyde is added dropwise, and the system temperature is controlled at 90~100℃ for sulfonation reaction. S3. Discharge the material at room temperature to obtain sulfonated phenol formaldehyde condensate SPF; S4. Add sodium sulfite to a reaction vessel containing deionized water, and add NaOH to adjust the pH to alkaline. After stirring to dissolve and heating, add acetone dropwise, controlling the system temperature at 50~56℃. After the reaction, add formaldehyde dropwise, controlling the dropping rate so that the system temperature does not exceed 80℃. After the dropwise addition is completed, continue the reaction at 85~95℃, cool to room temperature and discharge to obtain sulfonated acetone formaldehyde condensate SAF-3. S5. Add SPF dropwise into SAF-3 and continue the reaction at 95℃. Cool to room temperature and discharge to obtain sulfonated modified phenolic-acetone formaldehyde copolymer PSAF.

[0007] Furthermore, in step S1, the molar ratio of sodium sulfite, sodium hydroxide, and water is 1:0.5:16.7.

[0008] Furthermore, in step S2, the molar ratio of phenol, sodium sulfite, and formaldehyde is 1:1:2.3.

[0009] Furthermore, in step S4, the molar ratio of acetone, sodium sulfite, and formaldehyde is 1:0.55:2.1.

[0010] Furthermore, in step S5, the amount of SPF used is 5.00g to 25.00g, preferably 20.00g.

[0011] Furthermore, the molar ratio of acetone to phenol is 1:1.

[0012] Furthermore, the NaOH is a solid, and the formaldehyde added in steps S2 and S4 is a 37% (w / w) aqueous solution of formaldehyde.

[0013] Furthermore, the reaction vessel is equipped with a thermometer and a condenser, and stirring is carried out throughout the process.

[0014] As a preferred embodiment, a method for preparing sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF) includes the following steps: S1. Add 12.60g of sodium sulfite and 9.41g of phenol to a reaction vessel containing 30.00g of deionized water, and adjust the pH to 10 with 2.00g of NaOH. S2. After stirring to dissolve and heating, add 18.33g of formaldehyde dropwise, control the system temperature at 90~100℃, and carry out the sulfonation reaction for 1~3 hours. S3. Discharge the material at room temperature to obtain sulfonated phenol formaldehyde condensate SPF; S4. Add 6.90g of sodium sulfite to a reaction vessel containing 25.00g of deionized water, and add 1.70g of NaOH to adjust the pH to 10. After stirring to dissolve and heating, add 5.80g of acetone dropwise, controlling the system temperature at 50~56℃. After reacting for 1 h, add 17.00g of formaldehyde dropwise, controlling the dropping rate so that the system temperature does not exceed 80℃. After the dropwise addition is completed, continue the reaction at 85~95℃ for 1 h, then cool to room temperature and discharge to obtain sulfonated acetone formaldehyde condensate SAF-3. S5. Take 20.00g of SPF and add it dropwise into SAF-3. Continue the reaction at 95℃ for 1.5 h, then cool to room temperature and discharge to obtain sulfonated modified phenolic-acetone formaldehyde copolymer PSAF.

[0015] A sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF) prepared according to the preparation method described above.

[0016] Application of a sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF) in the preparation of coal-water slurry, oilfield chemicals, and water treatment agents.

[0017] Compared with the prior art, the present invention has the following advantages: This invention organically integrates aliphatic and phenolic structures through a chemical grafting process. It retains the advantages of readily available and low-cost raw materials of aliphatic dispersants while also possessing the characteristics of strong adsorption and good stability of phenolic dispersants. This effectively solves the technical pain points of low dispersion efficiency, poor adaptability, and difficulty in balancing cost and performance in existing technologies. It simplifies the preparation process, reduces application costs, and fills the technical gap in the industry that combines low cost and high performance. The overall dispersion effect and application adaptability are significantly improved, which can meet the preparation requirements of high-quality coal-water slurry and is suitable for large-scale industrial application. Attached Figure Description

[0018] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0019] The present invention will be further described below with reference to embodiments. Example 1

[0020] A method for sulfonating and modifying phenolic-acetone-formaldehyde copolymer (PSAF) with an acetone to phenol molar ratio of 1:0.07 (the proportion of raw materials added to the final product PSAF). Add 30.00g of deionized water, 12.60g of sodium sulfite, and 9.41g of phenol to a three-necked flask equipped with a thermometer and a condenser. Add 2.00g of solid NaOH to adjust the pH to 10. After stirring to dissolve, raise the temperature and slowly add 18.33g of a 37% formaldehyde aqueous solution. Control the system temperature at 90~100°C and sulfonate for 1~3 hours. After cooling to room temperature, discharge the product to obtain sulfonated phenol formaldehyde condensate SPF (72.34g), in which the molar ratio of phenol, sodium sulfite, and formaldehyde is 1:1:2.3. 25.00 g of deionized water, 6.90 g of sodium sulfite, and 1.70 g of solid NaOH were added to a three-necked flask equipped with a thermometer and a condenser. After stirring and dissolving, the mixture was heated, and 5.80 g of acetone was slowly added dropwise while maintaining the system temperature at 50-56°C. After reacting at this temperature for 1 hour, 17.00 g of a 37% formaldehyde aqueous solution was slowly added dropwise while controlling the dropping rate to keep the system temperature below 80°C. After the addition was completed, the reaction was continued at 85-95°C for 1 hour. The mixture was then cooled to room temperature and discharged to obtain SAF-3. The molar ratio of acetone, sodium sulfite, and formaldehyde was 1:0.55:2.1. Add 5.00g of the prepared SPF to the above SAF-3 system, control the system temperature to rise to 95°C, continue to keep the reaction at this temperature for 1.5h, and then discharge the material at room temperature to obtain a dark red liquid PSAF with a solid content of about 36.3%.

[0021] In a 250ml beaker, 0.5% PSAF (by mass of coal), 72g water, and 136g of Zhongjin gasification coal powder with a moisture content of 10% were added. After stirring for 5 minutes, the concentration, viscosity, and stability were tested. The results were compared with those of commercial SAF, as shown in Table 1. Table 1 shows that the coal-water slurry prepared from the PSAF synthesized in this invention exhibits low viscosity and good stability.

[0022] Table 1. Properties of coal-water slurry prepared with different additives Example 2

[0023] A method for preparing sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF) with a molar ratio of acetone to phenol of 1:0.2 (the proportion of raw materials added to the final product PSAF). Add 30.00g of deionized water, 12.60g of sodium sulfite, and 9.41g of phenol to a three-necked flask equipped with a thermometer and a condenser. Add 2.00g of solid NaOH to adjust the pH to 10. After stirring to dissolve, raise the temperature and slowly add 18.33g of a 37% formaldehyde aqueous solution. Control the system temperature at 90~100°C and sulfonate for 1~3 hours. After cooling to room temperature, discharge the product to obtain sulfonated phenol formaldehyde condensate SPF, wherein the molar ratio of phenol, sodium sulfite, and formaldehyde is 1:1:2.3. 25.00 g of deionized water, 6.90 g of sodium sulfite, and 1.70 g of solid NaOH were added to a three-necked flask equipped with a thermometer and a condenser. After stirring and dissolving, the mixture was heated, and 5.80 g of acetone was slowly added dropwise while maintaining the system temperature at 50-56°C. After reacting at this temperature for 1 hour, 17.00 g of a 37% formaldehyde aqueous solution was slowly added dropwise while controlling the dropping rate to keep the system temperature below 80°C. After the addition was completed, the reaction was continued at 85-95°C for 1 hour. The mixture was then cooled to room temperature and discharged to obtain SAF-3. The molar ratio of acetone, sodium sulfite, and formaldehyde was 1:0.55:2.1. Add 15.00g of the prepared SPF to the above SAF-3 system, control the system temperature to rise to 95°C, continue to keep the reaction at this temperature for 1.5h, and then discharge the material at room temperature to obtain a dark red liquid PSAF with a solid content of about 36.5%.

[0024] In a 250ml beaker, 0.5% PSAF (by mass of coal), 72g water, and 136g of Zhongjin gasification coal powder with a moisture content of 10% were added. After stirring for 5 minutes, the concentration, viscosity, and stability were tested. The results were compared with those of commercial SAF, as shown in Table 2. Table 2 shows that the coal-water slurry prepared from the PSAF synthesized in this invention has low viscosity and good stability.

[0025] Table 2 Performance of coal-water slurry prepared with different additives Example 3

[0026] A method for preparing sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF) with a molar ratio of acetone to phenol of 1:0.277 (the proportion of raw materials added to the final product PSAF). Add 30.00g of deionized water, 12.60g of sodium sulfite, and 9.41g of phenol to a three-necked flask equipped with a thermometer and a condenser. Add 2.00g of solid NaOH to adjust the pH to 10. After stirring to dissolve, raise the temperature and slowly add 18.33g of a 37% formaldehyde aqueous solution. Control the system temperature at 90~100°C and sulfonate for 1~3 hours. After cooling to room temperature, discharge the product to obtain sulfonated phenol formaldehyde condensate SPF, wherein the molar ratio of phenol, sodium sulfite, and formaldehyde is 1:1:2.3. 25.00 g of deionized water, 6.90 g of sodium sulfite, and 1.70 g of solid NaOH were added to a three-necked flask equipped with a thermometer and a condenser. After stirring and dissolving, the mixture was heated, and 5.80 g of acetone was slowly added dropwise while maintaining the system temperature at 50-56°C. After reacting at this temperature for 1 hour, 17.00 g of a 37% formaldehyde aqueous solution was slowly added dropwise while controlling the dropping rate to keep the system temperature below 80°C. After the addition was completed, the reaction was continued at 85-95°C for 1 hour. The mixture was then cooled to room temperature and discharged to obtain SAF-3. The molar ratio of acetone, sodium sulfite, and formaldehyde was 1:0.55:2.1. Add 20.00g of the prepared SPF to the above SAF-3 system, control the system temperature to rise to 95°C, continue to keep the reaction at this temperature for 1.5h, and then discharge the material at room temperature to obtain a dark red liquid PSAF with a solid content of about 36.4%.

[0027] In a 250ml beaker, 0.5% PSAF (by mass of coal), 72g water, and 136g of Zhongjin gasification coal powder with a moisture content of 10% were added. After stirring for 5 minutes, the concentration, viscosity, and stability were tested. The results were compared with those of commercial SAF, as shown in Table 3. Table 3 shows that the coal-water slurry prepared from the PSAF synthesized in this invention has low viscosity and good stability.

[0028] Table 3 Performance of coal-water slurry prepared with different additives Example 4

[0029] A method for preparing sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF) with a molar ratio of acetone to phenol of 1:0.35 (the proportion of raw materials added to the final product PSAF). Add 30.00g of deionized water, 12.60g of sodium sulfite, and 9.41g of phenol to a three-necked flask equipped with a thermometer and a condenser. Add 2.00g of solid NaOH to adjust the pH to 10. After stirring to dissolve, raise the temperature and slowly add 18.33g of a 37% formaldehyde aqueous solution. Control the system temperature at 90~100°C and sulfonate for 1~3 hours. After cooling to room temperature, discharge the product to obtain sulfonated phenol formaldehyde condensate SPF, wherein the molar ratio of phenol, sodium sulfite, and formaldehyde is 1:1:2.3. 25.00 g of deionized water, 6.90 g of sodium sulfite, and 1.70 g of solid NaOH were added to a three-necked flask equipped with a thermometer and a condenser. After stirring and dissolving, the mixture was heated, and 5.80 g of acetone was slowly added dropwise while maintaining the system temperature at 50-56°C. After reacting at this temperature for 1 hour, 17.00 g of a 37% formaldehyde aqueous solution was slowly added dropwise while controlling the dropping rate to keep the system temperature below 80°C. After the addition was completed, the reaction was continued at 85-95°C for 1 hour. The mixture was then cooled to room temperature and discharged to obtain SAF-3. The molar ratio of acetone, sodium sulfite, and formaldehyde was 1:0.55:2.1. Add 25.00g of the prepared SPF to the above SAF-3 system, control the system temperature to rise to 95°C, continue to keep the reaction at this temperature for 1.5h, and then discharge the material at room temperature to obtain a dark red liquid PSAF with a solid content of about 36.2%.

[0030] In a 250ml beaker, 0.5% PSAF (based on coal mass), 72g water, and 136g of Zhongjin gasification coal powder with a moisture content of 10% were added. After stirring for 5 minutes, the concentration, viscosity, and stability were tested. The results were compared with commercial SAF, as shown in Table 4. Table 4 shows that the coal-water slurry prepared from the PSAF synthesized in this invention has low viscosity and good stability.

[0031] Table 4. Properties of coal-water slurry prepared with different additives The results from Examples 1-4 show that as the amount of SPF added increases, the concentration of the coal-water slurry gradually increases and the viscosity gradually decreases, indicating that the dispersion performance is continuously improved. When the amount of SPF added is 20 g, the resulting coal-water slurry has the highest concentration and lowest viscosity, exhibiting the best overall performance. When the amount of SPF added is further increased to 25 g, the viscosity increases slightly, indicating that excessive SPF may lead to enhanced intermolecular interactions, thereby affecting the system's flowability. Therefore, the preferred amount of SPF added is 15-20 g, and more preferably 20 g.

[0032] In addition, sulfonated modified phenolic-acetone-formaldehyde copolymer (PSAF) can also be used in oilfield chemicals and water treatment agents.

[0033] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a sulfonically modified phenol-formaldehyde-acetone copolymer PSAF, characterized by, Includes the following steps: S1. Add sodium sulfite and phenol to a reaction vessel containing deionized water, and adjust the pH to alkaline with NaOH. S2. After stirring to dissolve and heating, formaldehyde is added dropwise, and the system temperature is controlled at 90~100℃ for sulfonation reaction. S3. Discharge the material at room temperature to obtain sulfonated phenol formaldehyde condensate SPF; S4. Add sodium sulfite to a reaction vessel containing deionized water, and add NaOH to adjust the pH to alkaline. After stirring to dissolve and heating, add acetone dropwise, controlling the system temperature at 50~56℃. After the reaction, add formaldehyde dropwise, controlling the dropping rate so that the system temperature does not exceed 80℃. After the dropwise addition is completed, continue the reaction at 85~95℃, cool to room temperature and discharge to obtain sulfonated acetone formaldehyde condensate SAF-3. S5. Add SPF dropwise into SAF-3 and continue the reaction at 95℃. Cool to room temperature and discharge to obtain sulfonated modified phenolic-acetone formaldehyde copolymer PSAF.

2. The preparation method according to claim 1, characterized in that, In step S1, the molar ratio of sodium sulfite, sodium hydroxide, and water is 1:0.5:16.

7.

3. The preparation method according to claim 1, characterized in that, In step S2, the molar ratio of phenol, sodium sulfite, and formaldehyde is 1:1:2.

3.

4. The preparation method according to claim 1, characterized in that, In step S4, the molar ratio of acetone, sodium sulfite, and formaldehyde is 1:0.55:2.

1.

5. The preparation method according to claim 1, characterized in that, In step S5, the amount of SPF used is 5.00g to 25.00g.

6. The preparation method according to claim 1, characterized in that, The molar ratio of acetone to phenol is 1:

1.

7. The preparation method according to claim 1, characterized in that, The NaOH is a solid, and the formaldehyde added in steps S2 and S4 is a 37% (w / w) aqueous solution of formaldehyde.

8. The preparation method according to claim 1, characterized in that, The reaction vessel is equipped with a thermometer and a condenser, and the entire process is carried out using a stirring device.

9. The sulfonated modified phenolic-acetone-formaldehyde copolymer PSAF prepared by the preparation method according to any one of claims 1 to 7.

10. The application of the sulfonated modified phenolic-acetone-formaldehyde copolymer PSAF according to claim 9 in the preparation of coal-water slurry, oilfield chemicals, and water treatment agents.

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