A phenylene alkylene macromolecular polymer crosslinking agent and its application

Abstract

The application belongs to the field of resin crosslinking modification, and discloses a phenylene alkylene polymer crosslinking agent and application thereof, wherein the crosslinking agent comprises rigid polycoumarone main chain structure units and side chain structure units with crosslinking active sites and long-chain alkyl groups. Since the polymer main chain does not contain heteroatoms such as sulfur, ether and oxygen, the tendency of radical electrophilic attack is significantly reduced, and the crosslinked resin is endowed with excellent chemical oxidation resistance and anti-aging performance. The application also provides a composite crosslinked resin prepared by copolymerization and crosslinking of the crosslinking agent and synthetic resins such as SBS or EM, and application of the composite crosslinked resin in preparation of anion exchange resins. The crosslinking agent is designed by controllable copolymerization of multifunctional units, which not only realizes the synergistic improvement of tensile strength and elongation at break of the modified resin, overcomes the technical bottleneck of "rigidity-toughness imbalance" in traditional crosslinking technology, but also significantly improves the conversion efficiency of polymerized monomers and the morphological regularity of the final product, and reduces the content of fine powder and the adhesion tendency.

Description

Technical Field

[0001] This invention belongs to the field of resin crosslinking modification, specifically relating to a benzenealkylene polymer crosslinking agent and its application. Background Technology

[0002] Synthetic resins are key raw materials for manufacturing materials such as plastics and coatings. Although conventional thermoplastic elastomers have high elongation at break, excellent elastic recovery and flexibility, the molecular chains of the resin are only physically entangled and do not have a stable chemical cross-linking network. Under long-term stress or high temperature and thermal aging environments, molecular chain slippage, stress relaxation and plastic deformation are very likely to occur, making it difficult to adapt to the harsh working conditions of high strength and high durability.

[0003] To cope with complex working conditions and meet the specific needs of different fields, modification of pure resins is essential. Among these modifications, chemical crosslinking is the most effective and stable method. By introducing crosslinking agents, stable three-dimensional crosslinked structures can be constructed within the polymer network, effectively constraining the slippage of molecular chains. This not only significantly improves the strength, rigidity, and aging resistance of materials but also, to some extent, mitigates physical morphological defects caused by low polymerization degrees in resins. It is a core process in the design and production of modern resin materials.

[0004] Currently, most widely used crosslinking modification strategies employ small-molecule crosslinking agents in a single molecular form. This traditional system reveals three inherent defects in practical applications, making it impossible to achieve synergistic performance optimization: (1) Performance trade-off: Traditional small molecule crosslinking agents can improve the strength and rigidity of materials, but they restrict the movement of molecular chains and significantly sacrifice the elongation at break and flexibility, resulting in a problem that rigidity and toughness cannot be balanced; simple physical blending modification cannot form a stable covalent crosslinking network, resulting in limited strength improvement, and poor heat resistance, aging resistance and deformation resistance.

[0005] (2) Poor stability of cross-linked network: Traditional monomolecular cross-linked systems have few sites and low network regularity. Under thermal aging, temperature change and continuous stress conditions, cross-linked bonds are prone to breakage and failure, causing the network structure to collapse, resulting in rapid decay of material mechanical properties and insufficient long-term durability.

[0006] (3) Weak modifiability and adaptability: Traditional crosslinking agents have fixed structures and no adjustable segments or functional modification sites. They cannot accurately control the crosslinking density and network flexibility according to the resin characteristics and application requirements, making it difficult to achieve customized performance optimization and limiting the range of adaptability.

[0007] To address the pain points of "loss" and "imbalance between rigidity and toughness" in small molecule crosslinking agents, polymeric crosslinking agents have emerged. Their long-chain structure not only allows for the grafting of abundant reactive crosslinking sites but also enables them to form deep physical entanglements with the crosslinked resin, effectively inhibiting migration and loss at high temperatures. At the same time, the polymer backbone provides a larger spatial spacing, constructing a long-span crosslinking network that can improve rigidity while retaining the tensile toughness of the original resin.

[0008] Although polymeric crosslinking agents theoretically overcome the limitations of small molecules, conventional polymeric crosslinking systems and some resin matrices still face new challenges in practical polymerization applications and production processes. Due to the heterogeneity of polymerization or the limitations of reaction conditions, some polymeric crosslinking networks may have relatively low degrees of polymerization. Furthermore, insufficient polymerization can lead to the precipitated resin solids being powdery after drying. Because such resin powders have low density, they not only increase the difficulty of collection and post-processing but also easily scatter during actual storage and transportation, significantly negatively impacting environmental hygiene and safety management in the production workshop.

[0009] Therefore, in order to address the problems existing in conventional polymer systems, it is particularly important to carry out directional structural modification and design of polymer crosslinking agents. Summary of the Invention

[0010] The purpose of this invention is to overcome at least one deficiency of the prior art and to provide a benzenealkylene polymer crosslinking agent and its application.

[0011] The technical solution adopted in this invention is: In a first aspect, the present invention provides a benzylidene polymer crosslinking agent, the benzylidene polymer crosslinking agent having the following structural units: The structural unit shown in Equation 1A is as follows: ; At least one structural unit from either Equation 2A or Equation 2B: ; In the formula, q represents an integer between 0 and 5; The R 20 R 30 R 40 R 50 R 60 R 70 R 80 and R 90 Each group is independently selected from hydrogen, halide, alkyl, alkenyl, alkynyl, or aryl, and the alkyl, alkenyl, alkynyl, or aryl group is optionally substituted with a halide, and wherein R 30 and R60 Optionally, a halide or alkyl-substituted five- or six-membered ring can be attached; The R1 and R3 groups are each independently selected from any one of perfluoroalkyl, benzyl, aryl or alkyl, and the aryl or benzyl groups are optionally replaced with fluorides; The R2 group is selected from any one of halogen, alkenyl, alkynyl, and cyano, and the alkenyl, alkynyl, or cyano group is optionally replaced by a halide; The R4 group is selected from halogens, C1-C... 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12 Alkyne, cyano, or haloaryl; the R5, R6, R7, and R8 groups are each independently hydrogen, halogen, or C1-C. 12 Haloalkyl, C1-C 12 Alkyl, C2-C 12 alkenyl, C2-C 12 Groups including alkynyl, cyano, aryl, haloaryl, C3-C6 cycloalkyl, and 5-6 heteroaryl groups; The R 4、 The aryl, cycloalkyl, and heteroaryl groups contained in R5, R6, R7, and R8 may optionally be replaced by one or more alkyl groups selected from C1-C6 and halogens; The R 18 The group is selected from alkylene groups, wherein the number of carbon atoms in the alkylene group is any integer between 1 and 11. Optionally, the alkylene oxide polymer crosslinking agent further has the structural units shown in Formula 3A and Formula 3B: ; The R9, R 10 Each group is independently selected from any one of perfluoroalkyl, benzyl, aryl or alkyl, and the aryl or benzyl group is optionally substituted with a fluoride; The R 11 R 12 R 13 R 14 R 15 R 16 Each is independently any one of hydrogen, fluoride, alkyl, aryl, and the alkyl or aryl group is optionally replaced by a fluoride; The R 17 The group is selected from alkylene groups, wherein the number of carbon atoms in the alkylene group is any integer between 1 and 11. Specifically, the number of moles of the structural unit represented by Formula 1A in the alkylene diphenylene polymer crosslinking agent is equal to the sum of the number of moles of the structural units represented by Formulas 2A, 2B, 3A, and 3B.

[0012] Specifically, R1, R3, R9, R 10 The groups are each independently selected from trifluoromethyl and pentafluoroethyl. Specifically, the structural formula of the alkylene oxide polymer crosslinking agent is as follows: ; In the formula, m, n, and x are any values ​​between 0 and 100; The R 100 R 120 Each group is independently selected from trifluoromethyl or pentafluoroethyl; The R 110 R 130 Each group is independently selected from C4-C7 straight-chain alkyl, C6-C10 aryl, C7-C10 straight-chain aralkyl, C8-C10 straight-chain arene, or a halogenated form of the aforementioned groups. Specifically, the R 110 R 130 Each group is independently selected from styryl, phenylpropyl, phenyl, butyl, heptyl, or halogenated forms of the aforementioned groups. Specifically, the R 110 R 130 When the group is a halogenated product with a straight chain, its halogenation site is at the end of the straight chain. Specifically, the alkylene oxide polymer crosslinking agent is prepared by the following method: The polymer is prepared by mixing monomers of formula 1A, 2A or 2B and optionally formula 3A or 3B under a catalyst via a superacid reaction. The catalyst is one or a combination of trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, and heptafluorobutyric acid.

[0013] In a second aspect, the present invention provides a composite crosslinking resin, which is obtained by copolymerization and crosslinking of a alkylene oxide polymer crosslinking agent provided in the first aspect with a synthetic resin, wherein the synthetic resin is selected from SBS or EM resin.

[0014] The third aspect concerns the application of the alkylene oxide polymer crosslinking agent provided in the first aspect or the composite crosslinking resin provided in the second aspect in the preparation of anion exchange resins.

[0015] The beneficial effects of this invention are: The alkylene polyimide crosslinking agent described in this invention has significant advantages over conventional small molecule crosslinking agents in terms of molecular structure and crosslinking efficiency, specifically in the following aspects: On the one hand, the polymer crosslinking agent possesses higher molecular strength; on the other hand, the polyphenylene structure introduced into its polymer backbone contributes the necessary rigidity, while the alternating long alkane chains can moderately adjust the chain segment flexibility, thereby maintaining a balance between material ductility and overall rigidity. This polymer crosslinking agent not only possesses functional group reactivity similar to that of single long-chain compound crosslinking agents, but also, due to its "rigid-flexible" molecular design, can simultaneously introduce reinforcing and toughening phases into the crosslinking network, thereby further optimizing the mechanical properties of the resulting crosslinked resin.

[0016] Furthermore, the long-chain structure of this crosslinking agent is rich in reactive crosslinking sites, and the larger spatial spacing between each reactive group helps to construct a network structure with longer and more effective crosslinking segments within the resin. This structure can more uniformly disperse stress, delay crack propagation, and ultimately achieve a synergistic improvement in tensile strength and elongation at break, effectively overcoming the technical bottleneck of the trade-off between strength and toughness in traditional crosslinking technologies.

[0017] The alkylene oxide polymer crosslinking agent described in this invention has a main chain structure free of heteroatoms such as sulfur, ether, and oxygen, thus effectively avoiding the structural risk of unstable electron-rich sites formed on the aromatic ring due to the electron-donating effect of such heteroatoms. This molecular design significantly reduces the electrophilic attack tendency of hydroxyl radicals on the polymer backbone, thereby endowing the crosslinked resin with excellent chemical oxidation resistance and anti-aging properties. As a result, the service life and performance retention of the crosslinked resin in harsh oxidizing or corrosive environments are greatly extended, demonstrating significant durability advantages.

[0018] The alkylene oxide polymer crosslinking agent provided by this invention can effectively increase the molecular weight of the polymer during the crosslinking process, and synergistically with its branching modification effect, improve the conversion efficiency of the polymer monomers and the morphological regularity of the final product. During the precipitation and granulation stages, this crosslinking agent helps to form particles with more uniform morphology and denser surfaces, significantly reducing the content of fine powder and the tendency to agglomerate. This morphological advantage provides significant improvement for dust control in subsequent material transportation, storage, and processing, which is beneficial to the stable and clean operation of industrial production. Attached Figure Description

[0019] Figure 1 This is a physical image of the crosslinked resin from Example 2 (TP0-CF3CF5-B4A2-10Ole-SBS10).

[0020] Figure 2 This is a picture of the dried crosslinked resin particles of Example 5 (TP70-CF5CF3-B4B2-10-EM10).

[0021] Figure 3This is a photograph of the cross-linked resin particles filtered after precipitation in Example 7 (TP100-CF3-A1A3-10-EM10).

[0022] Figure 4 This is a picture of the resin after drying in Comparative Example 4 (C1-EM3). Detailed Implementation

[0023] This invention provides a benzenealkylene polymer crosslinking agent, wherein the benzenealkylene polymer crosslinking agent has the following structural units: The structural unit shown in Equation 1A is as follows: ; At least one structural unit from either Equation 2A or Equation 2B: ; In the formula, q represents an integer between 0 and 5; The R 20 R 30 R 40 R 50 R 60 R 70 R 80 and R 90 Each group is independently selected from hydrogen, halide, alkyl, alkenyl, alkynyl, or aryl, and the alkyl, alkenyl, alkynyl, or aryl group is optionally substituted with a halide, and wherein R 30 and R 60 Optionally, a halide or alkyl-substituted five- or six-membered ring can be attached; The R1 and R3 groups are each independently selected from any one of perfluoroalkyl, benzyl, aryl or alkyl, and the aryl or benzyl groups are optionally replaced with fluorides; The R2 group is selected from any one of halogen, alkenyl, alkynyl, and cyano, and the alkenyl, alkynyl, or cyano group is optionally replaced by a halide; The R4 group is selected from halogens, C1-C... 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12 Alkyne, cyano, and haloaryl groups; R5, R6, R7, and R8 groups are each independently hydrogen, halogen, or C1-C. 12 Haloalkyl, C1-C 12 Alkyl, C2-C 12 alkenyl, C2-C 12 The group comprises alkynyl, cyano, aryl, haloaryl, C3-C6 cycloalkyl, and 5-6 heteroaryl groups; wherein the aryl, cycloalkyl, and heteroaryl groups are optionally substituted by one or more substituted groups selected from C1-C6 alkyl groups and halogens; The R 18 The group is selected from alkylene groups, wherein the number of carbon atoms in the alkylene group is any integer between 1 and 11. The sum of the number of moles of structural units in Formulas 2A, 2B, 3A, and 3B is 1 compared to the mole ratio of structural unit in Formula 1A.

[0024] Optionally, the alkylene oxide polymer crosslinking agent further has the structural units shown in Formula 3A and Formula 3B: ; The R9, R 10 Each group is independently selected from any one of perfluoroalkyl, benzyl, aryl or alkyl, and the aryl or benzyl group is optionally substituted with a fluoride; The R 11 R 12 R 13 R 14 R 15 R 16 Each is independently any one of hydrogen, fluoride, alkyl, aryl, and the alkyl or aryl group is optionally replaced by a fluoride; The R 17 The group is selected from alkylene groups, wherein the number of carbon atoms in the alkylene group is any integer between 1 and 11. Specifically, the number of moles of the structural unit represented by Formula 1A in the alkylene diphenylene polymer crosslinking agent is equal to the sum of the number of moles of structural units represented by Formulas 2A, 2B, 3A, and 3B.

[0025] Preferably, R1, R3, R9, R 10 The groups are each independently selected from trifluoromethyl and pentafluoroethyl. As an example, a method for synthesizing a 3A-structured monomer is provided: To synthesize the ketone monomer 1,1,1,2,2-pentafluoroundecane-3-one, dichloromethane (100 ml) and nonanoyl chloride (4 g, 1 eq) were added to a 250 ml three-necked flask and stirred until homogeneous. The mixture was then cooled to 0 °C. Pentafluoropropionic anhydride (42.12 g, 6 eq) was added dropwise with stirring, and pyridine solution (14.33 g pyridine dissolved in 20 ml dichloromethane) was added dropwise while maintaining the temperature below 5 °C. The mixture was kept at 0 °C and stirred for 30 min, then raised to room temperature (25 °C) and stirred for 3 h. The reaction mixture was then cooled to 0 °C, and ice water (50 ml) was added dropwise, followed by stirring for 30 min. The mixture was then heated to 50 °C and stirred for 20 h.

[0026] After the reaction was completed, the mixture was allowed to stand and separate into layers. The organic phase was collected, and the aqueous phase was extracted with dichloromethane (2 x 15 ml). The combined organic phases were washed successively with deionized water, saturated sodium carbonate, and saturated sodium chloride solution. The organic phase was dried over anhydrous sodium sulfate and filtered. The solution was evaporated to dryness at 30°C to obtain 5.78 g of a concentrated orange-red crude product (yield 98.1%). The product was purified by silica gel column chromatography using a petroleum ether / ethyl acetate eluent prepared in a 10 / 10 ratio. The final product was a pale yellow liquid, 1,1,1,2,2-pentafluoroundecane-3-one (4.79 g, yield approximately 81.2%). The synthetic equation is as follows: . As another example, a method for synthesizing a monomer with a 2B structure is provided, and the reaction equation is as follows: ; The brominated trifluoroacetophenone monomer was obtained via Friedel-Crafts acylation. Dichloromethane (300 mL) and 0.22 mol of aluminum trichloride were added to a flask, and the mixture was stirred at a temperature below 5 °C. Trifluoroacetic anhydride (0.13 mol) was added to the flask, and the mixture was stirred for 15 min. A diluted solution of 1-bromo-3-phenylpropane (0.1 mol, 50 mL dichloromethane) was added dropwise. After the addition was complete, the reaction was carried out at 0 °C for 16 h. When the reaction was complete, the mixture was poured into ice water, extracted with DEE, and then evaporated. The fraction collected at 120–125 °C was collected by vacuum distillation to give 26.6 g (90% yield) of a clear yellow liquid.

[0027] Specifically, the polymer crosslinking agent can be prepared by a method comprising the following steps: The polymer crosslinking agent is prepared by mixing monomers of formula (1A), formula (2A) or formula (2B) and optionally formula (3A) or formula (3B) in the presence of a catalyst via a superacid reaction.

[0028] Step 1: Dissolve monomers of formula (2A) or (2B) and optionally monomers of formula (3A) or (3B) as a single component or a mixture, and monomers of formula (1A) as a single component or a mixture, in a first solvent. Cool the mixture to 0°C using an ice bath, add the catalyst dropwise, and polymerize the mixture under ice bath conditions for 2 hours to 2 days. After the reaction is complete, add a second solvent to quench and dissolve the polymer. Pour the polymer into a precipitation solvent to obtain a white solid. Filter the solid, rinse it several times with deionized water, and then dry it under vacuum at 80°C for 12 hours.

[0029] The catalyst is one or a combination of trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, and heptafluorobutyric acid.

[0030] The first solvent is selected from dichloromethane, dichloroethane, trifluoroacetic acid, trifluoromethanesulfonic acid, chloroform, 1,1,2,2-tetrachloroethane, or a combination thereof.

[0031] The second solvent is one or a combination of dimethyl sulfoxide, N-methylpyrrolidone, N-butylpyrrolidone, and N,N-dimethylacetamide.

[0032] The precipitation solvent in step 1 is water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, tetrahydrofuran, or a combination thereof.

[0033] As an example, a method for preparing a polymeric crosslinking agent comprising, but not limited to, the present invention is provided: for example, optionally fluorinated ketone monomers, such as trifluoroacetophenone, and aromatic monomers such as terphenyl, are dissolved in an organic solvent (e.g., DCM) using a top-mounted stirrer. A polymerization catalyst is then added dropwise at 0°C, and the reaction is continued at this temperature for approximately 0–7 days. The resulting solution is slowly poured into an ethanol / water solution. The obtained solid is filtered, washed with water, and immersed in 1M sodium hydroxide at room temperature for approximately 1–48 hours. Finally, the product is filtered, washed with water, and completely dried under vacuum to obtain the target polymeric crosslinking agent.

[0034] The polymer crosslinking agent provided by this invention can be applied to crosslinking resins in different fields, including but not limited to PE modification, PP modification, PS modification, PU modification, ion exchange resins, etc.

[0035] The crosslinked polymer using this polymeric crosslinking agent can be prepared by a method comprising the following steps: (1) The polymer crosslinking agent and olefin monomers such as butadiene, propylene, and styrene are polymerized and crosslinked in the presence of organic solvent and polymerization catalyst to obtain the corresponding crosslinking resin.

[0036] The crosslinking agent in the polymer crosslinking agent structural monomer formula (2) has R2, R4 to R8 as alkenyl groups. The crosslinking agent and olefin monomer are copolymerized and crosslinked under a catalyst to obtain the corresponding crosslinked resin. Step 1: Dissolve the crosslinking agent with R2, R4 to R8 being alkenyyl groups in the polymer crosslinking agent structural monomer formula 2A or 2B in a solvent (NMP, DMF, DMSO, DMAc, THF, etc.), and copolymerize it with monomers such as propylene, vinyl chloride, styrene, butadiene, and isoprene in the presence of a dispersant and an initiator to obtain the crosslinking resin for application. (2) In an organic solvent, the polymer crosslinking agent of monomer formula 2A or 2B preferably contains halogens (Cl, Br), such as R2, R4 to R8. The corresponding crosslinked resin can be prepared by crosslinking with a resin containing a tertiary amine group through the Menshutkin reaction. Step 1: Dissolve the crosslinking agent (where R2, R4-R8 are halogens) and the resin containing tertiary amine groups in solvent 1, and react at 80°C for 5-10 hours. After the reaction, pour the reaction solution into precipitation solvent 2 to obtain a white solid. Filter the solid, rinse it several times with deionized water, and then vacuum dry it at 80°C for 12 hours. The crosslinked resin is then obtained. Step 2: Subsequently, the cross-linked resin can be further functionalized with ions as needed to obtain the corresponding functional anion exchange resin.

[0037] In step 1, the reaction solvent 1 includes, but is not limited to, dichloromethane, dichloroethane, ethyl acetate, tetrahydrofuran, NMP, DMF, DMSO, DMAc, or combinations thereof.

[0038] In step 1, the precipitation solvent 2 includes, but is not limited to, water, methanol, ethanol, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, or combinations thereof.

[0039] The cross-linked resins using polymeric cross-linking agents primarily achieve improved mechanical properties after cross-linking. Additional functional modifications can be achieved by introducing different side chain groups and their proportions, without significant differences in basic properties. All can be produced using known film-forming techniques such as casting, and molded according to their thermoplastic or thermosetting properties through methods such as compression molding, winding, injection molding, and extrusion.

[0040] The cross-linked modified resin obtained by applying a polymer cross-linking agent retains its application scope largely unchanged, and may even expand its application scenarios due to improved durability. For example, after film formation, it can be used in agricultural films, daily packaging bags, food and pharmaceutical packaging, fuel cells, electrolyzers, water purification membranes, etc.; after molding, it can be used in various industrial parts, synthetic fibers, and various pipe shells, etc.

[0041] This invention utilizes differentiated configuration screening and copolymerization ratio control of structural units such as Formula 1A, Formula 2A, and Formula 2B. Through systematic experimental verification, it has been shown that the introduction ratio and molecular configuration of these structural units can construct quantifiable and precisely controllable performance characteristics. This multi-dimensional molecular design strategy is the core technical path for precisely constructing cross-linked network systems and synergistically improving the comprehensive mechanical properties and environmental tolerance stability of modified resin matrices. The configuration design mechanism and technical gain effects of each functional structural unit are detailed below: 1. Main Chain Structural Unit (Formula 1A): Utilizing a rigid biphenyl backbone as the main chain structure of the crosslinking agent significantly enhances the overall structural rigidity and macroscopic mechanical strength of the crosslinking system, providing stable microscopic mechanical support for the modified resin system. This main chain structure is free of heteroatoms such as sulfur, ether, and oxygen, effectively avoiding electron-rich defect sites induced by the electron-donating effect of heteroatoms in the aromatic ring conjugated system. This eliminates the inherent defect of the polymer main chain being susceptible to degradation by active free radicals at the molecular structural level. This structural design significantly reduces the risk of electrophilic degradation of the polymer main chain backbone by hydroxyl radicals, greatly improving the chemical oxidation resistance and thermal aging resistance of the crosslinked modified resin, and effectively enhancing the material's performance retention and long-term service stability under harsh conditions such as strong oxidation and corrosion.

[0042] 2. Side-chain structural units (Formulas 2A, 2B, 3A, and 3B): The long-chain alkyl side chains introduced into the above structural units can significantly improve the conformational freedom and mobility of polymer molecular chains, optimize the segmental flexibility and deformation adaptability of the crosslinked network, and thus effectively improve the overall flexibility of the composite material. Experimental results show that the flexibility modification effect is positively correlated with the length of the alkyl side chain and the proportion of copolymer doping of the corresponding functional unit, enabling precise directional control of the material's flexibility index to meet the flexibility requirements of different application scenarios.

[0043] 3. Crosslinking Site Structural Units (Equations 2A and 2B): Equations 2A and 2B serve as the core functional comonomers supporting the crosslinking active sites. Their ratio parameters directly determine the effective crosslinking density and crosslinking reaction kinetic efficiency of the crosslinking system, and are key parameters for regulating the mechanical properties of composite materials, the integrity of the three-dimensional crosslinking network, and long-term service stability. By precisely controlling the ratio of the two types of functional monomers, the synergistic design goals of the system's rigidity and flexibility can be directionally matched, achieving high-precision and controllable optimization of the macroscopic mechanical properties of the crosslinked products.

[0044] In summary, this invention, based on the refined molecular design concept of controllable copolymerization of multifunctional units, achieves comprehensive performance improvement of the crosslinking system from three core dimensions: main chain rigidity optimization, precise control of side chain flexibility, and crosslinking density matching optimization. This design fundamentally solves the technical bottlenecks commonly found in traditional resin crosslinking modification systems, such as rigidity-toughness imbalance, poor weather resistance, and insufficient performance control precision. It achieves synergistic enhancement of material mechanical properties and long-term environmental durability, demonstrating significant technological innovation and engineering application value.

[0045] The following disclosure provides many different implementations or examples for different ways of implementing the present invention. Example 1

[0046] The polymer crosslinking agent prepared in this embodiment is named TP100-CF3-A1A2-10Ole, and then crosslinked with SBS10 resin to obtain TP100-CF3-A1A2-10Ole-SBS10. The specific reaction process equation is as follows (where z is the proportion of butadiene polymerization at the 1,2 position, which is usually 55%-90% in this process): The specific steps are as follows: (1) Synthesis of the polymeric crosslinking agent TP100-CF3-A1A2-10Ole. In a 100mL three-necked flask, 3.97g (0.01mol) of the product obtained by copolymerizing 10% 4-bromoethyl-trifluoroacetophenone with trifluoroacetophenone and linear terphenyl was dissolved in 40mL THF. A reflux condenser and a nitrogen balloon were prepared to purge air and provide nitrogen protection. 0.003mol of potassium tert-butoxide was dissolved and suspended in 5mL THF, and then slowly added dropwise to the flask while controlling the temperature. After the addition was complete, the mixture was kept at 40-70℃ and stirred for 4-8 hours.

[0047] The temperature was lowered to 10℃, and 20 ml of saturated NH4Cl aqueous solution was slowly added dropwise. The mixture was stirred at room temperature for 1-2 hours. The resulting white solid product was filtered and repeatedly washed with pure water with stirring. Finally, the white product was filtered again and dried under vacuum at 80℃ for 24 hours. The polymer yield was approximately 92.8%. The white solid product was the target polymer crosslinking agent. (2) Crosslinking polymerization (preparation of TP100-CF3-A1A2-10Ole-SBS10). Add 200 mL of anhydrous THF to a 500 mL three-necked round-bottom flask equipped with a top-mounted powerful mechanical stirrer, and purge with nitrogen. Cool to -10 °C, slowly add 0.8 mL of n-butyllithium solution, and stir for 15 min. Heat to 50 °C, add 30 g of styrene, and stir for 10 min to 90 min. Then cool to 40 °C, slowly add 60 g of butadiene dissolved in 100 mL of THF and TP100-CF3-A1A2-10Ole solution dissolved in THF (10 wt% relative to the total monomer amount), and heat to 60 °C, stirring for approximately 30 min to 3 h. Continue adding 30 g of styrene, and maintain the temperature at 60 °C, stirring for 10-90 min.

[0048] The temperature was lowered to 40℃, and 15 ml of anhydrous ethanol was slowly added dropwise while stirring for 10 min. 0.6 g of BHT (0.5 wt% relative to the total SBS) was added, and stirring was continued for 20 min. The solution was slowly poured into 1 L of hot water at 80℃ under high-speed stirring, resulting in the precipitation of a large amount of white flocculent matter. After the addition was complete, stirring was continued for 1 h. The solution was centrifuged, filtered, and washed repeatedly with pure water. After centrifugation and filtration, the white solid was transferred to 60℃ and vacuum dried for 12 h. The final product was a white elastic solid resin particle or block, which was the target crosslinking product. The yield was approximately 97.7%. Example 2

[0049] The polymer crosslinking agent prepared in this embodiment is named TP0-CF3CF5-B4A2-10Ole, and then crosslinked with SBS10 resin to obtain TPx-CF3CF5-B4A2-10Ole-SBS10. The specific reaction process equation is as follows (where z is the proportion of butadiene polymerization at the 1 and 2 positions, which is usually 55%-90% in this process): The specific steps are as follows: (1) Synthesis of the polymeric crosslinking agent TP0-CF3CF5-B4A2-10Ole. In a 100mL three-necked flask, 0.01mol of the product obtained by copolymerizing 10% 4-bromoethyl-pentafluorophenylacetone with trifluorodecanone and m-terphenyl was dissolved in 40mL THF with stirring. A reflux condenser and a nitrogen balloon were set up to purge air and provide nitrogen protection. 0.003mol of potassium tert-butoxide was dissolved with stirring and suspended in 5mL THF, and then slowly added dropwise to the flask while controlling the temperature. After the addition was complete, the mixture was kept at 40-70℃ and stirred for 4-8 hours.

[0050] The temperature was lowered to 10°C, and 20 ml of saturated NH4Cl aqueous solution was slowly added dropwise while stirring at room temperature for 1-2 hours. The resulting white solid product was filtered and repeatedly washed with pure water with stirring. Finally, the white product was filtered again and dried under vacuum at 80°C for 24 hours. The polymer yield was approximately 93.1%. The white solid product was the target polymer crosslinking agent. (2) The cross-linking polymerization steps are the same as in Example 1, except for the addition of a polymeric cross-linking agent. The final product is a white, elastic solid resin particle or block, which is the target cross-linking product. The yield is approximately 98.4%. Example 3

[0051] The polymer crosslinking agent prepared in this embodiment is named TP50-CF5-B4A2-10Ole, and then crosslinked with SBS10 resin to obtain TP50-CF5-B4A2-10Ole-SBS10. The specific reaction process equation is as follows (where z is the proportion of butadiene polymerization at the 1,2 positions, which is usually 55%-90% in this process): The specific steps are as follows: (1) Synthesis of the polymeric crosslinking agent TP50-CF5-B4A2-10Ole. In a 100mL three-necked flask, 0.01mol of the product obtained by copolymerizing 10% 4-bromoethyl-pentafluorophenylacetone with 1,1,1,2,2-pentafluoroundecane-3-one, linear terphenyl, and meta-terphenyl was stirred and dissolved in 40mL THF. A reflux condenser and a nitrogen balloon were prepared to purge air and provide nitrogen protection. 0.003mol of potassium tert-butoxide was stirred and dissolved, suspended in 5mL THF, and slowly added dropwise to the flask while controlling the temperature. After the addition was complete, the mixture was kept at 40-70℃ and stirred for 4-8 hours.

[0052] The temperature was lowered to 10℃, and 20 ml of saturated NH4Cl aqueous solution was slowly added dropwise. The mixture was stirred at room temperature for 1-2 hours. The resulting white solid product was filtered and repeatedly washed with pure water with stirring. Finally, the white product was filtered again and dried under vacuum at 80℃ for 24 hours. The polymer yield was approximately 93.6%. The white solid product was the target polymer crosslinking agent. (2) The cross-linking polymerization steps are the same as in Example 1, except for the addition of a polymeric cross-linking agent. The final product is a white, elastic solid resin particle or block, which is the target cross-linking product. The yield is approximately 97.9%. Example 4

[0053] The polymer crosslinking agent prepared in this embodiment is named TP100-CF5-B4A2-10Ole, and then crosslinked with SBS10 resin to obtain TP100-CF5-B4A2-10Ole-SBS10. The specific reaction process equation is as follows (where z is the proportion of butadiene polymerization at the 1,2 position, which is usually 55%-90% in this process): The specific steps are as follows: (1) Synthesis of the polymeric crosslinking agent TP100-CF5-B4A2-10Ole. In a 100mL three-necked flask, 0.01mol of the polymeric crosslinking agent obtained by copolymerizing 10% 4-bromoethyl-pentafluorophenylacetone with 1,1,1,2,2-pentafluoroheptane-3-one, linear terphenyl, and meta-terphenyl was dissolved in 40mL THF. A reflux condenser and a nitrogen balloon were prepared to purge air and provide nitrogen protection. 0.003mol of potassium tert-butoxide was dissolved and suspended in 5mL THF and slowly added dropwise to the flask while controlling the temperature. After the addition was complete, the mixture was kept at 40-70℃ and stirred for 4-8 hours.

[0054] The temperature was lowered to 10℃, and 20 ml of saturated NH4Cl aqueous solution was slowly added dropwise. The mixture was stirred at room temperature for 1-2 hours. The resulting white solid product was filtered and repeatedly washed with pure water with stirring. Finally, the white product was filtered again and dried under vacuum at 80℃ for 24 hours. The polymer yield was approximately 94.3%. The white solid product was the target polymer crosslinking agent. (2) The cross-linking polymerization step is the same as in Example 1, except for the addition of a polymeric cross-linking agent. The final product is a white, elastic solid resin particle or block, which is the target cross-linking product. The yield is approximately 97.7%. Example 5

[0055] The polymer crosslinking agent prepared in this embodiment is named TP70-CF5CF3-B4B2-10, and then crosslinked with EM10 resin to obtain TP100-CF5CF3-B4B2-10-EM10. The specific reaction process equation is as follows: The specific steps are as follows: (1) Synthesis of polymeric crosslinking agents. In a 250 mL three-necked flask equipped with a top mechanical stirrer, 6-bromotrifluorohexanone (2.33 g, 0.01 mol), 1,1,1,2,2-pentafluoroundecane-3-one (23.42 g, 0.09 mol), linear terphenyl (16.1 g, 0.07 mol), and meta-terphenyl (6.9 g, 0.03 mol) were dissolved in dichloromethane (100 mL). Then, trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were added dropwise over 30 minutes at 0 °C. The reaction was then continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white solid was filtered, washed with water, and immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white product was filtered, washed with water, and dried under vacuum at 80 °C for 12 hours to obtain 45.86 g of a white solid product. The yield of the polymer crosslinking agent was 97.6%.

[0056] (2) Synthesis of EM resin. In a 250 mL three-necked flask equipped with a top mechanical stirrer, N-methylpiperidinone (11.32 g, 0.1 mol) and linear terphenyl (23 g, 0.1 mol) were dissolved in dichloromethane (60 mL). Trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were then added dropwise over 30 minutes at 0 °C. The reaction was continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white fibrous product was filtered, washed with water, and dried under vacuum at 80 °C for 12 hours to obtain 31.4 g of a white solid product, with a yield of 96.6%.

[0057] (3) Crosslinking (TP70-CF5CF3-B4B2-10-EM10). In a 500 mL single-necked flask equipped with a magnetic stirrer, the above-mentioned polymeric crosslinking agent TP70-CF5CF3-B4B2-10 (4.6 g, 0.01 mol) was dissolved in a mixed solution (20 mL) of 1-methyl-2-pyrrolidone and tetrahydrofuran. At the same time, the polymer (32.5 g, 0.1 mol) from step (2) was dissolved in 1-methyl-2-pyrrolidone (320 mL). The mixture was added to the flask and stirred until homogeneous. The mixture was heated to 60 °C and stirred for 12 to 24 hours to obtain a pale yellow crosslinking reaction solution. Iodimethane (19.8 g, 0.2 mol) was then rapidly added to the crosslinking reaction solution. The mixture was stirred at room temperature for 12 h to 5 d. The resulting viscous orange-yellow solution was added dropwise to ethyl acetate. The yellow spherical solid particles were filtered, washed with water, and immersed in 1 M sodium hydroxide at room temperature for 2 hours. Finally, the off-white spherical solid resin particles were washed with water and dried under vacuum at 80°C for 24 hours to obtain orange-red solid resin particles, with a yield close to 100%. Example 6

[0058] The polymer crosslinking agent prepared in this embodiment is named TP70-CF5-B4A3-20, and then crosslinked with EM10 resin to obtain TP100-CF5-B4A3-20-EM10. The specific reaction process equation is as follows: (1) Synthesis of the polymeric crosslinking agent TP70-CF5-B4A3-20. In a 250 mL three-necked flask equipped with a top-mounted mechanical stirrer, 4-bromopropyl-pentafluorophenylacetone (6.90 g, 0.02 mol), 1,1,1,2,2-pentafluoroundecane-3-one (20.82 g, 0.08 mol), linear terphenyl (16.1 g, 0.07 mol), and meta-terphenyl (6.9 g, 0.03 mol) were dissolved in dichloromethane (100 mL). Then, trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were added dropwise over 30 minutes at 0 °C. The reaction was then continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white solid was filtered, washed with water, and then immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white product was filtered, washed with water, and dried under vacuum at 80°C for 12 hours to obtain 47.44 g of a white solid product. The yield of the polymer crosslinking agent was 96.9%.

[0059] (2) Synthetic resin. The specific operation is the same as step 2 of Example 5, yielding 31.7 g of white solid product, with a yield of 97.5%.

[0060] (3) Crosslinking (TP70-CF5-B4A3-20-EM10). The specific operation is the same as step 3 in Example 5, except that the polymer crosslinking agent used is different, and the final orange-red solid resin particles are obtained with a yield close to 100%. Example 7

[0061] The polymer crosslinking agent prepared in this embodiment is named TP100-CF3-A1A3-10, and then crosslinked with EM10 resin to obtain TP100-CF3-A1A3-10-EM10. The specific reaction process equation is as follows: (1) Synthesis of the polymeric crosslinking agent TP100-CF3-A1A3-10. In a 250 mL three-necked flask equipped with a top mechanical stirrer, 2.95 g (0.01 mol) of 4-bromopropyl-trifluoroacetophenone, 15.67 g (0.09 mol) of trifluoroacetophenone, and 23.0 g (0.1 mol) of linear terphenyl were dissolved in 100 mL of dichloromethane. Then, trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were added dropwise over 30 minutes at 0 °C. The reaction was continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white solid was filtered, washed with water, and immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white product was filtered, washed with water, and dried under vacuum at 80 °C for 12 hours to obtain 38.89 g of a white solid product. The yield of the polymeric crosslinking agent was 97.6%.

[0062] (2) Synthetic resin. The specific operation is the same as step 2 in Example 5, and a white solid product of 31.4 g is finally obtained, with a yield of 96.6%.

[0063] (3) Crosslinking (TP100-CF3-A1A3-10-EM10). The specific operation is the same as step 3 of Example 5, except that the polymer crosslinking agent used is different, and the final orange-red solid resin particles are obtained with a yield close to 100%. Example 8

[0064] The polymer crosslinking agent prepared in this embodiment is named TP70-CF3-A1A3-10, and then crosslinked with EM10 resin to obtain TP70-CF3-A1A3-10-EM10. The specific reaction process equation is as follows: (1) Synthesis of the polymeric crosslinking agent TP70-CF3-A1A3-10. In a 250 mL three-necked flask equipped with a top-mounted mechanical stirrer, 2.95 g (0.01 mol) of 4-bromopropyl-trifluoroacetophenone, 15.67 g (0.09 mol) of trifluoroacetophenone, 16.1 g (0.07 mol) of linear terphenyl, and 6.9 g (0.03 mol) of meta-terphenyl were dissolved in 100 mL of dichloromethane. Then, trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were added dropwise over 30 minutes at 0 °C. The reaction was then continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white solid was filtered, washed with water, and then immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white product was filtered, washed with water, and dried under vacuum at 80°C for 12 hours to obtain 39.09 g of a white solid product. The yield of the polymer crosslinking agent was 98.1%.

[0065] (2) Synthetic resin. The specific operation is the same as step 2 in Example 5, and a white solid product of 31.5 g is finally obtained, with a yield of 96.9%.

[0066] (3) Crosslinking (TP70-CF3-A1A3-10-EM10). The specific operation is the same as step 3 of Example 5, except that the polymer crosslinking agent used is different, and the final orange-red solid resin particles are obtained with a yield close to 100%. Example 9

[0067] The polymer crosslinking agent prepared in this embodiment is named TP70-CF5-B4A3-10, and then crosslinked with EM10 resin to obtain TP70-CF5-B4A3-10-EM10. The specific reaction process equation is as follows: (1) Synthesis of the polymeric crosslinking agent TP70-CF5-B4A3-10. In a 250 mL three-necked flask equipped with a top-mounted mechanical stirrer, 3.45 g (0.01 mol) of 4-bromopropyl-pentafluorophenylacetone, 19.63 g (0.09 mol) of 1,1,1,2,2-pentafluorooctane-3-one, 16.1 g (0.07 mol) of linear terphenyl, and 6.9 g (0.03 mol) of meta-terphenyl were dissolved in 100 mL of dichloromethane. Then, trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were added dropwise over 30 minutes at 0 °C. The reaction was then continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white solid was filtered, washed with water, and then immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white product was filtered, washed with water, and dried under vacuum at 80°C for 12 hours to obtain 44.10 g of a white solid product. The yield of the polymer crosslinking agent was 96.6%.

[0068] (2) Synthetic resin. The specific operation is the same as step 2 in Example 5, and a white solid product of 31.6 g is finally obtained, with a yield of 97.3%.

[0069] (3) Crosslinking (TP70-CF5-B4A3-10-EM10). The specific operation is the same as step 3 of Example 5, except that the polymer crosslinking agent used is different, and the final orange-red solid resin particles are obtained with a yield close to 100%. Example 10

[0070] The polymer crosslinking agent prepared in this embodiment is named TP100-CF5CF3-B4B2-10, and then crosslinked with EM10 resin to obtain TP100-CF5CF3-B4B2-10-EM10. The specific reaction process equation is as follows: (1) Synthesis of the polymeric crosslinking agent TP100-CF5CF3-B4B2-10. In a 250 mL three-necked flask equipped with a top mechanical stirrer, 2.33 g (0.01 mol) of 6-bromotrifluorohexanone, 23.42 g (0.09 mol) of 1,1,1,2,2-pentafluoroundecane-3-one, and 23.0 g (0.1 mol) of terphenyl were dissolved in 100 mL of dichloromethane. Then, trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were added dropwise over 30 minutes at 0 °C. The reaction was then continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white solid was filtered, washed with water, and immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white product was filtered, washed with water, and dried under vacuum at 80 °C for 12 hours to obtain 45.83 g of a white solid product. The yield of the polymer crosslinking agent was 97.6%.

[0071] (2) Synthetic resin. The specific operation is the same as step 2 in Example 5, and a white solid product of 31.9 g is finally obtained, with a yield of 98.2%.

[0072] (3) Crosslinking (TP100-CF5CF3-B4B2-10-EM10). The specific operation is the same as step 3 in Example 5, except that the polymer crosslinking agent used is different, and the final orange-red solid resin particles are obtained with a yield close to 100%. Comparative Example 1

[0073] This comparative example is a blank control of pure SBS resin without the addition of a polymeric crosslinking agent. The specific SBS resin preparation method is the same as step 2 of Example 1, except that no polymeric crosslinking agent is added, resulting in white elastic solid resin particles or lumps. The yield is approximately 97.9%. Comparative Example 2

[0074] The comparative example illustrates a specific method for preparing star-shaped SBS resin as follows: Add 200 mL of anhydrous THF to a 500 mL three-necked round-bottom flask equipped with a top-mounted powerful mechanical stirrer, and purge with nitrogen. Cool to -10 °C, and slowly add 0.8 mL of n-butyllithium solution, stirring for 15 min. Raise the temperature to 50 °C, and add 30 g of styrene dropwise, stirring for 10 to 90 min. Then cool to 40 °C, and slowly add 60 g of butadiene dissolved in 100 mL of THF solution, raising the temperature to 60 °C and stirring for approximately 30 min to 3 h. Continue adding 30 g of styrene dropwise, maintaining the temperature at 60 °C and stirring for 10-90 min.

[0075] Cool to 25℃, dilute 0.06 mL of SiCl4 with 10 mL of anhydrous THF to prepare a dilute solution, and slowly add the diluted SiCl4 / THF solution dropwise (completely over 5-10 minutes) into the reaction flask. After the addition is complete, continue stirring the reaction at 40-50℃ for 30-60 minutes. Then, 15 ml of anhydrous ethanol was slowly added dropwise, and the mixture was stirred for 10 min. 0.6 g of BHT (0.5 wt% relative to the total SBS) was added, and the mixture was stirred for 20 min. The solution was slowly poured into 1 L of hot water at 80°C under high-speed stirring, resulting in the precipitation of a large amount of white flocculent matter. After the addition was complete, stirring was continued for 1 h. The mixture was centrifuged, filtered, and washed repeatedly with pure water. After centrifugation and filtration, the white solid was transferred to 60°C and vacuum dried for 12 h. Finally, white elastic solid resin particles or lumps were obtained. The yield was approximately 97.9%. The star-shaped SBS resin prepared in this manner was used for sample preparation and testing. Comparative Example 3

[0076] This comparative example illustrates a specific method for preparing vulcanized SBS resin as follows: Preparation of vulcanized SBS: 50g of linear SBS prepared using the same process as in Comparative Example 1 was added to a mixer. The temperature was raised to 80℃, and after wrapping the rollers, 2g of ZnO, 0.5g of stearic acid, 5g of silica, and 0.3g of antioxidant RD were added to the mixer in sequence. The mixture was mixed for 3-5 minutes to form a masterbatch, and then passed through a thin slurry five times to ensure uniformity. Subsequently, 10g of naphthenic oil was slowly added, and the mixture was continued until smooth. The temperature was then controlled below 70℃, and 0.4g of MBT was added and mixed for 3 minutes. Finally, 0.7g of sulfur was added and mixed, and then passed through a thin slurry three times. The total mixing time was controlled within 15 minutes. After adjusting the roller gap to approximately 2mm, the mixture was sheeted and allowed to cool naturally. It was then cut into small pieces and left to stand in a cool, dry place for 24 hours.

[0077] In the flat vulcanizing machine, the mold is preheated to 155 ℃, the above material is quickly added to the mold and the mold is closed. After the mold is closed for 30 seconds, it is opened for about 1 second to remove air bubbles. The pressure is set at 12 MPa and the molding process takes about 10 minutes to vulcanize. Comparative Example 4

[0078] The crosslinking resin prepared in this comparative example is named C1-EM3, and the specific reaction equation is as follows: The specific steps are as follows: (1) Resin Synthesis. In a 250 mL three-necked flask equipped with a top-mounted mechanical stirrer, N-methylpiperidone (11.32 g, 0.1 mol) and straight-line terphenyl (23 g, 0.1 mol) were dissolved in dichloromethane (60 mL). Trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were then added dropwise over 30 minutes at 0 °C. The reaction was continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white fibrous product was filtered, washed with water, and dried under vacuum at 80 °C for 12 hours to obtain 31.6 g of a white solid product, with a yield of 97.1%.

[0079] (2) Crosslinking (C1-EM3). In a 500 mL single-necked flask equipped with a magnetic stirrer, 1,4-dibromobutane (0.003 mol) was dissolved in a mixed solution (20 mL) of 1-methyl-2-pyrrolidone and tetrahydrofuran. Simultaneously, the polymer (32.5 g, 0.1 mol) from step (1) was dissolved in 1-methyl-2-pyrrolidone (320 mL). The mixture was added to the flask and stirred until homogeneous. The mixture was heated to 60 °C and stirred for 12 h to 2 d to obtain a pale yellow crosslinking reaction solution. Iodomethane (19.8 g, 0.2 mol) was then rapidly added to the crosslinking reaction solution. The mixture was stirred at room temperature for 12 h to 5 d. The resulting viscous orange-yellow solution was added dropwise to ethyl acetate. The yellow solid particles were filtered, washed with water, and immersed in 1 M sodium hydroxide at room temperature for 2 hours. Finally, the pale yellow solid resin particles were washed with water and dried under vacuum at 80 °C for 24 h, with a yield close to 100%. Comparative Example 5

[0080] The crosslinking resin prepared in this comparative example is named C2-EM3, and the specific reaction equation is as follows: The specific steps are as follows: (1) Synthetic resin. Refer to step (1) of Comparative Example 4 above for resin synthesis.

[0081] (2) Crosslinking (C2-EM3). In a 500 mL single-necked flask equipped with a magnetic stirrer, 0.003 mol of 1,3,5-tris(bromomethyl)benzene was dissolved in a 20 mL mixture of 1-methyl-2-pyrrolidone and tetrahydrofuran. Simultaneously, 0.1 mol of the polymer from step (1) was dissolved in 320 mL of 1-methyl-2-pyrrolidone. The mixture was then added to the flask and stirred until homogeneous. The mixture was heated to 60 °C and stirred for 12 h to 2 d to obtain a pale yellow crosslinking reaction solution. Iodomethane (19.8 g, 0.2 mol) was then rapidly added to the crosslinking reaction solution. The mixture was stirred at room temperature for 12 h to 5 d. The resulting viscous orange-yellow solution was added dropwise to ethyl acetate. The yellow solid was filtered, washed with water, and immersed in 1 M sodium hydroxide for 2 hours at room temperature. Finally, the pale yellow solid resin was washed with water and dried under vacuum at 80 °C for 24 h, with a yield close to 100%. Comparative Example 6

[0082] The crosslinking resin prepared in this comparative example is named D1-EM3, and the specific reaction equation is as follows: The specific steps are as follows: (1) Synthesis of crosslinking resin (D1-EM3). In a 250 mL three-necked flask equipped with a top mechanical stirrer, N-methylpiperidone (11.32 g, 0.1 mol), 9,9-spirodifluorene (0.95 g, 0.003 mol), and linear terphenyl (22.3 g, 0.097 mol) were dissolved in dichloromethane (60 mL). Trifluoroacetic acid (7.7 mL) and trifluoromethanesulfonic acid (TFSA) (79.6 mL) were then added dropwise over 30 minutes at 0 °C. The reaction was continued at this temperature for 4–48 hours. The resulting viscous brown solution was slowly poured into an ethanol / water solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M sodium hydroxide at room temperature for 12 hours. Finally, the white fibrous product was filtered, washed with water, and dried under vacuum at 80 °C for 12 hours to obtain a white solid product with a yield of approximately 98.3%. The polymer obtained above was completely dissolved in 1-methyl-2-pyrrolidone (350 ml), and then iodomethane (19.8 g, 0.2 mol) was rapidly added to the solution. The reaction was stirred at room temperature for 12 h to 5 d. The resulting viscous orange-yellow solution was added dropwise to ethyl acetate. The yellow solid was filtered, washed with water, and immersed in 1M sodium hydroxide at room temperature for 2 hours. Finally, the pale yellow solid resin was washed with water and dried under vacuum at 80 °C for 24 h, with a yield close to 100%. Comparative Example 7

[0083] This comparative example only synthesizes the resin, and the specific operation is the same as the resin synthesis in step (1) of comparative example 4.

[0084] Mechanical property testing The final products of Examples 1-4 and Comparative Examples 1-3 were placed in a mold and hot-pressed at 150°C and 10MPa for 5-10 minutes. After cooling and demolding, samples with a thickness of 2±0.2 mm were obtained. Following GB / T 528-2009, at least five parallel dumbbell-shaped specimens were cut from the obtained samples using a cutting tool. The specimens were then placed in an environment of 23±2°C and 50%RH for 24 hours. Their mechanical properties were tested using a tensile testing machine.

[0085] Table 1 shows the comparative results of mechanical property tests of crosslinked polymers using the polymer crosslinking agent described in this invention under different process ratios in the above non-limiting examples: Table 1 sample Tensile strength Elongation at break Comparative Example 1 26.4MPa 244.8% Comparative Example 2 32.4MPa 177.3% Comparative Example 3 31.5MPa 167.7% Example 1 36.2MPa 249.2% Example 2 34.9MPa 262.3% Example 3 35.6MPa 256.1% Example 4 35.8MPa 250.6% The test results in Table 1 show that: After crosslinking modification of SBS resin with the phenylenealkyl polymer crosslinking agent described in this invention, its mechanical properties are significantly and synergistically enhanced. Specifically, the tensile strength of the modified resin is increased by more than 32% compared to the unmodified pure SBS resin, while its elongation at break is completely maintained and slightly improved. This indicates that this invention overcomes the technical defects of traditional star-shaped modification (Comparative Example 2) and traditional vulcanization crosslinking (Comparative Example 3) that sacrifice toughness while effectively and significantly improving the material strength, and successfully achieves simultaneous optimization of strength and toughness. Experiments also show that to enhance the crosslinking effect, such as in traditional vulcanization processes, the amount of sulfur needs to be increased. Although this increases tensile strength, it leads to hardening of the resin material and makes subsequent processing difficult.

[0086] Anion exchange membrane performance testing The final products of Examples 5-10 and Comparative Examples 4-7 were used as test subjects, and the specific operation was as follows: (1) Membrane preparation and hydroxide ion exchange. 1.0 g of the test sample was dissolved in NMP (15 mL), cast onto a glass or stainless steel plate, and dried at 60–100 °C for 5–24 h to form a membrane. The membrane was then vacuum dried at 80–150 °C for 5–24 h, resulting in a membrane thickness between 10 and 100 μm. The membrane (in bromide form) was peeled off from the glass plate in contact with deionized water. The membrane was then subjected to hydroxide ion exchange in a 1 M sodium hydroxide solution at 80 °C to obtain an anion exchange membrane in hydroxide form.

[0087] (2) Fenton's reagent test and alkali resistance test: Fenton's reagent (3% hydrogen peroxide aqueous solution, 2 ppm Fe) was used. 2 +The oxidative stability of the membrane was tested. 50 mg of the dry membrane was immersed in Fenton's reagent at 80°C. After 1 hour, the membrane was removed from Fenton's reagent, washed with distilled water, and equilibrated in distilled water for at least 24 hours. The membrane was then dried and weighed. The residual mass was calculated based on the membrane mass after immersion in the Fenton test at 80°C for 1 hour. (3) Mechanical properties and mechanical stability tests. Six cross-linked membranes of each group with an area of ​​2*5cm were taken and kept at 40% and 90% relative humidity (RH) for 300 hours respectively, with three measurements taken at each humidity level. The mechanical properties test method refers to the mechanical properties test method of proton exchange membrane GB / T 20042.3-2022.

[0088] The test results are shown in Table 2 below: Table 2 sample Tensile strength (MPa) Elongation at break (%) Weight loss rate (%) in 1-hour Fenton test Comparative Example 4 38.4 26.7 2.17 Comparative Example 5 39.1 25.1 2.18 Comparative Example 6 43.9 22.8 1.60 Comparative Example 7 36.7 27.4 2.75 Example 5 44.2 38.2 0.99 Example 6 47.3 38.3 0.79 Example 7 45.1 32.9 1.19 Example 8 44.3 34.6 1.38 Example 9 44.7 36.1 0.80 Example 10 44.3 37.9 1.18 As can be seen from the table, the technical solution provided by this invention achieves a comprehensive and unexpected synergistic enhancement effect in key performance compared with the prior art, as specifically reflected as follows: 1. Breakthrough improvement in mechanical properties: In terms of tensile strength, Examples 5-10 of the present invention (44.2-47.3 MPa) showed an improvement of up to 20.4% to 28.8% compared to the blank Comparative Example 7 (36.7 MPa), and were significantly better than Comparative Example 4 (38.4 MPa), demonstrating the outstanding effect of the present invention in enhancing the tensile strength of materials.

[0089] Regarding elongation at break, Examples 5-10 (32.9-38.3%) of the present invention not only avoided the decreasing toughness trend shown in Comparative Examples 4 (26.7%), 5 (25.1%), and 6 (22.8%), but also achieved a significant improvement of approximately 23% to 43% compared to Comparative Example 7 (27.4%). This result confirms that the present invention effectively overcomes the technical bottleneck of the "strength-toughness mutual exclusion effect" in the field of material strengthening, achieving a synergistic improvement in the mechanical properties of materials.

[0090] 2. Improved resistance to aging (chemical oxidation): After rigorous Fenton reagent (1 hour) aging tests, the weight loss rates (0.79%-1.39%) of Examples 5-10 of this invention were significantly lower than those of Comparative Example 7 (2.75%) and Comparative Example 4 (2.17%). This data fully demonstrates that this invention endows the material with excellent long-term stability and durability.

[0091] 3. Improved shape, size, and uniformity of distribution: Furthermore, the crosslinking agent of the present invention can achieve multi-dimensional control of the apparent properties of resins during the crosslinking modification process. Experiments (attached) Figure 1-4 The results show that, under the same process parameters, the resin modified by this crosslinking agent exhibits significant optimization in the precipitation stage: the morphology, size, and uniformity of the crosslinked polymer particles are significantly improved; thereby reducing the amount of fine dust generated and effectively controlling dust pollution in the production process.

[0092] The above is a further detailed description of the present invention and should not be considered as a limitation on the specific implementation of the present invention. For those skilled in the art, simple deductions or substitutions made without departing from the concept of the present invention are all within the protection scope of the present invention.

Claims

1. A alkylene diphenylene polymer crosslinking agent, characterized in that, The alkylene oxide polymer crosslinking agent has the following structural units: 1) The structural unit shown in Equation 1A below: ； 2) At least one structural unit from formula 2A or formula 2B: ； In the formula, q represents an integer between 0 and 5; The R 20 R 30 R 40 R 50 R 60 R 70 R 80 and R 90 Each group is independently selected from hydrogen, halide, alkyl, alkenyl, alkynyl, or aryl, and the alkyl, alkenyl, alkynyl, or aryl group is optionally substituted with a halide, and wherein R 30 and R 60 Optionally, a halide or alkyl-substituted five- or six-membered ring can be attached; The R1 and R3 groups are each independently selected from any one of perfluoroalkyl, benzyl, aryl or alkyl, and the aryl or benzyl groups are optionally replaced with fluorides; The R2 group is selected from any one of halogen, alkenyl, alkynyl, and cyano, and the alkenyl, alkynyl, or cyano group is optionally substituted with a halide; The R4 group is selected from halogens, C1-C... 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12 Alkyne, cyano, or haloaryl; the R5, R6, R7, and R8 groups are each independently hydrogen, halogen, or C1-C. 12 Haloalkyl, C1-C 12 Alkyl, C2-C 12 alkenyl, C2-C 12 Groups including alkynyl, cyano, aryl, haloaryl, C3-C6 cycloalkyl, and 5-6 heteroaryl groups; The R 4、 The aryl, cycloalkyl, and heteroaryl groups contained in R5, R6, R7, and R8 may optionally be replaced by one or more alkyl groups selected from C1-C6 and halogens; The R 18 The group is selected from alkylene groups, wherein the number of carbon atoms in the alkylene group is any integer between 1 and 11.

2. The alkylene diphenylene polymer crosslinking agent according to claim 1, characterized in that, The alkylene oxide polymer crosslinking agent also has the structural units shown in Formula 3A and Formula 3B: ； The R9, R 10 Each group is independently selected from any one of perfluoroalkyl, benzyl, aryl or alkyl, and the aryl or benzyl group is optionally substituted with a fluoride; The R 11 R 12 R 13 R 14 R 15 R 16 Each is independently any one of hydrogen, fluoride, alkyl, and aryl, and the alkyl or aryl group is optionally replaced by a fluoride; The R 17 The group is selected from alkylene groups, wherein the number of carbon atoms in the alkylene group is any integer between 1 and 11.

3. The alkylene diphenylene polymer crosslinking agent according to claim 1 or 2, characterized in that, The number of moles of the structural unit shown in Formula 1A in the alkylene diphenylene polymer crosslinking agent is equal to the sum of the number of moles of the structural units shown in Formulas 2A, 2B, 3A, and 3B.

4. The alkylene diphenylene polymer crosslinking agent according to claim 1 or 2, characterized in that, The R1, R3, R9, R 10 Each group is independently selected from trifluoromethyl or pentafluoroethyl.

5. The alkylene diphenylene polymer crosslinking agent according to claims 1-4, characterized in that, The structural formula of the alkylene oxide polymer crosslinking agent is as follows: ; In the formula, m, n, and x are any values ​​between 0 and 100; The R 100 R 120 Each group is independently selected from trifluoromethyl or pentafluoroethyl; The R 110 R 130 Each group is independently selected from C4-C7 straight-chain alkyl, C6-C10 aryl, C7-C10 straight-chain aralkyl, C8-C10 straight-chain arene, or a halogenated form of the aforementioned groups.

6. The alkylene diphenylene polymer crosslinking agent according to claim 1, characterized in that, The R 110 R 130 Each group is independently selected from styryl, phenylpropyl, phenyl, butyl, heptyl, or a halogenated form of the aforementioned groups.

7. The alkylene diphenylene polymer crosslinking agent according to claim 5 or 6, characterized in that, The R 110 R 130 When the group is a halogenated product with a straight chain, its halogenation site is at the end of the straight chain.

8. The alkylene diphenylene polymer crosslinking agent according to claim 1, characterized in that, The alkylene oxide polymer crosslinking agent is prepared by the following method: The polymer is prepared by mixing monomers of formula 1A, 2A or 2B and optionally formula 3A or 3B under a catalyst via a superacid reaction. The catalyst is one or a combination of trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, and heptafluorobutyric acid.

9. A composite crosslinking resin, characterized in that, It is prepared by copolymerization and crosslinking of the alkylene oxide polymer crosslinking agent according to claim 1 with a synthetic resin, wherein the synthetic resin is selected from SBS or EM resin.

10. The application of the alkylene diphenylene polymer crosslinking agent of claim 1 or the composite crosslinking resin of claim 9 in the preparation of anion exchange resins.

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