Polystyrene-like polymers degradable under acidic conditions and methods for their preparation
By embedding easily broken covalent bonds and introducing specific substituent groups into the polymer backbone, the problem of the difficulty in degrading polymer materials under acidic conditions has been solved, achieving efficient degradation and expanding the scope of applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GREATER BAY AREA UNIV (IN PREPARATION)
- Filing Date
- 2026-02-06
- Publication Date
- 2026-05-29
AI Technical Summary
Existing polymer materials are difficult to degrade under acidic conditions, leading to serious plastic pollution problems and limiting their application in the biomedical field.
Ethylene oxide monomers are used to insert easily broken covalent bonds into the polymer backbone through free radical ring-opening polymerization, and specific substituent groups are introduced to improve their degradation performance under acidic conditions. Polymers containing benzyloxy structural segments are then obtained through catalytic hydrogenation.
This technology enables efficient degradation of polymers under acidic conditions, improves monomer conversion and polymer molecular weight, and expands the application range of polymer materials.
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Figure CN122103545A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer materials technology, specifically relating to a polystyrene-like polymer that is degradable under acidic conditions and its preparation method. Background Technology
[0002] Free radical polymerization is a crucial method for producing polymer materials. In the global polymer market, over 40% of polymers are prepared via free radical polymerization, such as widely used general-purpose polymers like low-density polyethylene, polystyrene, polyvinyl chloride, polyacrylate, and polyvinyl acetate, all obtained from their respective vinyl monomers through free radical polymerization. However, these polymers possess a highly stable carbon-carbon backbone structure, making them degradeable only under harsh conditions. This contributes to the increasingly serious global plastic pollution problem and limits their application in the biomedical field.
[0003] Therefore, improving the biodegradability of polymer materials has become one of the important strategies for reducing plastic pollution and expanding the application range of polymer materials. Summary of the Invention
[0004] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the present invention proposes a polystyrene-like polymer that is degradable under acidic conditions and a method for preparing the same. This polystyrene-like polymer can degrade into small molecule compounds under acidic conditions and exhibits excellent degradation performance.
[0005] The inventive concept of this invention is as follows: This invention uses vinyl ethylene oxide (VO) monomers to synthesize polystyrene-like polymers, and embeds easily broken covalent bonds in the polymer backbone through free radical ring-opening polymerization to improve its responsive degradation performance under acidic conditions.
[0006] Specifically, the VO monomer used in this invention is modified by introducing different substituent groups at the 1 and 3 positions of the VO structure. (e.g., substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups): After a free radical ring-opening polymerization reaction, the resulting polymer backbone will contain enol ether structural segments. These segments can degrade under acidic conditions, thus giving the obtained polymer PSI the property of being degradable under acidic conditions. Simultaneously, polymer PSI can be catalytically hydrogenated to obtain another novel polystyrene-like polymer, PSII. Because this polymer backbone contains benzyloxy groups, it can also degrade under acidic conditions.
[0007] Furthermore, introducing a substituent at the 3-position of the VO structure enhances the free radical polymerization reactivity of the VO monomer, leading to highly efficient free radical polymerization and consequently increasing monomer conversion and polymer molecular weight. Introducing a substituent at the 1-position of the VO structure results in a benzyloxyether structural fragment in the polymer backbone, which enables the polymer to degrade under acidic conditions. Introducing substituents at other sites not only increases synthetic difficulty but also results in poor polymer degradation performance.
[0008] To address the aforementioned technical problems, a first aspect of the present invention provides a polystyrene-like polymer, comprising polymer PSI or polymer PSII, wherein polymer PSII is a catalytic hydrogenation product of polymer PSI, and the structural formulas of polymer PSI and polymer PSII are shown in formula (1) and formula (2), respectively: Equation (1), Equation (2); Wherein: R1 and R2 are independently selected from any one of substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups, wherein the substitution is by at least one of halogen, methoxy, ester, cyano, amide, carbonyl, and alkyl groups; n is an integer greater than 0.
[0009] In some embodiments of the present invention, the heteroaryl group is selected from any one of pyridyl, furanyl, and thiophene.
[0010] A second aspect of the present invention provides a method for preparing the polystyrene-like polymer described in the first aspect of the present invention, comprising the following steps: (1) Synthesize vinyl ethylene oxide monomers, i.e., VO monomers, the structural formula of which is shown in formula (3): Equation (3); (2) The VO monomer undergoes a free radical homopolymerization reaction to obtain the polymer PSI; (3) The polymer PSI is subjected to catalytic hydrogenation to obtain the polymer PSII.
[0011] In some embodiments of the present invention, the synthetic route of the VO monomer is as follows: ; The synthesis process of the VO monomer includes the following steps: adding the brominated product and dimethyl sulfide to water for reaction; then adding an aldehyde compound and a first organic solvent, cooling, and continuing the reaction under alkaline conditions to obtain the VO monomer.
[0012] In some embodiments of the present invention, the first organic solvent is selected from at least one of isopropanol and dioxane.
[0013] In some embodiments of the present invention, the cooling temperature range is -5°C to 5°C.
[0014] In some embodiments of the present invention, the continued reaction time is 10-15 hours.
[0015] In some embodiments of the present invention, after the reaction continues under alkaline conditions, the step of separating and purifying the reaction product is further included, namely, adding saturated ammonium chloride and ethyl acetate to the reaction solution, separating the liquids, then washing 3-5 times with an organic phase saturated sodium chloride solution, drying, and then purifying by rotary column chromatography or recrystallization to obtain the VO monomer.
[0016] In some embodiments of the present invention, the preparation process of the polymer PSI includes the following steps: The VO monomer and initiator were mixed and heated under anaerobic conditions to carry out a free radical homopolymerization reaction, thereby obtaining the polymer PSI.
[0017] In some embodiments of the present invention, the initiator is selected from at least one of organic peroxides and azo compounds; for example, di-tert-butyl peroxide (DTBP), azobisisobutyronitrile (AIBN), etc.
[0018] In some embodiments of the present invention, a solvent may be added to the VO monomer and the initiator for mixing together. The solvent is used to dissolve the VO monomer, such as chlorobenzene, xylene, and anisole.
[0019] In some embodiments of the present invention, the molar ratio of the VO monomer to the initiator is 1:(0.0001-0.1). For example, the molar ratio of the VO monomer to the initiator is 1:0.0001, 1:0.0005, 1:0.001, 1:0.005, 1:0.01, 1:0.05, or 1:0.1, etc., including but not limited to the listed values. Other unlisted values within the range of these values also apply.
[0020] In some embodiments of the present invention, the heating temperature is 50-150°C. For example, the heating temperature is 50°C, 80°C, 100°C, 120°C, or 150°C, etc., including but not limited to the listed values. At the same time, other unlisted values within the range of the listed values also apply.
[0021] In some embodiments of the present invention, the free radical homopolymerization reaction time is 3-28 hours. For example, the free radical homopolymerization reaction time is 3 hours, 5 hours, 10 hours, 15 hours, 20 hours, 24 hours, or 28 hours, etc., including but not limited to the listed values. At the same time, other unlisted values within the range of the listed values also apply.
[0022] In some embodiments of the present invention, the preparation process of the polymer PSII includes the following steps: The polymer PSI is dissolved in a second organic solvent, a catalyst is added, and a catalytic hydrogenation reaction is carried out under a hydrogen atmosphere to obtain the polymer PSII.
[0023] In some embodiments of the present invention, the catalyst comprises a metal catalyst, wherein the active component of the metal catalyst is selected from at least one of nickel, palladium, platinum, rhodium, and ruthenium.
[0024] In some embodiments of the present invention, the second organic solvent is an organic solvent that can dissolve polymer PSI, such as tetrahydrofuran, dioxane, toluene, etc.
[0025] In some embodiments of the present invention, the molar ratio of the polymer PSI to the catalyst is 1:(0.0005-0.5); for example, the molar ratio of the polymer PSI to the catalyst is 1:0.0005, 1:0.001, 1:0.01, 1:0.1 or 1:0.5, etc., including but not limited to the listed values. At the same time, other unlisted values within the range of the listed values are also applicable.
[0026] In some embodiments of the present invention, the catalytic hydrogenation reaction time is 3-48 hours; for example, the catalytic hydrogenation time is 3 hours, 8 hours, 12 hours, 24 hours, 36 hours or 48 hours, etc., including but not limited to the listed values, and other unlisted values within the range of the listed values are also applicable.
[0027] In some embodiments of the present invention, the pressure of the hydrogen atmosphere is 0.1-10 Mbar; for example, the pressure of the hydrogen atmosphere is 0.1 Mbar, 1 Mbar, 4 Mbar, 8 Mbar or 10 Mbar, etc., including but not limited to the listed values, and other unlisted values within the range of the listed values also apply.
[0028] A third aspect of the present invention provides a polymeric material whose raw materials include the polystyrene-like polymer described in the first aspect of the present invention.
[0029] In some embodiments of the present invention, the polymeric material includes biomedical polymeric materials, photoresist polymeric materials, etc., all of which can be degraded under acidic conditions.
[0030] Compared with the prior art, the above-described technical solution of the present invention has at least the following technical effects or advantages: (1) This invention synthesizes a novel VO monomer by introducing specific substituents at the 1 and 3 positions of the VO structure, and uses this monomer to prepare a novel polystyrene-like polymer containing an enol ether structural segment in the main chain through a free radical ring-opening polymerization reaction. This type of polymer can be degraded under acidic conditions. At the same time, another novel polymer containing a benzyloxy structural segment can be prepared by catalytic hydrogenation of this polymer. Similarly, this type of polymer can also be degraded under acidic conditions.
[0031] (2) The VO monomer of the present invention has the advantages of simple synthesis method, strong structural controllability and good stability. Using this VO monomer to synthesize polystyrene-like polymers is beneficial to improve the free radical polymerization activity of VO monomer, enabling efficient free radical polymerization, improving monomer conversion rate and polymer molecular weight, and achieving a number average molecular weight of polymer greater than 10,000. Attached Figure Description
[0032] Figure 1 The polystyrene-like polymer PSI-1 prepared in Example 1 of this invention 1 H-NMR spectrum; Figure 2 The polystyrene-like polymer PSII-1 prepared in Example 1 of this invention 1 H-NMR spectrum; Figure 3 The polystyrene-like polymer PSI-2 prepared in Example 2 of this invention 1 H-NMR spectrum; Figure 4 The polystyrene-like polymer PSI-3 prepared in Example 3 of this invention 1 H-NMR spectrum; Figure 5 The GPC test results of the degradation products of the polystyrene-like polymer PSI-1 prepared in Example 1 of this invention under acidic conditions; Figure 6 The GPC test results are for the degradation products of the polystyrene-like polymer PSII-1 prepared in Example 1 of this invention under acidic conditions. Detailed Implementation
[0033] The present invention will now be described in detail with reference to embodiments to facilitate understanding of the invention by those skilled in the art. It is particularly important to note that the embodiments are merely illustrative of the invention and should not be construed as limiting the scope of protection of the invention. Non-essential improvements and adjustments made to the invention by those skilled in the art based on the above description should still fall within the scope of protection of the invention. Furthermore, all raw materials mentioned below, unless otherwise specified, are commercially available products; all process steps or preparation methods not mentioned in detail are process steps or preparation methods known to those skilled in the art.
[0034] Example 1 A method for preparing a polystyrene-like polymer includes the following steps: (1) The synthesis route and steps of 1,3-diphenylvinyl ethylene oxide monomer (VO1) are as follows:
[0035] (3-bromoprop-1-en-2-yl)benzene (19.7 g, 0.1 mol) and dimethyl sulfide (6.82 g, 0.11 mol) were placed in a reaction flask, and 10 mL of water was added. The mixture was then reacted overnight at room temperature. Excess dimethyl sulfide was removed by rotary evaporation, and then 20 mL of isopropanol and benzaldehyde (10.6 g, 0.1 mol) were added. The reaction mixture was cooled to 0 °C, and then sodium hydroxide solution (4.0 g dissolved in 4 mL of water) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours. 50 mL of protective ammonium chloride and 50 mL of ethyl acetate were added to the reaction flask, and the mixture was separated. The organic phase was washed three times with saturated sodium chloride solution, dried, and purified by rotary column chromatography to obtain 1,3-diphenylvinyl ethylene oxide (VO1, 15.54 g). 1 H NMR (400 MHz, CDCl3) δ 7.45 – 7.28 (m, 10H), 5.51 (s, 1H),5.46 (s, 1H), 3.72 (d, J = 2.0 Hz, 1H), 3.68 (d, J = 2 Hz, 1H). (2) The synthesis route and steps of the polystyrene-like polymer PSI-1 are as follows:
[0036] 1,3-Diphenylvinyl ethylene oxide (VO1, 2.22 g) was dissolved in 2 mL of chlorobenzene, and di-tert-butyl peroxide (DTBP, 7.3 mg) was added. Nitrogen gas was bubbled through to remove oxygen, and the mixture was stirred at 125 °C for 24 hours. The reaction solution was poured into methanol, filtered, and 2.0 g of polystyrene-like polymer PSI-1 was obtained in 90% yield (GPC test results: [missing information]). Mn 31200, :1.85; polystyrene is a standard.
[0037] (3) The synthesis route and steps of the polystyrene-like polymer PSII-1 are as follows:
[0038] 1.0 g of polystyrene-like polymer PSI-1 was dissolved in 5 mL of THF, and 200 mg of palladium on carbon was added. The mixture was then reacted at room temperature for 48 hours under a 4 M bar hydrogen atmosphere. The palladium on carbon was subsequently filtered off, and the filtrate was poured into methanol to obtain 0.8 g of polystyrene-like polymer PSII-1 (GPC test results: [missing information]). :27100, PDI:1.85; polystyrene is a standard product).
[0039] Example 2 A method for preparing a polystyrene-like polymer includes the following steps: (1) The synthesis route and steps of 1-(4-fluorophenyl-3-phenylvinyl ethylene oxide monomer (VO2) are as follows:
[0040] (3-bromoprop-1-en-2-yl)benzene (9.85 g, 0.05 mol) and dimethyl sulfide (3.41 g, 0.055 mol) were placed in a reaction flask, and 5 mL of water was added. The mixture was then reacted overnight at room temperature. Excess dimethyl sulfide was removed by rotary evaporation, and then 10 mL of isopropanol and 4-fluorobenzaldehyde (6.2 g, 0.05 mol) were added. The reaction mixture was cooled to 0 °C, and then sodium hydroxide solution (2 g dissolved in 2 mL of water) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours. 25 mL of saturated ammonium chloride and 25 mL of ethyl acetate were added to the reaction flask, and the mixture was separated. The organic phase was washed three times with saturated sodium chloride solution, dried, and purified by rotary column chromatography to obtain 1-(4-fluoro)phenyl-3-phenylvinyl ethylene oxide (VO2, 9.0 g). 1 H NMR (500 MHz, CDCl3) δ 7.43 – 7.38 (m, 2H), 7.38 –7.26 (m, 5H), 7.09 – 7.01 (m, 2H), 5.50 (d, J = 1.1 Hz, 1H), 5.45 (d, J = 1.1Hz, 1H), 3.69 (d, J = 2.0 Hz, 1H), 3.63 (d, J = 2.0, 2.0 Hz, 1H). (2) The synthesis route and steps of the polystyrene-like polymer PSI-2 are as follows:
[0041] 1-(4-fluoro)phenyl-3-phenylvinyl ethylene oxide (VO2, 2.40 g) was dissolved in 2 mL of chlorobenzene, and di-tert-butyl peroxide (DTBP, 7.3 mg) was added. Nitrogen gas was bubbled through to remove oxygen, and the mixture was stirred at 125 °C for 24 hours. The reaction solution was poured into methanol, filtered, and 2.2 g of a polystyrene-like polymer PSI-2 was obtained in 92% yield (GPC test results: [missing information]). Mn :30300, PDI:1.75; polystyrene is a standard product).
[0042] (3) The synthesis route and steps of the polystyrene-like polymer PSII-2 are as follows:
[0043] 1.0 g of polystyrene-like polymer PSI-2 was dissolved in 5 mL of THF, and 200 mg of palladium on carbon was added. The mixture was then reacted at room temperature for 48 hours under a 4 M bar hydrogen atmosphere. The palladium on carbon was subsequently filtered off, and the filtrate was poured into methanol. Filtration yielded 0.75 g of polystyrene-like polymer PSII-2 (GPC test results: [not provided]). Mn :26100, 1.75; polystyrene is a standard.
[0044] Example 3 A method for preparing a polystyrene-like polymer includes the following steps: (1) The synthesis of 1-(3,4-dimethoxy)phenyl-3-phenylvinyl ethylene oxide monomer (VO3) is described below, including the following synthetic route and steps:
[0045] (3-bromoprop-1-en-2-yl)benzene (3.94 g, 0.02 mol) and dimethyl sulfide (1.55 g, 0.025 mol) were placed in a reaction flask, and 5 mL of water was added. The mixture was then reacted overnight at room temperature. Excess dimethyl sulfide was removed by rotary evaporation, and then 10 mL of isopropanol and 3,4-dimethoxybenzaldehyde (3.32 g, 0.02 mol) were added. The reaction mixture was cooled to 0 °C, and then sodium hydroxide solution (0.8 g dissolved in 2 mL of water) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours. 25 mL of saturated ammonium chloride and 25 mL of ethyl acetate were added to the reaction flask, and the mixture was separated. The organic phase was washed three times with saturated sodium chloride solution, dried, and purified by rotary column chromatography to obtain 1-(3,4-dimethoxy)phenyl-3-phenylvinyl ethylene oxide (VO3, 3.69 g). 1H NMR (500 MHz, CDCl3) δ 7.46 –7.38 (m, 2H), 7.37 – 7.26 (m, 3H), 6.94 (dd, J = 8.2, 2.0 Hz, 1H), 6.89 – 6.82(m, 2H), 5.50 (s, 1H), 5.45 (s, 1H), 3.87 (s, 6H), 3.67 (s, 2H). (2) The synthesis route and steps of the polystyrene-like polymer PSI-3 are as follows:
[0046] 1-(3,4-dimethoxy)phenyl-3-phenylvinyl ethylene oxide (VO3, 2.80 g) was dissolved in 2 mL of chlorobenzene, and di-tert-butyl peroxide (DTBP, 7.3 mg) was added. Nitrogen gas was bubbled through to remove oxygen, and the mixture was stirred at 125 °C for 24 hours. The reaction solution was poured into methanol, filtered, and 2.38 g of polystyrene-like polymer PSI-3 was obtained in 85% yield (GPC test results: [missing information]). Mn :28300, PDI:1.77; polystyrene is a standard product).
[0047] (3) The synthesis route and steps of the polystyrene-like polymer PSII-3 are as follows:
[0048] 1.0 g of polystyrene-like polymer PSI-3 was dissolved in 5 mL of THF, and 200 mg of palladium on carbon was added. The mixture was then reacted at room temperature for 48 hours under a 4 M bar hydrogen atmosphere. The palladium on carbon was subsequently filtered off, and the filtrate was poured into methanol. Filtration yielded 0.65 g of polystyrene-like polymer PSII-3 (GPC test results: [missing information]). Mn :23800, :1.79; polystyrene is a standard.
[0049] Example 4 A method for preparing a polystyrene-like polymer includes the following steps: (1) The synthesis route and steps of 1-phenyl-3-(4-methyl)phenylvinyl ethylene oxide monomer (VO4) are as follows:
[0050] 4-(3-bromoprop-1-en-2-yl)toluene (4.22 g, 0.02 mol) and dimethyl sulfide (1.55 g, 0.025 mol) were placed in a reaction flask, and 5 mL of water was added. The mixture was then reacted overnight at room temperature. Excess dimethyl sulfide was removed by rotary evaporation, and then 10 mL of isopropanol and benzaldehyde (2.12 g, 0.02 mol) were added. The reaction mixture was cooled to 0 °C, and then sodium hydroxide solution (0.8 g dissolved in 2 mL of water) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours. 25 mL of saturated ammonium chloride and 25 mL of ethyl acetate were added to the reaction flask, and the mixture was separated. The organic phase was washed three times with saturated sodium chloride solution, dried, and purified by rotary column chromatography to obtain 1-phenyl-3-(4-methyl)phenylvinyl ethylene oxide (VO4, 3.3 g). 1 H NMR (500 MHz, CDCl3) δ 7.43 – 7.27 (m, 7H),7.10 (d, J = 8.8 Hz, 2H), 5.44 (d, J = 1.1 Hz, 1H), 5.37 (d, J = 1.1 Hz, 1H), 3.69 (d, J = 2.0 Hz, 1H), 3.63 (d, J = 2.0 Hz, 1H), 2.30 (s, 3H). (2) The synthesis route and steps of the polystyrene-like polymer PSI-4 are as follows:
[0051] 1-Phenyl-3-(4-methyl)phenylvinyl ethylene oxide (VO4, 2.36 g) was dissolved in 2 mL of chlorobenzene, and di-tert-butyl peroxide (DTBP, 7.3 mg) was added. Nitrogen gas was bubbled through to remove oxygen, and the mixture was stirred at 125 °C for 24 hours. The reaction solution was poured into methanol, filtered, and 2.14 g of polystyrene-like polymer PSI-4 was obtained in 91% yield (GPC test results: [missing information]). Mn :29200, PDI:1.83; polystyrene is a standard product).
[0052] (3) The synthesis route and steps of the polystyrene-like polymer PSII-4 are as follows:
[0053] 1.0 g of polystyrene-like polymer PSI-4 was dissolved in 5 mL of THF, and 200 mg of palladium on carbon was added. The mixture was then reacted at room temperature for 48 hours under a 4 M bar hydrogen atmosphere. The palladium on carbon was subsequently filtered off, and the filtrate was poured into methanol. Filtration yielded 0.82 g of polystyrene-like polymer PSII-4 (GPC test results: [missing information]). Mn 27800, :1.69; polystyrene is a standard.
[0054] Example 5 A method for preparing a polystyrene-like polymer includes the following steps: (1) The synthesis route and steps of 1-phenyl-3-(4-methoxy)phenyl vinyl ethylene oxide monomer (VO5) are as follows:
[0055] 4-(3-bromoprop-1-en-2-yl)methoxybenzene (4.54 g, 0.02 mol) and dimethyl sulfide (1.55 g, 0.025 mol) were placed in a reaction flask, and 5 mL of water was added. The mixture was then reacted overnight at room temperature. Excess dimethyl sulfide was removed by rotary evaporation, and then 10 mL of isopropanol and benzaldehyde (2.12 g, 0.02 mol) were added. The reaction mixture was cooled to 0 °C, and then sodium hydroxide solution (0.8 g dissolved in 2 mL of water) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 12 hours. 25 mL of saturated ammonium chloride and 25 mL of ethyl acetate were added to the reaction flask, and the mixture was separated. The organic phase was washed three times with saturated sodium chloride solution, dried, and purified by rotary column chromatography to obtain 1-phenyl-3-(4-methoxy)phenyl vinyl ethylene oxide (VO5, 3.0 g). 1 H NMR (500 MHz, CDCl3) δ 7.43 – 7.27(m, 7H), 6.82 (d, J = 9.0 Hz, 2H), 5.38 (d, J = 1.1 Hz, 1H), 5.32 (d, J = 1.1Hz, 1H), 3.75 (s, 3H), 3.66 (d, J = 1.8 Hz, 1H), 3.61 (d, J = 2.0, Hz, 1H). (2) The synthesis route and steps of the polystyrene-like polymer PSI-5 are as follows:
[0056] 1-Phenyl-3-(4-methoxy)phenylvinyl ethylene oxide (VO5, 2.52 g) was dissolved in 2 mL of chlorobenzene, and di-tert-butyl peroxide (DTBP, 7.3 mg) was added. Nitrogen gas was bubbled through to remove oxygen, and the mixture was stirred at 125 °C for 24 hours. The reaction solution was poured into methanol, filtered, and 2.21 g of polystyrene-like polymer PSI-5 was obtained in 88% yield (GPC test results: [missing information]). Mn 32200, :1.79; polystyrene is a standard.
[0057] (3) The synthesis route and steps of the polystyrene-like polymer PSII-5 are as follows:
[0058] 1.0 g of polystyrene-like polymer PSI-5 was dissolved in 5 mL of THF, and 200 mg of palladium on carbon was added. The mixture was then reacted at room temperature for 48 hours under a 4 M bar hydrogen atmosphere. The palladium on carbon was subsequently filtered off, and the filtrate was poured into methanol. Filtration yielded 0.72 g of polystyrene-like polymer PSII-5 (GPC test results: [missing information]). M n:24900, :1.83; polystyrene is a standard.
[0059] Performance testing The polystyrene-like polymer PSI-1 (121 mg) prepared in Example 1 was dissolved in 2 mL of DCM, trifluoroacetic acid was added, and the mixture was stirred overnight at room temperature. The solution was then evaporated to dryness, and the molecular weights of the polymer and the remaining product were determined by GPC. The results are as follows: Figure 5 As shown. By Figure 5 It can be seen that the molecular weight of polymer PSI-1 degraded from 31200 to 450, indicating that PSI-1 can be degraded into small molecule compounds under acidic conditions and has good degradability.
[0060] The polystyrene-like polymer PSII-1 (122 mg) prepared in Example 1 was dissolved in 2 mL of DCM, trifluoroacetic acid was added, and the mixture was stirred overnight at room temperature. The solution was then evaporated to dryness, and the molecular weights of the polymer and the remaining product were determined by GPC. The results are as follows: Figure 6 As shown. By Figure 6 It can be seen that the molecular weight of polymer PSII-1 decreased from 27100 to 280, indicating that PSII-1 can also be degraded into small molecule compounds under acidic conditions, demonstrating good degradability.
[0061] For those skilled in the art, several simple deductions or substitutions can be made without departing from the inventive concept, without requiring creative effort. Therefore, any simple improvements made to this invention by those skilled in the art based on the disclosure of this invention should be within the scope of protection of this invention. The above embodiments are preferred embodiments of this invention, and all processes similar to this invention and equivalent changes should fall within the scope of protection of this invention.
Claims
1. A polystyrene-like polymer, characterized in that, This includes polymer PSI or polymer PSII, wherein polymer PSII is the product of the catalytic hydrogenation reaction of polymer PSI, and the structural formulas of polymer PSI and polymer PSII are shown in formula (1) and formula (2), respectively: Equation (1), Equation (2); Wherein: R1 and R2 are independently selected from any one of substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups, wherein the substitution is by at least one of halogen, methoxy, ester, cyano, amide, carbonyl, and alkyl groups; n is an integer greater than 0.
2. The polystyrene-like polymer according to claim 1, characterized in that, The heteroaryl group is selected from any one of pyridyl, furanyl, and thiophene.
3. A method for preparing a polystyrene-like polymer as described in any one of claims 1-2, characterized in that, Includes the following steps: (1) Synthesize vinyl ethylene oxide monomers, i.e., VO monomers, the structural formula of which is shown in formula (3): Equation (3); (2) The VO monomer undergoes a free radical homopolymerization reaction to obtain the polymer PSI; (3) The polymer PSI is subjected to catalytic hydrogenation to obtain the polymer PSII.
4. The method for preparing the polystyrene-like polymer according to claim 3, characterized in that, The synthetic route for the VO monomer is as follows: ； The synthesis process of the VO monomer includes the following steps: adding the brominated product and dimethyl sulfide to water for reaction; then adding an aldehyde compound and a first organic solvent, cooling, and continuing the reaction under alkaline conditions to obtain the VO monomer.
5. The method for preparing the polystyrene-like polymer according to claim 4, characterized in that, The cooling temperature range is -5°C to 5°C.
6. The method for preparing the polystyrene-like polymer according to claim 3, characterized in that, The preparation process of the polymer PSI includes the following steps: The VO monomer was mixed with an initiator and heated under anaerobic conditions to carry out a free radical homopolymerization reaction, thereby obtaining the polymer PSI.
7. The method for preparing the polystyrene-like polymer according to claim 6, characterized in that, The initiator is selected from at least one of organic peroxides and azo compounds; And / or, the molar ratio of the VO monomer to the initiator is 1:(0.0001-0.1). And / or, the heating temperature is 50-150°C.
8. The method for preparing the polystyrene-like polymer according to claim 3, characterized in that, The preparation process of the polymer PSII includes the following steps: The polymer PSI is dissolved in a second organic solvent, a catalyst is added, and a catalytic hydrogenation reaction is carried out under a hydrogen atmosphere to obtain the polymer PSII.
9. The method for preparing the polystyrene-like polymer according to claim 8, characterized in that, The catalyst includes a metal catalyst; And / or, the molar ratio of the polymer PSI to the catalyst is 1:(0.0001-0.5).
10. A polymer material, characterized in that, The raw materials for its preparation include the polystyrene-like polymers described in any one of claims 1-2.