Method for preparing modified monomer polymer containing polyhydroxy phenolic groups through thermally initiated free radical polymerization reaction

Abstract

The invention belongs to the technical field of polyhydroxy phenolic group modified compound polymerization, and particularly relates to a polyhydroxy phenolic group modified acrylic acid derivative polymer which does not need a protecting group and can be directly prepared through free radical polymerization reaction and a preparation method of the polyhydroxy phenolic group modified acrylic acid derivative polymer. The method comprises the following steps: dissolving a polyhydroxy phenolic group modified acrylic acid derivative monomer or the polyhydroxy phenolic group modified acrylic acid derivative monomer and other acrylic acid derivative monomers into a specific polar aprotic solvent or a mixed solvent of the specific polar aprotic solvent for (co) polymerization in an inert atmosphere by adopting a specific free radical initiator at 10-45 DEG C, thereby effectively inhibiting related side reactions of polyhydroxy phenolic groups. The polymer and the copolymer have the advantages of high molecular weight, narrow molecular weight distribution (PDI is less than or equal to 1.3) and high content (1-100%) of polyhydroxy phenolic group modified acrylic acid derivative monomers. According to the method, polyhydroxy phenol groups do not need to be protected, high stability and high yield (greater than or equal to 90%) of polymerization reaction are ensured, and generation of branched chains and cross-linked macromolecules is remarkably reduced. The process is simple and convenient, low in cost, easy for large-scale production, and suitable for development and application of polyhydroxy phenol group modified high polymer materials.

Description

Technical Field

[0001] This invention relates to the field of polymerization technology for compounds modified with polyhydroxyphenol groups, and specifically to a method for preparing high-quality acrylic derivative monomer polymers containing polyhydroxyphenol groups modified by direct thermal initiation free radical polymerization without the need for protecting groups. Background Technology

[0002] Synthesizing monomers modified with polyhydroxyphenolic groups through molecular design and introducing them into the polymer backbone using free radical polymerization is one of the core strategies for developing high-performance adhesive polymer materials.

[0003] However, polyhydroxyphenolic groups exhibit high reactivity and readily undergo chain transfer reactions with growing chain radicals during thermally initiated free radical polymerization, leading to chain branching and termination. These reactions not only significantly reduce the average molecular weight and broaden the molecular weight distribution of the polymer but also easily generate branched and cross-linked structures, and in severe cases, even form insoluble gels, thereby significantly reducing polymer yield and the content of polyhydroxyphenolic modified monomers in the polymer. Therefore, the direct preparation of polyhydroxyphenolic modified polymers using thermally initiated free radical polymerization still faces technical bottlenecks.

[0004] To avoid the aforementioned side reactions, traditional methods often employ a "protection-deprotection" strategy, which involves temporarily protecting the phenolic hydroxyl groups by introducing protecting groups such as methoxymethyl groups, followed by deprotection under acidic conditions after polymerization. Zhan et al. (ACSSustainable Chemistry & Engineering, 2016, 4(7):3857-63; Biomacromolecules, 2017, 18(9):2959-66) synthesized high molecular weight catechol and pyrogallol modified polymers using this method. Although this strategy can effectively suppress side reactions caused by polyhydroxyphenolic groups and ensure the high molecular weight and controllable structure of the synthesized polymer, its synthesis process is cumbersome, complex, and costly in both economic and environmental aspects. Furthermore, the deprotection process may be incomplete or trigger main chain degradation, significantly limiting its practical industrial application.

[0005] Compared with the traditional "protection-deprotection" strategy, the ability to directly modify monomers with unprotected polyhydroxyphenolic groups for free radical polymerization would undoubtedly greatly simplify the process and reduce production costs, offering significant technical and economic advantages. However, existing research has shown that under unprotected conditions, simply optimizing conventional thermally initiated free radical polymerization conditions is insufficient to effectively suppress side reactions such as chain transfer and chain termination. For example, Yang et al. (Polymer Chemistry, 2015, 6(16):3121-30) reported that in a copolymerization system using dopamine methacrylamide (DMA) and 2-methoxyethyl methacrylate as raw materials, when the DMA content in the total monomers was low, the molecular weight distribution of the resulting polymer was consistently greater than 1.9, and the degree of branching of the polymer increased significantly with increasing DMA content in the total monomers. When the DMA content in the total monomer molar amount exceeded 25%, it easily led to the formation of insoluble crosslinking gels. PUERTAS-BARTOLOMé et al. (European Polymer Journal, 2018, 98:47-55) found that thermally initiated free radical polymerization could only produce low molecular weight copolymers with a catechol-modified methacrylate molar content of 0.9-13.5%, with a yield of only about 15%. Hennig H et al. (Molecules, 2022, 27(13):4027) also found that thermally initiated free radical polymerization was difficult to synthesize copolymers with a DMA molar content exceeding 30 mol%.

[0006] Therefore, when the polyhydroxyphenol groups are not temporarily protected by protecting groups, the preparation of polymers with modified monomers containing polyhydroxyphenol groups by direct thermal initiation free radical polymerization still faces the following problems: (1) high degree of branching, easy formation of insoluble cross-linked gels, and low yield of soluble polymers; (2) the polymer is a polydisperse system with low molecular weight and wide molecular weight distribution; (3) high molecular weight polymers with high content of polyhydroxyphenol group modified monomers are difficult to synthesize, which restricts the further improvement of material properties.

[0007] Therefore, there is an urgent need to develop a new method that can efficiently synthesize high-quality polymers containing polyhydroxyphenolic groups-modified monomers through thermally initiated free radical polymerization without the need for protecting groups, in order to break through the existing technological bottlenecks and meet the application needs of high-performance functional polymer materials. Summary of the Invention

[0008] This invention addresses the technical challenges of polyhydroxyphenol-modified monomers being prone to chain transfer and chain termination reactions during thermally initiated free radical polymerization, making it difficult to achieve high-content polyhydroxyphenol-modified monomers, high molecular weight, narrow molecular weight distribution, and high soluble polymer yield. It provides a method for efficiently preparing high-quality, high-content polyhydroxyphenol-modified acrylic derivative monomer polymers directly through thermally initiated free radical polymerization without the need for protecting groups.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] Under an inert atmosphere, polyhydroxyphenol-modified acrylic derivative monomers, along with other acrylic derivative monomers and a thermal initiator, are dissolved in a polar aprotic solvent or a mixture thereof, and subjected to free radical polymerization at 10–45°C. This effectively suppresses chain transfer and chain termination side reactions involving polyhydroxyphenol groups, thereby preparing soluble polymers or copolymers with high molecular weight, narrow molecular weight distribution, and high polyhydroxyphenol content.

[0011] This invention is the first to propose a method that effectively weakens the reactivity of polyhydroxyphenolic groups and free radicals by synergistically controlling polymerization temperature and polar aprotic solvent environment. Without any chemical protection steps, high-quality monomer polymers modified with polyhydroxyphenolic groups can be efficiently prepared by thermally initiated free radical polymerization, which has significant innovation and broad application prospects.

[0012] This invention provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The method is characterized by using a thermal initiator in a polar aprotic solvent or a mixture thereof at 10–45°C to initiate the free radical polymerization of polyhydroxyphenolic group-modified acrylic derivative monomers, or their free radical copolymerization with other acrylic derivative monomers, to prepare polyhydroxyphenolic group-modified acrylic derivative polymers or copolymers thereof, without the need to protect the monomer side chain groups.

[0013] The polyhydroxyphenolic group modified acrylic derivative monomer is at least one of acrylate monomers and / or acrylamide monomers containing a diphenol, triphenol, tetraphenol or pentphenol structure;

[0014] The other acrylic derivative monomers are at least one of acrylate monomers and / or acrylamide monomers containing special functional groups;

[0015] The thermal initiator is a low-temperature thermal initiator.

[0016] As described above, the monomers of acrylic derivatives modified with polyhydroxyphenol groups are at least one of acrylate monomers or acrylamide monomers containing a diphenol structure or a triphenol structure.

[0017] The other acrylic derivative monomers mentioned above are at least one of conventional acrylate monomers, acrylamide monomers, and acrylic monomers containing special functional groups.

[0018] As mentioned above, the thermal initiator is at least one of 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile) or 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride.

[0019] As described above, the polar aprotic solvent is at least one of N,N-dimethylformamide and dimethyl sulfoxide, or a mixture of the above-mentioned polar aprotic solvents and water.

[0020] The free radical polymerization reaction temperature is 25-45℃ and the reaction time is 2-24h, as described above.

[0021] As described above, based on the total amount of acrylic derivative monomers modified with polyhydroxyphenol groups and other acrylic derivative monomers, the polyhydroxyphenol group-modified acrylic derivative monomers account for 1% to 100% of the total molar amount of monomers; the total concentration of monomers in the mixed solvent is 0.02 to 1.0 mol / L; and the amount of initiator is 0.5% to 10% of the total molar amount of monomers.

[0022] The conversion rate of polyhydroxyphenolic group-modified acrylic derivative monomers by the free radical polymer method described above is not less than 90%; the actual composition of the monomer in the polymer chain of the obtained polymer differs from the composition of the raw materials by no more than 10%; the molecular weight distribution (PDI) of the obtained polymer is not greater than 1.3, and the total yield is not less than 90%.

[0023] The mechanism of this invention is as follows:

[0024] This invention proposes an innovative synergistic regulation strategy by thoroughly investigating the effects of polymerization temperature and polar aprotic solvents on the free radical polymerization process of polyhydroxyphenol-modified acrylic monomers. This strategy achieves efficient and high-content polymerization of polyhydroxyphenol-modified monomers without the need for protecting groups.

[0025] In terms of specific mechanisms, the polymerization temperature is controlled at 10-45℃ by using a low-temperature thermal initiator, which to some extent reduces the chain transfer and chain termination reaction rates between polyhydroxyphenolic groups and growing chain free radicals, and slows down the side reaction process. At the same time, the use of polar aprotic solvents (such as DMF, DMSO, etc.) effectively "passivates" the reactivity of phenolic hydroxyl groups through hydrogen bonding with them, reduces the abstraction of hydroxyl hydrogen by free radicals, and thus inhibits the occurrence of side reactions such as chain transfer and chain termination.

[0026] However, the innovation of this invention lies not merely in simply adding these two methods together, but in discovering and utilizing the significant synergistic effect between them—a non-obvious and previously undisclosed technological breakthrough. Through systematic experiments, this invention has found that when using low-temperature polymerization conditions alone, side reactions remain difficult to control effectively when faced with high levels of polyhydroxyphenolic monomers in the raw materials. The polymers often exhibit polydispersity, low molecular weight, wide distribution, and significantly lower molar content of polyhydroxyphenolic modified monomers than the raw materials. Using polar aprotic solvents alone also fails to completely solve the aforementioned problems caused by the introduction of high-content polyhydroxyphenolic modified monomers. Only by combining low-temperature polymerization technology with a polar aprotic solvent system can an unexpected synergistic inhibition effect be produced, significantly improving the stability of the polymerization reaction and achieving the preparation of high-quality polymers with high molecular weight, narrow distribution, and controllable polyhydroxyphenolic monomer content. The discovery of this synergistic effect and its application in this invention overcomes the bottleneck of traditional free radical polymerization technology in the introduction of polyhydroxyphenolic modified monomers, demonstrating significant creativity and practicality, and providing a novel and efficient technical path for the industrial production of high-performance functional polymers.

[0027] The beneficial effects of this invention are as follows:

[0028] (1) The protection-free process greatly simplifies the synthesis process and reduces the cost of raw materials and energy consumption;

[0029] (2) It significantly increases the content of polyhydroxyphenolic monomers in polymers, and can be controlled within the range of 1 mol% to 100 mol%.

[0030] (3) High molecular weight and narrow molecular weight distribution polymer products were prepared, and the polymer yield and monomer conversion rate were both higher than 90%, which is far superior to the existing thermally initiated free radical polymerization preparation method.

[0031] (4) Effectively suppress branching and cross-linking side reactions to obtain soluble and monodisperse monomer polymers containing polyhydroxyphenolic groups;

[0032] (5) The monomer polymer containing polyhydroxyphenolic groups prepared has better adhesion properties than polymers prepared by existing thermally initiated free radical polymerization;

[0033] (6) It has a wide range of applications, mild process conditions, and is easy to promote industrialization. It is expected to further promote the practical application of monomer polymers containing polyhydroxyphenol groups in the fields of fiber interface modification and medical adhesive materials. Attached Figure Description

[0034] Figure 1 The polymers prepared for Examples 1, 2, and 3 1 H NMR spectrum.

[0035] Figure 2 The polymer prepared for Example 4 1 H NMR spectrum.

[0036] Figure 3 The polymerization kinetics of thermally initiated free radical processes in Examples 1, 2, 3, and 4 are shown.

[0037] Figure 4 Examples 1, 2, 3, 4 and Comparative Example 3, and the molecular weight and molecular weight distribution of the resulting polymers are described.

[0038] Figure 5 The particle size distribution diagram of the polymer in aqueous solution was prepared for Example 1.

[0039] Figure 6 The maximum adhesion speed and adhesion mass corresponding to the polymers prepared in Example 1 and Comparative Example 2 are shown. Detailed Implementation

[0040] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0041] Table 1 Comparison of monomers and structural formulas used in preferred embodiments of the present invention

[0042]

[0043]

[0044] The following are the test methods for the relevant performance indicators in each embodiment and comparative example:

[0045] (1) Polymerization kinetics: using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1¹H NMR was used to quantitatively analyze the monomer conversion rate during thermally initiated free radical polymerization. The process included the following steps: First, during the thermally initiated free radical polymerization, a time gradient sampling method was used to monitor the progress of the reaction. A portion of the reaction solution was taken from each time point using a microsampler, quenched with liquid nitrogen, and then subjected to further analysis. 1 ¹H NMR analysis was performed. Then, the monomer conversion was calculated using the following formula by comparing the integrated area of ​​the residual double-bonded hydrogen atoms in the monomer with the initial area (the area at reaction time 0):

[0046]

[0047] Where f is the initial molar ratio of the feed.

[0048] (2) Molecular weight and molecular weight distribution: The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (PDI) of the polymer were characterized by gel permeation chromatography (GPC). The procedure included the following steps: using dimethyl sulfoxide (DMSO) containing 0.1 mol / L lithium bromide as the mobile phase (flow rate set at 0.5 mL / min, column temperature at 80 °C), the sample was quantified using a polymethyl methacrylate (PMMA) standard curve for calibration.

[0049] (3) Polymer dispersibility study: Dynamic light scattering (DLS) was used to study the dispersibility of the polymer in aqueous solution. The steps included: 1 mg of polymer sample was weighed and dissolved in 2 mL of aqueous solution. The test was performed using a polystyrene cuvette, with an equilibration time of 2 min and a test temperature of 25 °C.

[0050] (4) Polymer Adhesion Test: The adhesion and assembly behavior and adhesion rate of the self-adhesive biomimetic polymer on the material surface were quantitatively analyzed using a quartz microcrystalline balance (QCM). The steps included: A blank chip with a uniformly coated aramid film was placed into the QCM channel detection module, maintained at 25°C throughout, with a peristaltic pump flow rate of 70 μL / min. First, an aqueous solution containing 0.6 M sodium chloride (working solution) was continuously pumped into the QCM detection module for 10 minutes. Then, the mobile phase was changed to a mixture of an aqueous solution containing 1 mg:1 mL polymer and the biomimetic polymer, maintained for 20 minutes. Finally, the working solution was reintroduced for 10 minutes to thoroughly rinse the weakly adhered polymer on the surface until a new equilibrium was reached. The amount of biomimetic polymer adhering to the aramid surface was then obtained, and the polymer adhesion rate was calculated.

[0051] Example 1

[0052] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0053] (1) Preparation of raw materials;

[0054] Polyhydroxyphenolic group modified acrylic derivative monomer: A3;

[0055] Other acrylic acid derivative monomers: B1

[0056] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0057] Solvent: N,N-dimethylformamide / water (v:v = 4:1);

[0058] (2) 215.6 mg (0.667 mmol) of initiator, 830.41 mg (3.5 mmol) of A3 monomer and 839.54 mg (6.5 mmol) of B1 monomer were added to 100 ml of N,N-dimethylformamide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 45 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymer of A3 and B1.

[0059] The test results showed that: the conversion rate of A3 monomer after the reaction was 94.8%; the polymer yield was 95.6%; the actual molar content of A3 in the polymer was 34.1%, which was basically consistent with the theoretical molar content of 35%; the molecular weight of the polymer was 93244 g / mol, the PDI was 1.131, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 14.49 ng·cm⁻¹. -2 ·s -1 The adhesion mass is 1054 ng·cm -2 .

[0060] Comparative Example 1

[0061] A method for preparing polyhydroxyphenolic group modified acrylic derivative polymers during thermally initiated free radical polymerization is basically the same as in Example 1, except that the solvent is water.

[0062] The test results showed that the conversion rate of A3 monomer after the reaction was 91.2%, and the polymer yield was 86.2%. The actual molar content of A3 in the polymer was 29.8%, which deviated from the theoretical molar content of 35%. The number-average molecular weight of the obtained polymer containing A3 monomer was 69704 g / mol, the PDI was 1.594, and the polymer was polydisperse in solution. The maximum adhesion velocity of the polymer to the matrix material surface was 7.498 ng·cm. -2 ·s -1 The adhesion mass was 642.7 ng·cm. -2

[0063] Comparing Comparative Example 1 and Example 1, it can be seen that since Example 1 is a mixed solution of polar aprotic solvents, its synergistic effect with optimized low-temperature reaction conditions can improve the yield and prepare a monodisperse, high molecular weight, narrow molecular weight distribution, and higher A3 molar content polymer product, and the polymer has better adhesion properties.

[0064] Comparative Example 2

[0065] A method for preparing polyhydroxyphenolic group modified acrylic derivative polymers during thermally initiated free radical polymerization is basically the same as in Example 1, except that the initiator is azobisisobutyronitrile.

[0066] Test results showed that a large amount of insoluble gel products were generated after polymerization, accounting for 60% of the total polymer product; the conversion rate of A3 monomer after the reaction was 31.3%, and the polymer yield was 35.3%; the actual molar content of A3 in the polymer was 23.4%, which deviated significantly from the theoretical molar content of 35%; the number-average molecular weight of the polymer containing A3 monomer was 43244 / mol, the PDI of the polymer containing A3 monomer was 3.01, and the polymer dispersion in solution was polydisperse. The maximum adhesion velocity of the polymer to the matrix material surface was 4.755 ng·cm. -2 ·s -1 The adhesion mass was 511.4 ng·cm. -2 .

[0067] Comparing Comparative Example 2 and Example 1, it can be seen that since the low-temperature thermal initiator in Example 1 is used, its synergistic effect with the optimized reaction conditions can improve the yield of monodisperse, high molecular weight, narrow molecular weight distribution, and higher A1 molar content polymer products.

[0068] Comparative Example 3

[0069] A method for preparing polyhydroxyphenolic group modified acrylic derivative polymers during thermally initiated free radical polymerization is basically the same as in Example 1, except that the initiator is azobisisoheptanenitrile.

[0070] Test results showed that insoluble gel products were formed after polymerization, accounting for 45.1% of the total polymer product; the conversion rate of A3 monomer after the reaction was only 52.1%, and the polymer yield was 56.3%; the actual molar content of A3 in the polymer was 26.5%, which deviated significantly from the theoretical molar content of 35%; the number average molecular weight of the obtained polymer containing A3 monomer was 67000 g / mol, the PDI of the polymer containing A3 monomer was 1.643, and the polymer was polydisperse in solution. The maximum adhesion velocity of the polymer to the matrix material surface was 6.480 ng·cm. -2 ·s -1 The adhesion mass was 571.4 ng·cm. -2 .

[0071] Comparing Comparative Example 3 with Example 1, it can be seen that since the low-temperature thermal initiator in Example 1 is used, its synergistic effect with the optimized reaction conditions can improve the yield of monodisperse, high molecular weight, narrow molecular weight distribution, and higher A3 molar content polymer products, and the polymer has better adhesion properties.

[0072] Example 2

[0073] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0074] (1) Preparation of raw materials;

[0075] Polyhydroxyphenolic group modified acrylic derivative monomer: A3;

[0076] Other acrylic acid derivative monomers: B1

[0077] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0078] Solvent: N,N-dimethylformamide / water (v:v = 4:1);

[0079] (2) 215.6 mg (0.667 mmol) of initiator, 593.2 mg (2.5 mmol) of A3 monomer and 968.7 mg (7.5 mmol) of B1 monomer were added to 100 ml of N,N-dimethylformamide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 45 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymer of A3 and B1.

[0080] The test results showed that: the conversion rate of A3 monomer after the reaction was 90.86%; the polymer yield was 95.4%; the actual molar content of A3 in the polymer was 24.2%, which was basically consistent with the theoretical molar content of 25%; the molecular weight of the polymer was 75585 g / mol, the PDI was 1.150, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 13.34 ng·cm. -2 ·s -1 The adhesion mass was 835.4 ng·cm. -2 .

[0081] Example 3

[0082] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0083] (1) Preparation of raw materials;

[0084] Polyhydroxyphenolic group modified acrylic derivative monomer: A3;

[0085] Other acrylic acid derivative monomers: B1

[0086] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0087] Solvent: N,N-dimethylformamide / water (v:v = 4:1);

[0088] (2) 215.6 mg (0.667 mmol) of initiator, 1.186 g (5.0 mmol) of A3 monomer and 645.8 mg (5.0 mmol) of B1 monomer were added to 100 ml of N,N-dimethylformamide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 45 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymer of A3 and B1.

[0089] The test results showed that: the conversion rate of A3 monomer after the reaction was 90.46%; the polymer yield was 96.2%; the actual molar content of A3 in the polymer was 50.1%, which was basically consistent with the theoretical molar content of 50%; the molecular weight of the polymer was 98762 g / mol, the PDI was 1.127, and the polymer was monodisperse in the solution; the maximum adhesion rate of the polymer on the surface of the aramid material was 15.84 ng·cm. -2 ·s -1 The adhesion mass is 1138 ng·cm-2 .

[0090] Example 4

[0091] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0092] (1) Preparation of raw materials;

[0093] Polyhydroxyphenolic group modified acrylic derivative monomer: A1;

[0094] Other acrylic acid derivative monomers: B1

[0095] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0096] Solvent: N,N-dimethylformamide / water (v:v = 4:1);

[0097] (2) 215.6 mg (0.667 mmol) of initiator, 777.4 mg (3.5 mmol) of A1 monomer and 839.5 mg (6.5 mmol) of B1 monomer were added to 100 ml of N,N-dimethylformamide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 45 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymer of A1 and B1.

[0098] The test results showed that: the conversion rate of A1 monomer after the reaction was 94.91%; the polymer yield was 93.7%; the actual molar content of A1 in the polymer was 34.6%, which was basically consistent with the theoretical molar content of 35%; the molecular weight of the polymer was 99913 g / mol, the PDI was 1.255, and the polymer was monodisperse in the solution; the maximum adhesion rate of the polymer on the surface of the aramid material was 10.37 ng·cm. -2 ·s -1 The adhesion mass was 917.7 ng·cm. -2 .

[0099] Example 5

[0100] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0101] (1) Preparation of raw materials;

[0102] Polyhydroxyphenolic group modified acrylic derivative monomer: A1;

[0103] Initiator: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile);

[0104] Solvent: Dimethyl sulfoxide;

[0105] (2) 109.5 mg (0.667 mmol) of initiator and 2.213 g (10 mmol) of A1 monomer were added to 100 ml of dimethyl sulfoxide solution. The mixture was magnetically stirred at 500 rpm and heated to 30 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitate was placed on a vacuum line and dried under vacuum to obtain A1 homopolymer.

[0106] The test results showed that the conversion rate of A1 monomer was 90.41% after the reaction; the polymer yield was 93.40%; the actual molar content of A1 in the polymer was 100%, consistent with the theoretical molar content; the molecular weight of the polymer was 124687 g / mol, the PDI was 1.280, and the polymer was monodisperse in the solution.

[0107] Example 6

[0108] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0109] (1) Preparation of raw materials;

[0110] Polyhydroxyphenolic group modified acrylic derivative monomer: A2;

[0111] Other acrylic acid derivative monomers: B2

[0112] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0113] Solvent: N,N-dimethylformamide / water (v∶v=1∶1);

[0114] (2) 215.3 mg (0.667 mmol) of initiator, 1.036 g (5 mmol) of A2 monomer and 2.372 g (15 mmol) of B2 monomer were added to 100 ml of N,N-dimethylformamide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 45 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymers A2 and B2.

[0115] The test results showed that: the conversion rate of A2 monomer after the reaction was 92.3%; the polymer yield was 94.3%; the actual molar content of A2 in the polymer was 24.3%, which was basically consistent with the theoretical molar content of 25%; the molecular weight of the polymer was 97467 g / mol, the PDI was 1.140, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 12.75 ng·cm. -2 ·s -1 The adhesion mass was 765.4 ng·cm. -2 .

[0116] Example 7

[0117] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0118] (1) Preparation of raw materials;

[0119] Polyhydroxyphenolic group modified acrylic derivative monomer: A3;

[0120] Other acrylic acid derivative monomers: B3

[0121] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0122] Solvent: N,N-dimethylformamide / water (v∶v=2∶1);

[0123] (2) 184.9 mg (0.572 mmol) of initiator, 3.322 g (14 mmol) of A3 monomer and 4.061 g (26 mmol) of B3 monomer were added to 100 ml of N,N-dimethylformamide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 45 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymers of A3 and B3.

[0124] The test results showed that: the conversion rate of A3 monomer after the reaction was 95.4%; the polymer yield was 96.0%; the actual molar content of A3 in the polymer was 35.2%, which was basically consistent with the theoretical molar content of 35%; the molecular weight of the polymer was 104769 g / mol, the PDI was 1.250, and the polymer was monodisperse in the solution; the maximum adhesion velocity of the polymer on the surface of the aramid material was 14.65 ng·cm. -2 ·s -1 The adhesion mass was 986.5 ng·cm. -2 .

[0125] Example 8

[0126] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0127] (1) Preparation of raw materials;

[0128] Polyhydroxyphenolic group modified acrylic derivative monomer: A4;

[0129] Other acrylic acid derivative monomers: B4

[0130] Initiator: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile);

[0131] Solvent: Dimethyl sulfoxide / water (v∶v=1∶1);

[0132] (2) 215.6 mg (0.667 mmol) of initiator, 11.16 g (50 mmol) of A4 monomer and 6.409 mg (50 mmol) of B4 monomer were added to 100 ml of dimethyl sulfoxide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 40 °C for 5 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymers of A4 and B4.

[0133] The test results showed that: the conversion rate of A4 monomer after the reaction was 91.7%; the polymer yield was 93.1%; the actual molar content of A4 in the polymer was 50.2%, which was basically consistent with the theoretical molar content of 50%; the molecular weight of the polymer was 107346 g / mol, the PDI was 1.196, and the polymer dispersion in the solution was monodisperse; the maximum adhesion velocity of the polymer on the surface of the aramid material was 16.89 ng·cm. -2 ·s -1The adhesion mass was 1204.9 ng·cm. -2 .

[0134] Example 9

[0135] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0136] (1) Preparation of raw materials;

[0137] Polyhydroxyphenolic group modified acrylic derivative monomer: A5;

[0138] Other acrylic acid derivative monomers: B5

[0139] Initiator: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile);

[0140] Solvent: Dimethyl sulfoxide / water (v∶v=2∶1);

[0141] (2) 46.23 mg (0.143 mmol) of initiator, 556.0 mg (2.5 mmol) of A5 monomer and 1.179 g (7.5 mmol) of B5 monomer were added to 100 ml of dimethyl sulfoxide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 35 °C for 18 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymers of A5 and B5.

[0142] The test results showed that: the conversion rate of A5 monomer after the reaction was 90.3%; the polymer yield was 92.4%; the actual molar content of A5 in the polymer was 24.1%, which was basically consistent with the theoretical molar content of 25%; the molecular weight of the polymer was 94574 g / mol, the PDI was 1.220, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 11.67 ng·cm. -2 ·s -1 The adhesion mass was 876.3 ng·cm. -2 .

[0143] Example 10

[0144] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0145] (1) Preparation of raw materials;

[0146] Polyhydroxyphenolic group modified acrylic derivative monomer: A6;

[0147] Other acrylic acid derivative monomers: B6

[0148] Initiator: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile);

[0149] Solvent: Dimethyl sulfoxide;

[0150] (2) 46.96 mg (0.286 mmol) of initiator, 1.458 g (7 mmol) of A6 monomer and 2.018 g (13 mmol) of B6 monomer were added to 100 ml of dimethyl sulfoxide mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 15 °C for 24 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and vacuum dried to obtain the polymer of A6 and B6.

[0151] The test results showed that: the conversion rate of A6 monomer after the reaction was 90.6%; the polymer yield was 90.8%; the actual molar content of A6 in the polymer was 33.9%, which was basically consistent with the theoretical molar content of 35%; the molecular weight of the polymer was 117642 g / mol, the PDI was 1.180, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 14.37 ng·cm. -2 ·s -1 The adhesion mass was 946.5 ng·cm. -2 .

[0152] Example 11

[0153] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0154] (1) Preparation of raw materials;

[0155] Polyhydroxyphenolic group modified acrylic derivative monomer: A7;

[0156] Other acrylic acid derivative monomers: B7

[0157] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0158] Solvent: N,N-dimethylformamide / water (v:v = 4:1);

[0159] (2) 3.233 mg (0.01 mmol) of initiator, 2.382 g (10 mmol) of A7 monomer and 1.151 g (10 mmol) of B7 monomer were added to 100 ml of N,N-dimethylformamide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 35 °C for 24 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the A7 and B7 polymer.

[0160] The test results showed that the conversion rate of A7 monomer after the reaction was 94.8%; the polymer yield was 95.2%; the actual molar content of A7 in the polymer was 49.2%, which was basically consistent with the theoretical molar content of 50%; the molecular weight of the polymer was 187649 g / mol, the PDI was 1.170, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 17.01 ng·cm⁻¹. -2 ·s -1 The adhesion mass was 1037.9 ng·cm. -2 .

[0161] Example 12

[0162] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0163] (1) Preparation of raw materials;

[0164] Polyhydroxyphenolic group modified acrylic derivative monomer: A8;

[0165] Other acrylic acid derivative monomers: B8

[0166] Initiator: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile);

[0167] Solvent: N,N-dimethylformamide;

[0168] (2) 164.1 mg (0.999 mmol) of initiator, 1.682 g (7.5 mmol) of A3 monomer and 3.243 g (22.5 mmol) of B8 monomer were added to 100 ml of N,N-dimethylformamide solution. The mixture was magnetically stirred at 500 rpm and heated to 30 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymers of A8 and B8.

[0169] The test results showed that: the conversion rate of A8 monomer after the reaction was 92.7%; the polymer yield was 93.7%; the actual molar content of A8 in the polymer was 24.5%, which was basically consistent with the theoretical molar content of 25%; the molecular weight of the polymer was 117465 g / mol, the PDI was 1.230, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 10.47 ng·cm. -2 ·s -1 The adhesion mass was 942.3 ng·cm. -2 .

[0170] Example 13

[0171] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0172] (1) Preparation of raw materials;

[0173] Polyhydroxyphenolic group modified acrylic derivative monomer: A1;

[0174] Other acrylic acid derivative monomers: B9

[0175] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0176] Solvent: Dimethyl sulfoxide / water (v∶v=2∶1);

[0177] (2) 431.2 mg (1.334 mmol) of initiator, 1.549 g (7 mmol) of A1 monomer and 1.848 g (13 mmol) of B9 monomer were added to 100 ml of dimethyl sulfoxide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 45 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to the unsuitable solvent acetone. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and vacuum dried to obtain the polymer of A1 and B9.

[0178] The test results showed that: the conversion rate of A1 monomer after the reaction was 96.4%; the polymer yield was 97.0%; the actual molar content of A1 in the polymer was 34.7%, which was basically consistent with the theoretical molar content of 35%; the molecular weight of the polymer was 967435 g / mol, the PDI was 1.150, and the polymer was monodisperse in the solution; the maximum adhesion rate of the polymer on the surface of the aramid material was 15.30 ng·cm. -2 ·s -1 The adhesion mass was 1102.4 ng·cm.-2 .

[0179] Example 14

[0180] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0181] (1) Preparation of raw materials;

[0182] Polyhydroxyphenolic group modified acrylic derivative monomer: A2;

[0183] Other acrylic derivative monomers: B10

[0184] Initiator: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile);

[0185] Solvent: Dimethyl sulfoxide;

[0186] (2) 546.8 mg (3.33 mmol) of initiator, 10.36 g (50 mmol) of A2 monomer and 5.708 g (50 mmol) of B10 monomer were added to 100 ml of dimethyl sulfoxide solution. The mixture was magnetically stirred at 500 rpm and heated to 20 °C for 18 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitate was placed on a vacuum line and dried under vacuum to obtain the polymer of A2 and B10.

[0187] The test results showed that: the conversion rate of A2 monomer after the reaction was 95.2%; the polymer yield was 96.3%; the actual molar content of A2 in the polymer was 49.0%, which was basically consistent with the theoretical molar content of 50%; the molecular weight of the polymer was 134768 g / mol, the PDI was 1.190, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 16.32 ng·cm. -2 ·s -1 The adhesion mass was 1305.6 ng·cm. -2 .

[0188] Example 15

[0189] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0190] (1) Preparation of raw materials;

[0191] Polyhydroxyphenolic group modified acrylic derivative monomer: A3;

[0192] Other acrylic acid derivative monomers: B11

[0193] Initiator: 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile);

[0194] Solvent: N,N-dimethylformamide;

[0195] (2) 23.48 mg (0.143 mmol) of initiator, 593.2 mg (2.5 mmol) of A3 monomer and 1.074 g (7.5 mmol) of B11 monomer were added to 100 ml of N,N-dimethylformyl solution. The mixture was magnetically stirred at 500 rpm and heated to 35 °C for 8 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitate was placed on a vacuum line and dried under vacuum to obtain the polymer of A3 and B11.

[0196] The test results showed that: the conversion rate of A3 monomer after the reaction was 93.1%; the polymer yield was 94.5%; the actual molar content of A3 in the polymer was 25.3%, which was basically consistent with the theoretical molar content of 25%; the molecular weight of the polymer was 126791 g / mol, the PDI was 1.210, and the polymer was monodisperse in the solution; the maximum adhesion rate of the polymer on the surface of the aramid material was 10.68 ng·cm. -2 ·s -1 The adhesion mass was 846.7 ng·cm. -2 .

[0197] Example 16

[0198] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0199] (1) Preparation of raw materials;

[0200] Polyhydroxyphenolic group modified acrylic derivative monomer: A4;

[0201] Other acrylic derivative monomers: B12

[0202] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0203] Solvent: Dimethyl sulfoxide / water (v∶v=1∶1);

[0204] (2) 1.294 g (4.002 mmol) of initiator, 4.688 g (21 mmol) of A4 monomer and 5.506 g (39 mmol) of B12 monomer were added to 100 ml of dimethyl sulfoxide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 40 °C for 18 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and vacuum dried to obtain the polymer of A4 and B12.

[0205] The test results showed that: the conversion rate of A4 monomer after the reaction was 94.6%; the polymer yield was 96.1%; the actual molar content of A4 in the polymer was 35.2%, which was basically consistent with the theoretical molar content of 35%; the molecular weight of the polymer was 97641 g / mol, the PDI was 1.201, and the polymer dispersion in the solution was monodisperse; the maximum adhesion velocity of the polymer on the surface of the aramid material was 14.39 ng·cm. -2 ·s -1 The adhesion mass was 912.8 ng·cm. -2 .

[0206] Example 17

[0207] This embodiment provides a method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization. The steps are as follows:

[0208] (1) Preparation of raw materials;

[0209] Polyhydroxyphenolic group modified acrylic derivative monomer: A5;

[0210] Other acrylic acid derivative monomers: B1

[0211] Initiator: 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride;

[0212] Solvent: N,N-dimethylformamide / water (v:v = 4:1);

[0213] (2) 862.5 mg (2.668 mmol) of initiator, 4.445 g (20 mmol) of A5 monomer and 2.583 g (20 mmol) of B1 monomer were added to 100 ml of N,N-dimethylformamide / water mixed solution. The mixture was magnetically stirred at 500 rpm and heated to 45 °C for 12 h. After the reaction was completed, the reaction solution was added dropwise to acetone, a poor solvent. The insoluble matter was collected by centrifugation at 8000 rpm. The precipitated product was placed on a vacuum line and dried under vacuum to obtain the polymer of A5 and B1.

[0214] The test results showed that: the conversion rate of A5 monomer after the reaction was 93.5%; the polymer yield was 95.6%; the actual molar content of A5 in the polymer was 48.9%, which was basically consistent with the theoretical molar content of 50%; the molecular weight of the polymer was 104796 g / mol, the PDI was 1.163, and the polymer dispersion in the solution was monodisperse; the maximum adhesion rate of the polymer on the surface of the aramid material was 16.97 ng·cm. -2 ·s -1 The adhesion mass was 1275.6 ng·cm. -2 .

Claims

1. A method for suppressing side reactions of polyhydroxyphenolic compounds and preparing polyhydroxyphenolic group-modified acrylic derivative polymers during thermally initiated free radical polymerization, characterized in that: Under conditions where there is no need to protect the side chain groups of the monomer, a thermal initiator is used to initiate the free radical polymerization reaction of polyhydroxyphenol-modified acrylic derivative monomers or their free radical copolymerization reaction with other acrylic derivative monomers in a polar aprotic solvent or a mixture thereof at 10–45°C, thereby preparing polyhydroxyphenol-modified acrylic derivative polymers or their copolymers.

2. The method as described in claim 1, characterized in that, Includes the following steps: Polyhydroxyphenol-modified acrylic derivative monomers, other acrylic derivative monomers, and thermal initiators are dissolved in a polar aprotic solvent or a mixture thereof, and free radical polymerization is carried out at 10–45 °C under an inert atmosphere. After the reaction is completed, the product is purified to obtain a polymer or copolymer of polyhydroxyphenol-modified acrylic derivatives. Furthermore: The polyhydroxyphenolic group modified acrylic derivative monomer is at least one of acrylate monomers and / or acrylamide monomers containing a diphenol, triphenol, tetraphenol or pentphenol structure; The other acrylic derivative monomers are at least one of acrylate monomers and / or acrylamide monomers containing special functional groups; The thermal initiator is a low-temperature thermal initiator.

3. The method as described in claim 2, characterized in that, The thermal initiator is a thermal initiator with a 10-hour half-life and a temperature not exceeding 45°C.

4. The method as described in claim 3, characterized in that, The polyhydroxyphenolic group-modified acrylic derivative monomer is further defined as at least one of acrylate monomers and / or acrylamide monomers containing a diphenol or triphenol structure.

5. The method as described in claim 4, characterized in that, The polar aprotic solvent is further defined as at least one of N,N-dimethylformamide and dimethyl sulfoxide, or a mixture of the above polar aprotic solvent and water.

6. The method as described in claim 5, characterized in that, The thermal initiator is further defined as at least one of 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile) or 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride.

7. The method as described in claim 6, characterized in that, The polyhydroxyphenolic group-modified acrylic derivative monomer is further limited to at least one of the acrylamide monomers containing a diphenol structure or a triphenol structure.

8. The method as described in claim 7, characterized in that, The free radical polymerization reaction is preferably carried out at 25–45°C.

9. The method as described in claim 7, characterized in that: Based on the amount of raw materials added, the monomer of the polyhydroxyphenol group modified acrylic derivative is 1% to 100% of the total molar amount of monomer; the total concentration of monomer in the mixed solvent is 0.02 to 1.0 mol / L; and the amount of initiator is 0.5% to 10% of the total molar amount of monomer.

10. The method as described in claim 7, characterized in that, The conversion rate of the polyhydroxyphenolic group-modified acrylic derivative monomer is not less than 90%; the difference between the actual composition of the monomer in the polymer chain and the composition of the raw materials added in the obtained polymer does not exceed 10%; the molecular weight distribution (PDI) of the obtained polymer is not greater than 1.3, and the total yield is not less than 90%.

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