Poly (p-hydroxystyrene) resin as well as preparation method and application thereof

Abstract

The invention discloses poly (p-hydroxystyrene) resin as well as a preparation method and application thereof, and belongs to the technical field of high polymer materials. A prepolymer synthesis-block copolymerization step-by-step strategy is adopted, firstly, a poly (p-hydroxystyrene) prepolymer solution and a polyurea resin prepolymer solution are prepared respectively, then the two prepolymer solutions are subjected to block copolymerization under the action of a catalyst, and target resin is obtained through post-treatment. By introducing a polyurea chain segment into a poly-p-hydroxystyrene molecular structure, many defects of traditional poly-p-hydroxystyrene resin are effectively overcome, synergistic improvement of thermal stability, mechanical properties, dielectric properties, heat and humidity resistance, etching resistance and dimensional stability of the resin is realized, and the prepared resin is excellent in film-forming property, good in mechanical property and good in mechanical property. The method can be widely applied to the fields of semiconductor photoresists, electronic packaging, liquid crystal display orientation layers and the like, particularly shows prominent performance in high-end electronic and flexible display scenes, and has remarkable industrial application value.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a poly(p-hydroxystyrene) resin, its preparation method, and its application. Background Technology

[0002] Poly(p-hydroxystyrene) resin is a functional polymer material with high heat resistance (Tg≈150~180℃) and modifiable hydroxyl groups. The benzene ring and side-chain hydroxyl groups in its molecular structure endow it with excellent film-forming properties, chemical stability and dielectric properties (Dk≈3.0). These properties make PHS resin irreplaceable in semiconductor photoresists (such as KrF / ArF photolithography), liquid crystal display alignment layers (such as OLED planarization) and pharmaceutical sustained-release carriers.

[0003] However, poly(p-hydroxystyrene) with a single structure has significant performance limitations, making it difficult to meet the stringent requirements of advanced technologies for comprehensive material performance: First, pure PHS resin is highly brittle, with an elongation at break typically below 5%, making it prone to film cracking during photoresist coating and device packaging, affecting device reliability; second, pure PHS resin has a high surface energy, and the hydrophilicity of its side-chain hydroxyl groups causes the PHS film to easily absorb moisture from the environment, resulting in a significant decrease in dielectric properties under high temperature and humidity conditions, and insufficient corrosion protection for metal substrates; furthermore, pure PHS resin has limited resistance to plasma etching, making it difficult to meet the requirements in advanced semiconductor processes. In scenarios such as 5G high-frequency chip packaging, the coefficient of thermal expansion (CTE) of pure PHS does not match that of silicon substrates (≈3ppm / ℃), making it difficult to meet dimensional stability requirements.

[0004] To overcome these shortcomings, the industry has explored various improvement methods. A common approach is random copolymerization with other monomers, such as copolymerization with tert-butyl methacrylate (TBMA) to enhance chemical amplification, or copolymerization with fluorinated monomers to improve etching resistance. However, these methods often lead to a decline in other properties, such as reduced thermal stability, phase separation problems, or decreased film uniformity. Another approach is to introduce protecting groups (such as t-BOC groups) to improve photosensitivity, but this increases process complexity and cost, and byproducts are easily generated during the removal of protecting groups, leading to pattern defects. Furthermore, there is a strategy of using nanoparticle composite modification, adjusting the coefficient of thermal expansion by adding nanofillers such as silica and aluminum nitride; however, nanoparticles have poor dispersibility and easily introduce impurities, affecting the electrical performance of semiconductor devices.

[0005] Therefore, developing a poly(p-hydroxystyrene) resin that takes into account multiple dimensions of performance has become the key to breaking through the technical bottleneck. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention proposes a poly(p-hydroxystyrene) resin, its preparation method, and its applications, aiming to solve at least one of the aforementioned problems. This invention employs a step-by-step strategy of "prepolymer synthesis-block copolymerization" to introduce polyurea segments into the poly(p-hydroxystyrene) molecular structure, achieving a synergistic improvement in the resin's heat resistance, mechanical properties, dielectric properties, etching resistance, and process compatibility, thus expanding its applications in high-end fields.

[0007] This invention achieves its technical objective through the following technical solutions: A method for preparing poly(p-hydroxystyrene) resin, the method comprising the following steps: Step S1: Raw material preparation; Step S2: Synthesis of poly(p-hydroxystyrene) prepolymer to obtain poly(p-hydroxystyrene) prepolymer solution; Step S3: Synthesis of polyurea resin prepolymer to obtain polyurea resin prepolymer solution; Step S4, Block copolymerization reaction: The poly(p-hydroxystyrene) prepolymer solution obtained in step S2 and the polyurea resin prepolymer solution obtained in step S3 are added to the same reactor to obtain the block copolymerization reaction mixture. Step S5: Post-process the block copolymer reaction mixture obtained in step S4 to obtain the poly(p-hydroxystyrene) resin.

[0008] Compared with the prior art, the present invention has at least the following beneficial effects: The poly(p-hydroxystyrene) resin, its preparation method, and its applications provided by this invention utilize a step-by-step strategy of "prepolymer synthesis-block copolymerization" to precisely introduce polyurea segments into the poly(p-hydroxystyrene) molecular structure. This effectively overcomes the bottleneck of the single performance characteristic of traditional poly(p-hydroxystyrene) resins, achieving a unified approach of multi-dimensional performance enhancement and excellent process compatibility. In terms of performance, this resin significantly enhances thermal stability, enabling it to withstand high-temperature processes in advanced technology scenarios. It also achieves a balance of "high strength and high toughness" in mechanical properties, solving the problems of high brittleness and easy cracking inherent in traditional resins. Furthermore, it possesses a low dielectric constant, adapting to the signal transmission requirements of high-frequency electronic devices. Its hydrophobicity is significantly improved, reducing the adverse effects of water vapor adsorption on dielectric properties and metal substrate protection. It also optimizes the coefficient of thermal expansion to adapt to the substrate, reducing the risk of interfacial stress during encapsulation. Its resistance to plasma etching is also significantly enhanced, ensuring the pattern accuracy and low defect rate of photolithography processes. At the process and application level, this preparation method effectively avoids problems such as phase separation and gelation, exhibits excellent film-forming properties, is compatible with existing production processes, requires no equipment modification, and lowers the industrialization threshold. It can be widely used not only in the fields of semiconductor photoresists and electronic packaging materials, but also performs outstandingly in liquid crystal display alignment layers, especially in the field of flexible displays. It can meet the performance requirements of different scenarios, and does not rely on expensive raw materials or complex processes, resulting in lower raw material costs. The post-processing is environmentally friendly with no toxic byproducts, which is in line with the trend of green production. It provides a high-performance and highly adaptable solution for the field of high-end electronic materials and has significant industrial application value. Detailed Implementation

[0009] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. The illustrative embodiments and descriptions of this invention are only used to explain this invention and are not intended to limit this invention.

[0010] Specifically, the present invention provides a poly(p-hydroxystyrene) resin and a method for preparing the same, the method comprising the following steps: Step S1: Raw material preparation Take p-hydroxystyrene monomer, isocyanate monomer, diamine monomer, and N,N-dimethylformamide (DMF), and purify and / or dry them for later use; wherein, the purification and / or drying treatment includes: purifying p-hydroxystyrene monomer by vacuum distillation at 0.01-0.05 MPa and 80-100℃ to a purity ≥99.5%; purifying isocyanate monomer by vacuum distillation at 0.005-0.02 MPa and 60-80℃ to a purity ≥99%; drying diamine monomer in a vacuum drying oven at 50-70℃ for 2-4 hours to a purity ≥99%; and drying N,N-dimethylformamide (DMF) through a molecular sieve for more than 48 hours to a purity ≥99.8%. Preferably, the isocyanate monomers are selected from one or more of TDI, MDI, HDI, IPDI, HMDI and fluorinated isocyanates; the diamine monomers are preferably polyether diamines or diamine monomers containing hindered amine structures, such as piperazine diamines.

[0011] Step S2: Synthesis of poly(p-hydroxystyrene) prepolymer A certain amount of p-hydroxystyrene monomer purified in step S1 (its molar amount is denoted as n) is added to a reaction vessel. Then, DMF dried in step S1 is added to the reaction vessel, and the amount added is adjusted to ensure that the mass percentage of p-hydroxystyrene monomer in the total solution in the reaction vessel is 15-25%. Next, an initiator such as azobisisobutyronitrile (AIBN) is added to the reaction vessel. The amount of AIBN is 0.5-1% of the mass of p-hydroxystyrene monomer. Under nitrogen protection, the mixture is stirred at a speed of 200-300 r / min and the reaction system in the reaction vessel is heated to 60-80℃ and reacted for 4-6 hours to obtain a poly(p-hydroxystyrene) prepolymer solution. In this step, when the reaction system inside the reactor is heated to 60-80°C, the initiator azobisisobutyronitrile (AIBN) first decomposes, generating isobutyronitrile free radicals and nitrogen gas. The exemplary reaction equation is as follows: ; Subsequently, the generated isobutyronitrile free radicals can initiate the opening of double bonds on the p-hydroxystyrene monomer, resulting in free radical polymerization to form a linear polymer chain, thereby obtaining poly(p-hydroxystyrene) prepolymer. The reaction equation is exemplarily shown below: ; Wherein, Ph represents a benzene ring, and x represents the degree of polymerization of the poly(p-hydroxystyrene) prepolymer; wherein, the number average molecular weight of the poly(p-hydroxystyrene) prepolymer obtained in step S2 is controlled at 5000~8000 Da.

[0012] Step S3: Synthesis of polyurea resin prepolymer In another reaction vessel, the dried isocyanate monomers (molar amount denoted as m) from step S1 and DMF solvent are added, making the mass percentage of isocyanate monomers 20-30% [isocyanate monomers / (isocyanate monomers + DMF)]. Then, under nitrogen protection, the mixture is stirred at 150-250 r / min and heated to 40-60℃. Next, a DMF solution containing diamine monomers (the mass percentage of diamine monomers in this solution is 10-20%) is slowly added dropwise, controlling the molar ratio of isocyanate monomers to diamine monomers to be approximately 1.05:1 to 1.10:1 (i.e., isocyanate monomers are slightly in excess). The addition time is controlled at 1-2 hours. After the addition is complete, the reaction continues for 2-3 hours to obtain a polyurea resin prepolymer solution. MDI is used as an example of isocyanate monomer, and its reaction equation is as follows: Wherein, R is the polyether backbone or the backbone containing the hindered amine structure, y represents the number of repetitions of the corresponding group, and M is the abbreviation of the corresponding group in the polyurea resin prepolymer; wherein, the number average molecular weight of the polyurea resin prepolymer obtained in step S3 is controlled at 3000~6000 Da.

[0013] Step S4, Block copolymerization reaction The poly(p-hydroxystyrene) prepolymer solution obtained in step S2 and the polyurea resin prepolymer solution obtained in step S3 are added to the same reactor. Under nitrogen protection, the mixture is stirred at a speed of 200-300 r / min and heated to 50-70℃. While stirring, dibutyltin dilaurate (DBTDL) is added to the same reactor at a rate of 0.1-0.3% of the total mass of the poly(p-hydroxystyrene) prepolymer solution and the polyurea resin prepolymer solution in the same reactor. The reaction is carried out for 6-8 hours to obtain a block copolymer reaction mixture. In this step, the reaction equations for the poly(p-hydroxystyrene) prepolymer and the polyurea resin prepolymer are exemplarily shown below: .

[0014] in," "Indicates the omitted p-hydroxystyrene group," "" indicates unshown blocks. It should be noted that due to the molecular structure limitations of urea-based materials, the actual product molecular structure after block copolymerization is a network structure. The above reaction equation is merely a schematic representation and does not represent the actual structure. During the block copolymerization reaction, dibutyltin dilaurate acts as an organic catalyst. By controlling the reaction temperature at 50-70℃ and the amount of organic catalyst added at 0.1-0.3%, the block copolymerization reaction rate can be maintained at 0.05-0.15 L•mol. -1 •s -1The range ensures that the selectivity of the chain growth reaction is ≥90%, suppressing homopolymerization side reactions.

[0015] Step S5, Post-processing The solution after the reaction in step S4 is poured into 10-15 times its volume of methanol to precipitate. The precipitate is collected by filtration and washed repeatedly with methanol. The precipitate is then dried in a vacuum drying oven at 40-60℃ for 12-24 hours until constant weight is obtained to obtain a block copolymer solid. The solid is dissolved in propylene glycol methyl ether acetate (PGMEA) to prepare a solution with a mass fraction of 10-15%. The solution is then filtered through a 0.2μm polytetrafluoroethylene (PTFE) filter membrane to obtain the final resin product.

[0016] Preferably, in the preparation method, the ratio of the molar amount n of the hydroxystyrene monomer to the molar amount m of the isocyanate monomer is controlled at n:m=(6~10):1.

[0017] Example 1 The poly(p-hydroxystyrene) resin in this embodiment was prepared using the aforementioned preparation method. In the preparation process, MDI was used as the isocyanate monomer, and polyether diamine was selected as the diamine monomer (specifically, Jeffamine® ED-600 series polyether amine purchased from Huntsman Corporation, USA). In step S2, 6 mol of p-hydroxystyrene monomer was used, and after adding DMF, the mass percentage of p-hydroxystyrene monomer in the total solution in the reactor was 20%. The amount of AIBN was 0.7% of the mass of p-hydroxystyrene monomer. Under nitrogen protection, the stirring speed was 200 r / min, and the reaction was carried out at 70°C for 5 hours. In step S3, 1 mol of MDI was used, and the mass percentage of MDI in DMF was 25%. Under nitrogen protection, the mixture was stirred at 200 r / min, heated to 50°C, and the DMF solution containing polyether diamine monomer was slowly added dropwise. The polyether diamine monomer, with a mass ratio of 20%, is added dropwise over 1 hour. After the addition is complete, the reaction continues for 2 hours to obtain a polyurea resin prepolymer solution. During this process, the molar ratio of MDI to polyether diamine monomer is controlled at 1.05:1. In step S4, under nitrogen protection, the mixture is stirred at a speed of 200 r / min, heated to 70°C, and 0.2% DBTDL is added. The reaction is carried out for 8 hours. In step S5, the solution after the reaction in step S4 is poured into 10 times its volume of methanol to precipitate the precipitate. The precipitate is then dried in a vacuum drying oven at 60°C for 12 hours until constant weight is achieved. A 15% mass fraction solution is prepared and then filtered through a 0.2 μm polytetrafluoroethylene (PTFE) filter membrane.

[0018] Example 2 The only difference between Example 2 and Example 1 is that in step S2, the amount of p-hydroxystyrene monomer used is 8 mol.

[0019] Example 3 The only difference between Example 3 and Example 1 is that in step S2, the amount of p-hydroxystyrene monomer used is 10 mol.

[0020] Comparative Example 1 The only difference between Comparative Example 1 and Example 1 is that in step S2, the amount of p-hydroxystyrene monomer used is 4 mol.

[0021] Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that in step S2, the amount of p-hydroxystyrene monomer used is 15 mol.

[0022] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that steps S3 and S4 are not involved. That is, after obtaining the poly(p-hydroxystyrene) prepolymer solution, post-processing is performed directly (omitting the synthesis of the polyurea resin prepolymer and the block copolymerization steps). The reacted solution is poured into 10 times its volume of methanol to precipitate the precipitate, which is then dried in a vacuum drying oven at 60°C for 12 hours until constant weight. A 15% (w / w) resin solution is then prepared and filtered through a 0.2 μm polytetrafluoroethylene (PTFE) membrane. In other words, pure poly(p-hydroxystyrene) resin is prepared without polyurea prepolymer preparation or block copolymerization.

[0023] Comparative Example 4 Comparative Example 4 is the same as Example 1, except that it does not include steps S2 to S4 of Example 1. Instead, the substances used in steps S2 to S4 (p-hydroxystyrene monomer, DMF, AIBN, MDI, polyether diamine monomer, etc.) are weighed in equal mass and mixed directly. The mixture is stirred at 200 r / min, heated to 60°C, and reacted for 8 hours. After that, it is purified and a resin solution is prepared according to step S5 of Example 1.

[0024] Comparative Example 5 Comparative Example 5 is the same as Example 1, except that p-hydroxystyrene monomer and tert-butyl methacrylate (TBMA) are mixed in a 6:1 molar ratio, and then AIBN (0.7% of the mass of p-hydroxystyrene monomer) and DMF (20% of the total monomer mass) are added. The mixture is reacted at 70°C and 200 r / min for 5 hours, and the post-treatment is the same as step S5 of Example 1.

[0025] Comparative Example 6 The pure PHS resin of Comparative Example 3 was mixed with t-BOC anhydride at a mass ratio of 10:3 and reacted at 60°C for 4 hours under pyridine catalysis. The post-treatment was the same as step S5 of Example 1.

[0026] Performance testing Performance testing includes testing the following parameters: Glass transition temperature (Tg): Differential scanning calorimetry (DSC) was used at a heating rate of 10℃ / min under nitrogen atmosphere. Tensile properties: A universal testing machine was used, with a tensile rate of 5 mm / min and sample size of 10 mm × 4 mm × 0.2 mm. Dielectric constant: Tested using an impedance analyzer at a frequency of 1MHz at room temperature; Water contact angle: The contact angle was measured using a contact angle meter and deionized water titration. The average value was taken after 5 tests. Coefficient of thermal expansion (CTE): The resin solutions of each example and comparative example were mixed with aluminum nitride filler (particle size 50-100nm) at a mass ratio of 70:30 to prepare electronic encapsulation adhesive. Then, the coefficient of thermal expansion was measured using a thermomechanical analyzer (TMA) at a temperature range of 25-150℃ and a heating rate of 5℃ / min. Film formation and phase separation: The uniformity of the film surface was observed using an optical microscope (100x magnification). Photolithography defect rate: The resin solutions of each example and comparative example were mixed with 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine (photoinitiator) and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate (crosslinking agent) at a mass ratio of 85:10:5 to prepare a photoresist solution, and then the number of defects in the 36nm linewidth pattern was observed using a scanning electron microscope; Plasma etching loss rate: Photoresist solution was prepared with reference to photolithography defect rate test, and then inductively coupled plasma etching machine was used with CF4 / O2=3:1 and power 300W to calculate the mass loss per unit time; The test results are as follows:

[0027] As can be seen from the table above, the Tg values ​​(162-174℃) of Examples 1 to 3 are significantly higher than those of the comparative examples. Among them, Example 2 reaches 174℃, which is 23℃ higher than the pure PHS resin of Comparative Example 3 and 14℃ higher than the PHS resin protected by t-BOC of Comparative Example 6. This is due to the rigid network formed by the polyurea hard segment and the PHS benzene ring in the block structure, which has a much better thermal stability than the single protecting group modification (Comparative Example 6) or the random copolymer structure (Comparative Example 5). In terms of mechanical properties, the tensile strength (21-28 MPa) and elongation at break (84-158%) of the embodiments are superior to those of the comparative examples. For example, the elongation at break of Example 2 (132%) is 33 times that of pure PHS (4%) and 16.5 times that of PHS resin protected by t-BOC. This balance of "high strength and high toughness" may be due to the synergistic effect of "PHS hard segments providing rigid support and polyurea soft segments providing elastic buffering" in the block structure. In contrast, the comparative examples, lacking this structure, generally suffer from defects such as "embrittlement" or "insufficient strength". In terms of improved thermal expansion properties, after being compounded with aluminum nitride filler, the CTE value of the embodiments (14-19 ppm / ℃) is significantly lower than that of the comparative examples (24-37 ppm / ℃). The CTE of Example 2 (14 ppm / ℃) is the lowest, and it has better matching with silicon substrate (3 ppm / ℃). This characteristic is crucial for electronic packaging, as it can reduce the interfacial stress and cracking risk caused by expansion mismatch during thermal cycling. Furthermore, the dielectric constant of the embodiments is lower than that of the comparative examples, with the dielectric constant of Embodiment 2 being the lowest, meeting the requirements of high-frequency electronic devices for low-dielectric materials. Water contact angle testing shows that the hydrophobicity of the embodiments is significantly better than that of pure PHS. This is because the non-polar polyether structure of the polyurea segments reduces water molecule adsorption, avoiding dielectric loss in high-frequency signal transmission, making it particularly suitable for 5G RF devices and high-density packaging. Regarding film quality, all embodiments showed "excellent" results, with no gelation or phase separation. Comparative Example 1 (n:m=4:1) resulted in gelation due to excessive polyurea, while Comparative Example 4 (direct mixing) showed severe phase separation due to disordered reaction, proving that stepwise block copolymerization is key to ensuring film formation. In addition, when the resin material of this invention is prepared as a photoresist, the photolithography defect rate of the embodiments (0.01-0.03 defects / μm²) is significantly lower than that of the comparative examples, and the plasma etching loss rate (0.28-0.33% / min) is only about 1 / 9 of that of pure PHS (2.9% / min), demonstrating excellent photolithography performance.

[0028] It should also be noted that the poly(p-hydroxystyrene) resin of this invention can be applied not only to electronic packaging materials and semiconductor photoresists, but also has significant application potential in areas such as liquid crystal display alignment layers. Its high Tg (162-174°C) can withstand the high-temperature processes (such as annealing) of liquid crystal display devices; its excellent film uniformity (no phase separation) ensures a smooth alignment layer surface and reduces liquid crystal molecule alignment defects; its moderate hydrophobicity (96-109°) can regulate the pretilt angle of liquid crystal molecules, optimizing display contrast; and its low dielectric constant helps reduce the driving voltage of the display panel, improving energy efficiency. Compared to traditional polyimide alignment materials, the resin of this invention combines resistance to damp heat with process compatibility. In the bending durability test in the field of flexible displays, the sample in Example 2 retained more than 85% of its initial performance after 100,000 bends, far superior to polyimide materials (50-60%), demonstrating its technical advantages in cross-domain applications.

[0029] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing poly(p-hydroxystyrene) resin, the method comprising the following steps: Step S1: Raw material preparation; Step S2: Synthesis of poly(p-hydroxystyrene) prepolymer to obtain poly(p-hydroxystyrene) prepolymer solution; Step S3: Synthesis of polyurea resin prepolymer to obtain polyurea resin prepolymer solution; Step S4, Block copolymerization reaction: The poly(p-hydroxystyrene) prepolymer solution obtained in step S2 and the polyurea resin prepolymer solution obtained in step S3 are added to the same reactor to obtain the block copolymerization reaction mixture. Step S5: Post-process the block copolymer reaction mixture obtained in step S4 to obtain the poly(p-hydroxystyrene) resin.

2. The method for preparing poly(p-hydroxystyrene) resin as described in claim 1, characterized in that, In step S2, the molecular formula of the poly(p-hydroxystyrene) prepolymer is: ， Where Ph represents the benzene ring and x represents the degree of polymerization of the poly(p-hydroxystyrene) prepolymer.

3. The method for preparing poly(p-hydroxystyrene) resin as described in claim 1, characterized in that, Step S2 includes taking the purified p-hydroxystyrene monomer from step S1 and adding it to a reaction vessel. Then, adding the dried DMF from step S1 to the reaction vessel, adjusting the amount added to ensure that the mass percentage of p-hydroxystyrene monomer in the total solution in the reaction vessel is 15-25%. Next, adding azobisisobutyronitrile (AIBN) to the reaction vessel, with the amount of AIBN accounting for 0.5-1% of the mass of p-hydroxystyrene monomer, stirring at a speed of 200-300 r / min under nitrogen protection, and heating the reaction system in the reaction vessel to 60-80°C for 4-6 hours to obtain a poly(p-hydroxystyrene) prepolymer solution.

4. The method for preparing poly(p-hydroxystyrene) resin as described in claim 1, characterized in that, Step S3 includes, In another reaction vessel, the dried isocyanate monomers and DMF solvent from step S1 are added, so that the mass ratio of isocyanate monomers is 20-30%. Then, under nitrogen protection, the mixture is stirred at a speed of 150-250 r / min and heated to 40-60℃. Then, a DMF solution containing diamine monomers is slowly added dropwise, in which the mass ratio of diamine monomers is 10-20%. The molar ratio of isocyanate monomers to diamine monomers is controlled to be 1.05:1 to 1.10:

1. The addition time is controlled to be 1-2 hours. After the addition is complete, the reaction continues for 2-3 hours to obtain a polyurea resin prepolymer solution.

5. The method for preparing poly(p-hydroxystyrene) resin as described in claim 4, characterized in that, The isocyanate monomers are selected from one or more of TDI, MDI, HDI, IPDI, HMDI, and fluorinated isocyanates.

6. The method for preparing poly(p-hydroxystyrene) resin as described in claim 4, characterized in that, The diamine monomer is a polyether diamine monomer or a diamine monomer containing a hindered amine structure.

7. The method for preparing poly(p-hydroxystyrene) resin as described in claim 1, characterized in that, Step S4 includes adding the poly(p-hydroxystyrene) prepolymer solution obtained in step S2 and the polyurea resin prepolymer solution obtained in step S3 to the same reactor, stirring at a speed of 200-300 r / min under nitrogen protection, and heating to 50-70°C. While stirring, dibutyltin dilaurate is added to the same reactor in an amount of 0.1-0.3% of the total mass of the poly(p-hydroxystyrene) prepolymer solution and the polyurea resin prepolymer solution in the same reactor. The reaction is carried out for 6-8 hours to obtain a block copolymer reaction mixture.

8. A method for preparing a poly(p-hydroxystyrene) resin according to any one of claims 1-7, characterized in that, The ratio of the molar amount n of p-hydroxystyrene monomer to the molar amount m of isocyanate monomer is controlled at n:m=(6~10):

1.

9. A poly(p-hydroxystyrene) resin material prepared by any one of the preparation methods described in claims 1-8.

10. The application of the poly(p-hydroxystyrene) resin material of claim 9 in photoresists, electronic packaging, and / or, liquid crystal display alignment layers.

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