Star polymer for inhibiting crystallization wrapping phenomenon in hydrogenated bisphenol A production process and preparation method thereof
The star-shaped polymer prepared suppresses the crystallization and encapsulation phenomenon of hydrogenated bisphenol A, improves product purity and catalyst recovery rate, solves the problem of crystallization and encapsulation in the existing technology, and achieves efficient and environmentally friendly product quality improvement.
Patent Information
- Application Number
- CN202511789695.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-01
- Publication Date
- 2026-03-20
AI Technical Summary
Existing technologies are insufficient to effectively suppress crystallization and encapsulation during the production of hydrogenated bisphenol A, leading to reduced product purity and catalyst loss. Furthermore, commonly used methods may introduce new impurities.
A star-shaped polymer with polyacrylic acid as the main chain and polyethylene glycol as the side chain is used to suppress the occurrence of crystallization encapsulation phenomenon through hydrogen bonding between the carboxylic acid groups and the surface of hydrogenated bisphenol A crystals and the steric hindrance effect of the polyethylene glycol side chain.
It significantly improves the purity of hydrogenated bisphenol A and the catalyst recovery rate, increasing the purity from 98.2% to 99.6% and reducing the catalyst residue from 5.2 ppm to below 0.8 ppm, without introducing new impurities.
Smart Images
Figure FT_1 
Figure FT_2
Abstract
Description
[0001] This invention relates to the field of chemical production technology, specifically to a star-shaped polymer for suppressing crystallization and encapsulation phenomena during the production of hydrogenated bisphenol A and its preparation method. Background Technology
[0002] Hydrogenated bisphenol A (HBPA), as an important organic chemical raw material, is widely used in the synthesis of high-performance materials such as epoxy resins and polycarbonates. In the production process of hydrogenated bisphenol A, crystal encapsulation is a common and serious problem. When hydrogenated bisphenol A crystallizes from solution, it easily encapsulates impurities from the mother liquor, unreacted raw materials, and catalysts within the crystals, leading to reduced product purity, catalyst loss, and difficulties in subsequent processing.
[0003] Traditionally, various methods have been employed to suppress crystallization encapsulation. For example, controlling crystallization conditions such as temperature, cooling rate, and stirring speed can improve crystal growth morphology; however, these methods have limited effectiveness and cannot completely prevent encapsulation. Adding surfactants or dispersants is another common method; however, existing surfactants or dispersants have poor dispersion effects in hydrogenated bisphenol A systems and may introduce new impurities, affecting product quality.
[0004] Therefore, developing an efficient, environmentally friendly method that does not introduce new impurities to suppress crystallization encapsulation during the production of hydrogenated bisphenol A has significant industrial application value. Summary of the Invention
[0005] The purpose of this invention is to provide a star-shaped polymer for suppressing crystallization and encapsulation during the production of hydrogenated bisphenol A and its preparation method. This star-shaped polymer can effectively suppress crystallization and encapsulation, improve the product purity and catalyst recovery rate of hydrogenated bisphenol A, and does not introduce new impurities. Moreover, the preparation method is simple and environmentally friendly.
[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:
[0007] Synthesis of a star polymer for suppressing crystallization encapsulation during the production of hydrogenated bisphenol A. The star polymer has a star topology with polyacrylic acid as the main chain and polyethylene glycol as the side chain. Through hydrogen bonding between the carboxylic acid groups and the crystals, as well as the steric hindrance effect provided by the side chains, the occurrence of crystallization encapsulation is effectively suppressed.
[0008] Furthermore, the star-shaped polymer of the present invention is based on a multifunctional compound having at least three functional groups, such as pentaerythritol, diethylenetriamine, etc.
[0009] Furthermore, the star-shaped polymer extends from the core into multiple polyacrylic acid backbones, each with a molecular weight of 5,000-20,000 g / mol, preferably 8,000-15,000 g / mol.
[0010] Furthermore, polyethylene glycol side chains are grafted onto the polyacrylic acid backbone. The molecular weight of the polyethylene glycol side chains is 500-2,000 g / mol, preferably 1,000-1,500 g / mol. The grafting rate of the polyethylene glycol side chains is 20%-50% (molar ratio), preferably 30%-40%.
[0011] Furthermore, the method for preparing the star-shaped polymer includes the following steps:
[0012] 1. Synthesis of a star-shaped polyacrylic acid core: Using a multifunctional compound as an initiator, acrylic acid monomers are polymerized via atom transfer radical polymerization (ATRP) to form a star-shaped polyacrylic acid core with multiple polyacrylic acid chains as arms. The reaction conditions are: under inert gas protection, using CuBr / PMDETA as a catalyst system, a reaction temperature of 60-80℃, and a reaction time of 8-24 hours.
[0013] 2. Grafting of polyethylene glycol side chains: Star-shaped polyacrylic acid is esterified with polyethylene glycol monomethyl ether (mPEG-OH) in the presence of a catalyst, thereby grafting polyethylene glycol side chains onto the polyacrylic acid backbone. The preferred catalysts are N,N'-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP), the reaction solvent is dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF), the reaction temperature is 20-50℃, and the reaction time is 24-72 hours.
[0014] 3. Purification: After the reaction is complete, insoluble byproducts are removed by filtration, the reaction solution is then purified by dialyzing, and finally freeze-dried to obtain pure star polymer.
[0015] Compared with the prior art, this application has the following advantages and beneficial effects:
[0016] 1. Highly Effective Suppression of Crystallization Encapsulation: The star-shaped polymer of this invention effectively suppresses crystallization encapsulation through hydrogen bonding between the carboxylic acid groups and the hydroxyl groups on the surface of hydrogenated bisphenol A crystals, as well as the steric hindrance effect provided by the polyethylene glycol side chains, thereby improving the purity of hydrogenated bisphenol A. Experimental results show that after adding the star-shaped polymer of this invention, the purity of hydrogenated bisphenol A can be increased from 98.2% using conventional methods to over 99.6%, and the catalyst residue can be reduced from 5.2 ppm to below 0.8 ppm.
[0017] 2. Environmentally friendly and pollution-free: The star-shaped polymer of the present invention does not contain harmful substances and is easy to remove during subsequent processing, without introducing new impurities, thus meeting environmental protection requirements.
[0018] 3. Simple preparation method: The star polymer preparation method of the present invention adopts atom transfer radical polymerization and esterification reaction. The reaction conditions are mild, the operation is simple, and it is easy to carry out industrial production.
[0019] 4. Good thermal stability: The star-shaped polymer of the present invention has good thermal stability and can withstand high temperature conditions during the production of hydrogenated bisphenol A without decomposition or deterioration, thus ensuring its effect of inhibiting crystallization and encapsulation. Detailed Implementation
[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to represent selected embodiments of the invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0021] In the description of this invention, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined with "first" and "second" may explicitly or implicitly include one or more of that feature.
[0022] Example 1:
[0023] Under nitrogen protection, 1.3 g (5 mmol) pentaerythritol, 5.0 g (69 mmol) acrylic acid, 0.07 g (0.5 mmol) CuBr, and 0.10 g (0.5 mmol) PMDETA were dissolved in 50 mL of DMF and reacted at 60 °C for 8 hours. After the reaction was complete, the reaction solution was purified by passing it through a neutral alumina column to obtain star-shaped polyacrylic acid (Mn = 12,000 g / mol, PDI = 1.28). 2.0 g of the above star-shaped polyacrylic acid (COOH content approximately 10 mmol) was dissolved in 30 mL of DMSO, and 3.0 g (3 mmol) mPEG-OH (Mn = 1,000), 2.06 g (10 mmol) DCC, and 0.12 g (1 mmol) DMAP were added, and the mixture was reacted at room temperature for 48 hours. After the reaction was completed, the insoluble byproduct DCU was removed by filtration. The filtrate was then placed in a dialysis bag (molecular weight cutoff 8,000-14,000 Da) and dialyzed in deionized water for 3 days, with the water changed 3 times a day. Finally, the dialyzed solution was freeze-dried to obtain a white powdery star-shaped polymer PAA-PEG-1 (grafting rate 30%).
[0024] Example 2:
[0025] The star polymer PAA-PEG-2 was prepared according to the method of Example 1, except that in the polyethylene glycol side chain grafting step, 6.0 g (3 mmol) mPEG-OH (Mn=2,000) was used instead of 3.0 g (3 mmol) mPEG-OH (Mn=1,000) to obtain the star polymer PAA-PEG-2 (grafting rate 30%).
[0026] Example 3:
[0027] The star polymer PAA-PEG-3 was prepared according to the method of Example 1, except that in the grafting step of polyethylene glycol side chains, 4.5 g (4.5 mmol) mPEG-OH (Mn=1,000) was used instead of 3.0 g (3 mmol) mPEG-OH (Mn=1,000) to obtain star polymer PAA-PEG-3 (grafting rate 45%).
[0028] Application Example: Application of star-shaped polymers in suppressing the crystallization and encapsulation phenomenon of hydrogenated bisphenol A
[0029] In a 1L high-pressure reactor, 100g of bisphenol A, 200mL of methanol, and 5g of Pd / C catalyst were added. Hydrogen gas was introduced until the pressure reached 5MPa, and the reaction was carried out at 120℃ for 4 hours to obtain a hydrogenated bisphenol A solution. The reaction solution was cooled to room temperature, and the catalyst was removed by filtration to obtain a methanol solution of hydrogenated bisphenol A.
[0030] The methanol solution of hydrogenated bisphenol A was divided into four portions, and each portion was treated as follows:
[0031] 1. Control group: No star polymer was added; crystallization was performed directly. The solution was slowly cooled to 0°C with stirring and maintained for 1 hour. Then, the solution was filtered, the crystals were collected, washed three times with cold methanol, and dried under vacuum at 50°C to constant weight.
[0032] 2. Experimental Group 1: Add 0.3g (0.3wt%) of star-shaped polymer PAA-PEG-1 and crystallize it using the same method as the control group.
[0033] 3. Experimental Group 2: Add 0.3g (0.3wt%) of star-shaped polymer PAA-PEG-2 and crystallize it using the same method as the control group.
[0034] 4. Experimental Group 3: Add 0.3g (0.3wt%) of star-shaped polymer PAA-PEG-3 and crystallize it using the same method as the control group.
[0035] The purity of the obtained hydrogenated bisphenol A crystals and the amount of residual catalyst were analyzed. The results are as follows: Figure 2 As shown.
[0036] from Figure 2 It can be seen that after adding the star-shaped polymer of the present invention, the purity of hydrogenated bisphenol A is significantly improved, the residual amount of catalyst is greatly reduced, the average particle size is increased, and the content of mother liquor encapsulation is reduced, indicating that the star-shaped polymer of the present invention can effectively suppress the crystallization and encapsulation phenomenon in the production process of hydrogenated bisphenol A. Attached Figure Description
[0037] Figure 1 Schematic diagram of PAA-PEG star polymer
[0038] Figure 2 Results of purity analysis and catalyst residue detection of hydrogenated bisphenol A crystals.
Claims
1. A star-shaped polymer for suppressing crystallization and encapsulation during the production of hydrogenated bisphenol A, characterized in that, The star polymer has a star-shaped topology with polyacrylic acid as the main chain and polyethylene glycol as the side chain. The star polymer suppresses the occurrence of crystal encapsulation phenomenon through hydrogen bonding between the carboxylic acid groups and the crystals, as well as the steric hindrance effect provided by the side chains.
2. The star-shaped polymer according to claim 1, characterized in that, The star-shaped polymer has polyacrylic acid as the main chain, and the multifunctional compound is pentaerythritol or diethylenetriamine.
3. The star-shaped polymer according to claim 1, characterized in that, The molecular weight of each polyacrylic acid backbone is 5,000-20,000 g / mol.
4. The star-shaped polymer according to claim 1, characterized in that, The molecular weight of the polyethylene glycol side chain is 500-2,000 g / mol.
5. The star-shaped polymer according to claim 1, characterized in that, The grafting rate of the polyethylene glycol side chains is 20%-50% (molar ratio).
6. The method for preparing the star-shaped polymer, characterized in that, Includes the following steps: 1) Synthesis of star-shaped polyacrylic acid core: Using a multifunctional compound as an initiator, acrylic acid monomers are polymerized by atom transfer radical polymerization to form a star-shaped polyacrylic acid with a multifunctional compound as the core and multiple polyacrylic acid chains as arms; 2) Grafting of polyethylene glycol side chains: The star-shaped polyacrylic acid is esterified with polyethylene glycol monomethyl ether in the presence of a catalyst to graft polyethylene glycol side chains onto the polyacrylic acid backbone; 3) Purification treatment: After the reaction is completed, insoluble byproducts are removed by filtration, the reaction solution is then purified by dialyzing, and finally freeze-dried to obtain a pure star-shaped polymer.
7. The preparation method according to claim 10, characterized in that, In the core step of synthesizing star-shaped polyacrylic acid, the reaction conditions are as follows: under inert gas protection, using CuBr / PMDETA as a catalyst system, the reaction temperature is 60-80℃, and the reaction time is 8-24 hours.
8. The star-shaped polymer is used to suppress crystallization and encapsulation during the production of hydrogenated bisphenol A.
9. The application according to claim 9, characterized in that, In the crystallization process of hydrogenated bisphenol A, 0.1%-1.0% (mass percentage) of the star polymer is added to the solution, and then the process is carried out according to conventional crystallization procedures.