Star polymer for inhibiting crystallization wrapping phenomenon in hydrogenated bisphenol A production process and preparation method thereof
The star-shaped polymer prepared by the invention suppresses the crystallization and encapsulation phenomenon of hydrogenated bisphenol A, improves product purity and catalyst recovery rate, solves the problem of reduced product purity and catalyst loss caused by crystallization and encapsulation in the prior art, and achieves a highly efficient suppression effect that is environmentally friendly and pollution-free.
Patent Information
- Application Number
- CN202511185946.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-22
- Publication Date
- 2026-02-06
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. The crystallization encapsulation phenomenon is suppressed by hydrogen bonding and steric hindrance. The preparation method includes atom transfer radical polymerization and esterification reaction.
It significantly improves the purity of hydrogenated bisphenol A and the catalyst recovery rate, reduces catalyst residue, and does not introduce new impurities. It also has good thermal stability and environmental friendliness.
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Abstract
Description
[0001] The present application relates to the technical field of chemical production, and particularly relates to a star polymer for inhibiting crystallization encapsulation in the production process of hydrogenated bisphenol A and a preparation method thereof. BACKGROUND
[0002] Hydrogenated bisphenol A (HBPA) is an important organic chemical raw material and is widely used in the synthesis of high-performance materials such as epoxy resin and polycarbonate. In the production process of hydrogenated bisphenol A, crystallization encapsulation is a common and serious problem. When hydrogenated bisphenol A is crystallized from the solution, impurities, unreacted raw materials and catalysts in the mother liquor are easily encapsulated in the crystal, resulting in problems such as reduction of product purity, loss of catalyst and difficulty in subsequent processing.
[0003] Conventionally, in order to inhibit crystallization encapsulation, people have adopted various methods. For example, by controlling the crystallization conditions such as temperature, cooling rate, stirring speed, etc. to improve the growth morphology of the crystal, but the effect of these methods is limited and it is difficult to completely avoid the occurrence of encapsulation. In addition, adding a surfactant or dispersant is also a commonly used method, however, the existing surfactants or dispersants have poor dispersion effect in the hydrogenated bisphenol A system, and may introduce new impurities, affecting the product quality.
[0004] Therefore, it is of important industrial application value to develop a method which is efficient, environmentally friendly and does not introduce new impurities to inhibit the crystallization encapsulation in the production process of hydrogenated bisphenol A. SUMMARY
[0005] The purpose of the present application is to provide a star polymer for inhibiting crystallization encapsulation in the production process of hydrogenated bisphenol A and a preparation method thereof, which can effectively inhibit crystallization encapsulation, improve the product purity and catalyst recovery rate of hydrogenated bisphenol A, and does not introduce new impurities, and the preparation method is simple and environmentally friendly.
[0006] In order to achieve the above purpose, the present application is implemented by the following technical scheme:
[0007] The synthesis of a star polymer for inhibiting crystallization encapsulation in the production process of hydrogenated bisphenol A, the star polymer has a star topology structure with polyacrylic acid as the main chain and polyethylene glycol as the side chain, and effectively inhibits the occurrence of crystallization encapsulation through the hydrogen bond interaction between the carboxylic acid group and the crystallization substance and the steric hindrance effect provided by the side chain.
[0008] Further, the star polymer of the present application has a multi-functional compound as the core, and the multi-functional compound has at least three functional groups, such as pentaerythritol, diethylenetriamine, etc.
[0009] Further, the star polymer extends from the core a plurality of polyacrylic acid main chains, each of which has a molecular weight of 5,000-20,000 g / mol, preferably 8,000-15,000 g / mol.
[0010] Further, the polyacrylic acid main chain is grafted with a polyethylene glycol side chain, the polyethylene glycol side chain has a molecular weight of 500-2,000 g / mol, preferably 1,000-1,500 g / mol. The grafting rate of the polyethylene glycol side chain is 20%-50% (molar ratio), preferably 30%-40%.
[0011] Further, the preparation method of the star polymer comprises the following steps:
[0012] 1. Synthesis of star polyacrylic acid core: using a multi-functional compound as an initiator, the polymerization of acrylic acid monomers is initiated by the atom transfer radical polymerization (ATRP) method to form a star polyacrylic acid with the multi-functional compound as the core and a plurality of polyacrylic acid chains as the arms. The reaction conditions are as follows: under the protection of inert gas, CuBr / PMDETA is used as the catalyst system, the reaction temperature is 60-80℃, and the reaction time is 8-24 hours.
[0013] 2. Grafting of polyethylene glycol side chain: esterification reaction is carried out between the star polyacrylic acid and polyethylene glycol monomethyl ether (mPEG-OH) in the presence of a catalyst to graft the polyethylene glycol side chain onto the polyacrylic acid main chain. The catalyst is preferably N,N'-dicyclohexyl carbodiimide (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 treatment: after the reaction is completed, the insoluble by-products are removed by filtration, then the reaction solution is purified by dialysis, and finally the pure star polymer is obtained by freeze-drying.
[0015] Compared with the prior art, the present application has the following advantages and beneficial effects:
[0016] 1. Efficient inhibition of crystallization wrapping phenomenon: the star polymer of the present application can effectively inhibit the occurrence of the crystallization wrapping phenomenon through the hydrogen bonding between the carboxyl groups and the hydroxyl groups on the surface of the hydrogenated bisphenol A crystal, as well as the steric hindrance effect provided by the polyethylene glycol side chain, thereby improving the product purity of the hydrogenated bisphenol A. Experimental results show that after adding the star polymer of the present application, the purity of the hydrogenated bisphenol A can be increased from 98.2% by the traditional method to more than 99.6%, and the catalyst residue can be reduced from 5.2 ppm to less than 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. Attached Figure Description
[0020] Figure 1 This is a schematic diagram of the PAA-PEG star polymer.
[0021] Figure 2 The results are for purity analysis of hydrogenated bisphenol A crystals and detection of catalyst residue. Detailed Implementation
[0022] 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.
[0023] 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.
[0024] Example 1:
[0025] 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%).
[0026] Example 2:
[0027] 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%).
[0028] Example 3:
[0029] 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%).
[0030] Application Example: Application of star-shaped polymers in suppressing the crystallization and encapsulation phenomenon of hydrogenated bisphenol A
[0031] 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.
[0032] The methanol solution of hydrogenated bisphenol A was divided into four portions, and each portion was treated as follows:
[0033] 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.
[0034] 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.
[0035] 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.
[0036] 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.
[0037] 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.
[0038] 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.
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, the polymerization of acrylic acid monomers is initiated 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, so that the polyethylene glycol side chains are grafted onto the polyacrylic acid backbone. 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.
7. The preparation method according to claim 6, 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 8, 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.