A high-temperature-resistant polymerizable material composition and a preparation method thereof
By combining polyarylene ether copolymers with hyperbranched polysiloxanes and two-dimensional nanomaterials, the problems of high processing difficulty and insufficient toughness of high-performance polyarylene ether materials have been solved, enabling rapid molding and high strength performance of materials under high temperature environments, which are suitable for aerospace, electronic information, energy equipment and other fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANGHAI ASTRACE NEW MATERIAL TECH CO LTD
- Filing Date
- 2026-04-24
- Publication Date
- 2026-06-02
AI Technical Summary
Existing high-performance polyarylether materials are difficult to process in the high-temperature molten state, have high melt viscosity, long molding cycle, insufficient toughness and poor impact resistance after curing, and are difficult to meet the requirements of key components with high reliability.
A combination of polyarylene ether copolymers containing reactive heterocyclic structures, hyperbranched polysiloxanes containing unsaturated end groups, two-dimensional nanomaterials modified with organosilane surfaces, and free radical initiators is used to form a high-strength, tough, and high-temperature resistant material through photo-irradiation curing.
It achieves high thermal stability, good mechanical properties and rapid prototyping of materials, making it suitable for key components in high-temperature environments. It has excellent heat resistance and mechanical properties, and is applicable to aerospace, electronic information, energy equipment and other fields.
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Figure CN122127770A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of polymer composite materials technology, and in particular to a high-temperature resistant polymerizable material composition and its preparation method. Background Technology
[0002] High-performance polymer materials, as core foundational materials for strategic emerging industries, play an irreplaceable role in cutting-edge technology fields such as aerospace, electronic information, and energy equipment. Especially in extreme application scenarios such as peripheral components of aero-engines, structural components of hypersonic vehicles, deep well exploration equipment, and nuclear reactor auxiliary systems, materials not only need to withstand high-temperature thermal oxidation environments exceeding 300°C, but also must maintain excellent mechanical properties and dimensional stability. This places extremely stringent requirements on the comprehensive performance of polymer material systems.
[0003] High-performance engineering plastics based on polyarylethers, such as polyetheretherketone (PEEK) and polyaryletheronitriles (PANI), possess outstanding thermal stability, chemical inertness, and mechanical strength due to their dense aromatic ring structure in the molecular backbone, making them a key research focus in the field of high-temperature polymers. However, traditional polyarylether materials still face many challenges in practical applications: on the one hand, their processing usually requires high-temperature molten states, resulting in technical bottlenecks such as high processing temperatures, high melt viscosity, and long molding cycles; on the other hand, cured polyarylether materials often lack sufficient toughness and have poor impact resistance, making it difficult to meet the requirements of critical components with high reliability.
[0004] To address the aforementioned issues, researchers have attempted to improve the overall performance of polyarylether materials through strategies such as copolymerization modification, blending and composite, or nanofiller reinforcement. However, existing technologies still face technical challenges such as poor nanofiller dispersion, insufficient interfacial bonding strength, and complex curing processes, making it difficult to achieve synergistic optimization of the material's heat resistance, mechanical properties, and processing performance.
[0005] Therefore, how to develop a novel polymerizable material system that combines excellent heat resistance, good mechanical properties, and rapid prototyping has become a technical problem that urgently needs to be solved by those skilled in the art.
[0006] Therefore, this invention is proposed. Summary of the Invention
[0007] To address the aforementioned technical problems, this application provides a high-temperature resistant polymerizable material composition and its preparation method, aiming to solve the technical challenge that existing high-performance polymer materials cannot simultaneously achieve excellent heat resistance, mechanical properties, and rapid processing and molding, thereby providing a solution for high-end manufacturing fields that require high heat resistance and rapid molding or low-temperature curing.
[0008] In order to achieve the objective of this invention, the following technical solution is adopted: This invention provides a high-temperature resistant polymerizable material composition, comprising a polyarylene ether copolymer containing a reactive heterocyclic structure, a hyperbranched polysiloxane containing unsaturated end groups, a two-dimensional nanomaterial modified with an organosilane surface, and a free radical initiator; the mass ratio of the polyarylene ether copolymer containing the reactive heterocyclic structure to the hyperbranched polysiloxane containing unsaturated end groups is 1:(0.3-0.8), the amount of the two-dimensional nanomaterial modified with an organosilane surface is 1%-5% of the total mass of the polyarylene ether copolymer and the hyperbranched polysiloxane, and the amount of the free radical initiator is 0.5%-5% of the total mass of the polyarylene ether copolymer and the hyperbranched polysiloxane.
[0009] Wherein, the reactive heterocyclic structure is at least one of benzoxazinone, benzoxazole, or benzimidazole; the number-average molecular weight of the hyperbranched polysiloxane is 2000-5000 g / mol; the unsaturated end group is vinyl or allyl; and the two-dimensional nanomaterial is any one of layered metal oxide nanosheets, layered bimetallic hydroxide nanosheets, or MXene nanosheets.
[0010] Furthermore, the polyarylene ether copolymer is a polyarylene ether nitrile copolymer containing a benzoxazinone structure, and the molar percentage of the benzoxazinone structure in the main chain of the polyarylene ether copolymer is 10%-30%.
[0011] Furthermore, the hyperbranched polysiloxane is a hyperbranched structure prepared by a hydrolysis-condensation method from vinyltrimethoxysilane and tetramethyltetravinylcyclotetrasiloxane.
[0012] Furthermore, the two-dimensional nanomaterial is strontium titanate or barium titanate nanosheets with a thickness of 1-5 nm.
[0013] Furthermore, the free radical initiator is a binary photoinitiating system composed of metal nanoclusters and sulfur- or nitrogen-containing hydrogen donor compounds.
[0014] Furthermore, the metal nanoclusters are gold or silver nanoclusters with a particle size of 1-3 nm, the sulfur-containing hydrogen donor compound is a thiol compound, and the nitrogen-containing hydrogen donor compound is an amine compound.
[0015] The present invention also provides a method for preparing the above-described high-temperature resistant polymerizable material composition, comprising the following steps: S1: Hyperbranched polysiloxanes containing unsaturated end groups and two-dimensional nanomaterials modified with organosilane surfaces are dispersed in an organic solvent and premixed under ultrasonic assistance to form a uniform hybrid dispersion. S2: Dissolve a polyarylene ether copolymer containing a reactive heterocyclic structure in an aprotic polar solvent to prepare a solution; S3: Under shear conditions, the hybrid dispersion is added to the solution in step S2 and mixed evenly to form a casting solution; S4: Add a free radical initiator to the casting solution and cure it by light irradiation.
[0016] Furthermore, in step S1, the organic solvent is a mixed solvent prepared by mixing tetrahydrofuran and N,N-dimethylformamide in a volume ratio of 1:(2-4).
[0017] Furthermore, the ultrasonic power is 300-500W, and the ultrasonic time is 30-60min.
[0018] Furthermore, in step S4, the curing and molding process uses an LED light source with a wavelength of 365-405nm for light irradiation curing, with an irradiation intensity of 50-100 mW / cm² and an irradiation time of 10-30min.
[0019] The present invention has the following technical effects: (1) This application achieves a significant improvement in the heat resistance of materials through the organic composite of polyarylene ether copolymers and hyperbranched polysiloxanes. The polyarylene ether backbone containing rigid heterocyclic structures such as benzoxazinone endows the material with an intrinsic high glass transition temperature and excellent thermo-oxidative stability, while the three-dimensional cross-linked network formed by the hyperbranched polysiloxane under the action of free radical initiators further enhances the binding effect between molecular chains and restricts the free movement of chain segments at high temperatures. At the same time, the two-dimensional nanomaterials modified with organosilane are uniformly dispersed in the matrix. Their nanoscale layered structure can not only effectively block the diffusion path of thermal decomposition products, but also delay the heat conduction process through physical barrier effect.
[0020] (2) This application achieves a comprehensive improvement in the mechanical properties of materials through a combination of rigid and flexible molecular structure design and multiphase interface control. The rigid aromatic backbone of polyarylene copolymers provides a high strength and modulus basis for the system, while the unique spherical three-dimensional topology of hyperbranched polysiloxanes and their abundant flexible end segments can form stress dispersion centers in the matrix, effectively absorbing and dissipating external impact energy, overcoming the inherent defect of insufficient toughness in traditional polyarylene materials. More importantly, the two-dimensional nanomaterials modified with organosilanes form a strong chemical bond interface with the polymer matrix. Their ultra-high specific surface area and two-dimensional layered structure can efficiently transfer and bear stress, inducing toughening mechanisms such as crack deflection and creasing. Attached Figure Description
[0021] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0022] Figure 1 This is a flowchart of a method for preparing a high-temperature resistant polymerizable material composition according to this application. Detailed Implementation
[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0024] In a first aspect, this application provides a high-temperature resistant polymerizable material composition, comprising a polyarylene ether copolymer containing a reactive heterocyclic structure, a hyperbranched polysiloxane containing unsaturated end groups, a two-dimensional nanomaterial modified with an organosilane surface, and a free radical initiator; the mass ratio of the polyarylene ether copolymer containing the reactive heterocyclic structure to the hyperbranched polysiloxane containing unsaturated end groups is 1:(0.3-0.8), the amount of the two-dimensional nanomaterial modified with an organosilane surface is 1%-5% of the total mass of the polyarylene ether copolymer and the hyperbranched polysiloxane, and the amount of the free radical initiator is 0.5%-5% of the total mass of the polyarylene ether copolymer and the hyperbranched polysiloxane; Wherein, the reactive heterocyclic structure is at least one of benzoxazinone, benzoxazole, or benzimidazole; the number-average molecular weight of the hyperbranched polysiloxane is 2000-5000 g / mol; the unsaturated end group is vinyl or allyl; and the two-dimensional nanomaterial is any one of layered metal oxide nanosheets, layered bimetallic hydroxide nanosheets, or MXene nanosheets.
[0025] In some embodiments, the polyarylene ether copolymer is a polyarylene ether nitrile copolymer containing a benzoxazinone structure, and the molar percentage of the benzoxazinone structure in the main chain of the polyarylene ether copolymer is 10%-30%.
[0026] In some embodiments, the hyperbranched polysiloxane is a hyperbranched structure prepared by hydrolysis-condensation polymerization of vinyltrimethoxysilane and tetramethyltetravinylcyclotetrasiloxane.
[0027] In some embodiments, the two-dimensional nanomaterial is strontium titanate or barium titanate nanosheets with a thickness of 1-5 nm.
[0028] In some embodiments, the free radical initiator is a binary photoinitiating system composed of metal nanoclusters and sulfur- or nitrogen-containing hydrogen donor compounds.
[0029] In some embodiments, the metal nanoclusters are gold or silver nanoclusters with a particle size of 1-3 nm, the sulfur-containing hydrogen donor compound is a thiol compound, and the nitrogen-containing hydrogen donor compound is an amine compound.
[0030] Secondly, such as Figure 1 As shown, this application also provides a method for preparing the above-described high-temperature resistant polymerizable material composition, comprising the following steps: S1: Hyperbranched polysiloxanes containing unsaturated end groups and two-dimensional nanomaterials modified with organosilane surfaces are dispersed in an organic solvent and premixed under ultrasonic assistance to form a uniform hybrid dispersion. S2: Dissolve a polyarylene ether copolymer containing a reactive heterocyclic structure in an aprotic polar solvent to prepare a solution; S3: Under shear conditions, the hybrid dispersion is added to the solution in step S2 and mixed evenly to form a casting solution; S4: Add a free radical initiator to the casting solution and cure it by light irradiation.
[0031] In some embodiments, in step S1, the organic solvent is a mixed solvent prepared by mixing tetrahydrofuran and N,N-dimethylformamide in a volume ratio of 1:(2-4).
[0032] In some embodiments, the ultrasonic power is 300-500W and the ultrasonic time is 30-60min.
[0033] In some embodiments, in step S4, the curing process uses an LED light source with a wavelength of 365-405nm for light irradiation curing, with an irradiation intensity of 50-100 mW / cm² and an irradiation time of 10-30 min.
[0034] The following is a detailed explanation using specific embodiments: Example 1: S1: Preparation of hybrid dispersion Hyperbranched polysiloxanes are prepared via hydrolysis-condensation polymerization, with the specific steps as follows: Weigh 25.0 g (168.7 mmol) of vinyltrimethoxysilane (purchased from Aladdin Reagent Co., Ltd.) and 12.5 g (36.2 mmol) of tetramethyltetravinylcyclotetrasiloxane (purchased from Maclean Biotech Co., Ltd.), and add them to a 500 mL three-necked flask. Then add 150 mL of anhydrous ethanol and 15 mL of deionized water.
[0035] Under nitrogen protection, 0.1 mol / L hydrochloric acid solution was slowly added dropwise to adjust the pH of the reaction system to 3-4. The reaction system was then heated to 60°C and reacted for 10 hours under mechanical stirring.
[0036] After the reaction was completed, the reaction solution was transferred to a rotary evaporator and distilled under reduced pressure at 50°C to obtain a viscous crude product.
[0037] The crude product was dissolved in 50 mL of tetrahydrofuran and filtered to remove insoluble gel particles.
[0038] The filtrate was then subjected to rotary evaporation to remove tetrahydrofuran. The resulting product was dried in a vacuum drying oven at 60°C for 24 hours to obtain a pale yellow viscous liquid, which is a vinyl-terminated hyperbranched polysiloxane with a number average molecular weight of 2000 g / mol.
[0039] Weigh 30g of vinyl-terminated hyperbranched polysiloxane with a number average molecular weight of 2000g / mol. This hyperbranched polysiloxane was prepared by hydrolysis-condensation polymerization of vinyltrimethoxysilane (purchased from Aladdin Reagent Co., Ltd.) and tetramethyltetravinylcyclotetrasiloxane (purchased from Maclean Biotechnology Co., Ltd.).
[0040] Weigh 0.8g of strontium titanate nanosheets modified with vinyltrimethoxysilane (purchased from Nanjing Muke Nanotechnology Co., Ltd., thickness 1-5nm, sheet diameter 0.5-2μm).
[0041] The two raw materials were added to a mixed solvent prepared by mixing tetrahydrofuran (purchased from Sinopharm Chemical Reagent Co., Ltd.) and N,N-dimethylformamide (purchased from Sinopharm Chemical Reagent Co., Ltd.) at a volume ratio of 1:2.
[0042] The mixture was treated with an ultrasonic power of 300W for 60 minutes to form a homogeneous hybrid dispersion.
[0043] S2: Preparation of polyarylether copolymer solutions Weigh 100g of a polyarylene ether copolymer containing a benzimidazole structure (the molar percentage of benzimidazole structure in the main chain is 10%), dissolve it in N,N-dimethylacetamide (purchased from Sinopharm Chemical Reagent Co., Ltd.), prepare a 15% mass fraction solution, and stir until completely dissolved.
[0044] S3: Mixing of casting solution Under high-speed shearing conditions, the prepared hybrid dispersion was slowly added to the polyarylether copolymer solution, and shearing and mixing continued for 1 hour to obtain a uniform casting solution.
[0045] S4: Curing and molding A binary photoinitiator system consisting of gold nanoclusters and dodecyl mercaptan was added to the casting solution. Specifically, gold nanoclusters with a particle size of 1-3 nm (purchased from Sigma-Aldrich, dissolved in toluene, concentration 2 mg / mL) were selected as the photoinitiator component, and dodecyl mercaptan (purchased from Sinopharm Chemical Reagent Co., Ltd.) was added as the hydrogen donor. The total amount of initiator was 0.5% of the total mass of the polyarylene ether copolymer and the hyperbranched polysiloxane.
[0046] The mixed casting solution was cast into a film and then cured by light irradiation using an LED light source with a wavelength of 365nm. The irradiation intensity was 50mW / cm² and the irradiation time was 30min, resulting in a high-temperature resistant polymer material.
[0047] Example 2 S1: Preparation of hybrid dispersion The preparation of hyperbranched polysiloxanes is as follows: Weigh 60.0 g (404.9 mmol) of vinyltrimethoxysilane (purchased from Aladdin Reagent (Shanghai) Co., Ltd.) and 30.0 g (86.8 mmol) of tetramethyltetravinylcyclotetrasiloxane (purchased from Maclean Biochemical Technology Co., Ltd.), and add them to a 2L three-necked flask. Then add 350 mL of anhydrous ethanol (purchased from Sinopharm Chemical Reagent Co., Ltd.) and 35 mL of deionized water.
[0048] Under nitrogen protection, 0.1 mol / L hydrochloric acid solution was slowly added dropwise to adjust the pH of the reaction system to 3–4. The reaction system was then heated to 65°C and reacted for 12 hours with mechanical stirring.
[0049] After the reaction was completed, the reaction solution was transferred to a rotary evaporator and distilled under reduced pressure at 50°C to obtain a viscous crude product.
[0050] The crude product was dissolved in 120 mL of tetrahydrofuran and filtered to remove insoluble gel particles.
[0051] The filtrate was then subjected to rotary evaporation to remove tetrahydrofuran. The resulting product was dried in a vacuum drying oven at 60°C for 24 hours to obtain a pale yellow viscous liquid, which is a vinyl-terminated hyperbranched polysiloxane with a number average molecular weight of 5000 g / mol.
[0052] Weigh 80g of vinyl-terminated hyperbranched polysiloxane with a number average molecular weight of 5000g / mol. This hyperbranched polysiloxane was prepared by hydrolysis-condensation polymerization of vinyltrimethoxysilane (purchased from Aladdin Reagent (Shanghai) Co., Ltd.) and tetramethyltetravinylcyclotetrasiloxane (purchased from Maclean Biochemical Technology Co., Ltd.).
[0053] Weigh 9.0g of MXene nanosheets (purchased from Jilin Yi Technology Co., Ltd., thickness 1-3nm, diameter 1-5μm) that have been modified with vinyltriethoxysilane.
[0054] The two raw materials were added to a mixed solvent prepared by mixing tetrahydrofuran (purchased from Sinopharm Chemical Reagent Co., Ltd.) and N,N-dimethylformamide (purchased from Sinopharm Chemical Reagent Co., Ltd.) at a volume ratio of 1:4.
[0055] The mixture was treated with an ultrasonic power of 500W for 30 minutes to form a homogeneous hybrid dispersion.
[0056] S2: Preparation of polyarylether copolymer solutions Weigh 100g of polyarylene ether nitrile copolymer containing benzoxazinone structure (the molar percentage of benzoxazinone structure in the main chain is 30%), dissolve it in N-methylpyrrolidone (purchased from Sinopharm Chemical Reagent Co., Ltd.) to prepare a 15% mass fraction solution, and stir until completely dissolved.
[0057] S3: Mixing of casting solution Under high-speed shearing conditions, the prepared hybrid dispersion was slowly added to the polyarylether copolymer solution, and shearing and mixing continued for 1 hour to obtain a uniform casting solution.
[0058] S4: Curing and molding A binary photoinitiator system consisting of silver nanoclusters and triethylamine was added to the above casting solution. Specifically, silver nanoclusters with a particle size of 1-3 nm (purchased from Sigma-Aldrich) were selected as the photoinitiator component, and triethylamine (purchased from Sinopharm Chemical Reagent Co., Ltd.) was added as the hydrogen donor. The total amount of initiator was 5% of the total mass of the polyarylene ether copolymer and the hyperbranched polysiloxane.
[0059] The mixed casting solution was cast into a film and then cured by light irradiation using an LED light source with a wavelength of 405nm. The irradiation intensity was 100 mW / cm² and the irradiation time was 10 min, resulting in a high-temperature resistant polymer material.
[0060] Comparative Example 1 The specific preparation process is the same as in Example 2, except that no two-dimensional nanomaterials modified with organosilane are added.
[0061] Comparative Example 2 The specific preparation process is the same as in Example 2, except that conventional modified epoxy acrylate is used instead of polyarylene ether nitrile copolymer containing benzoxazole structure.
[0062] Comparative Example 3 The specific preparation process is the same as in Example 2, except that a conventional free radical initiator is used instead.
[0063] Experimental Example 1: Performance Comparison Test of High-Temperature Resistant Polymerizable Material Compositions I. Preparation of Experimental Samples The samples prepared in Examples 1-2 and Comparative Examples 1-3 were used to prepare three parallel samples for performance testing. The samples were prepared in two specifications: a thin film with a thickness of 2 mm and a sheet with a thickness of 5 mm.
[0064] II. Experimental Procedure Step 1: Sample numbering and pretreatment The six prepared samples were numbered as follows: E1: Sample of Example 1 E2: Sample from Example 2 C1: Comparative Example 1 Sample C2: Comparative Example 2 Sample C3: Comparative Example 3 Sample All samples were dried in a vacuum drying oven at 60°C for 24 hours to remove residual solvents and moisture.
[0065] Step 2: Glass transition temperature (Tg) test Turn on the instrument and introduce N2 atmosphere at a flow rate of 50 mL / min; Weigh 10 mg of each sample, place them in an aluminum sample dish, and press and seal them tightly; Set the heating program: increase the temperature from 50℃ to 400℃ at a rate of 10℃ / min; Record the DSC curve and take the midpoint of the heat flux change as the Tg value; Each group of samples was tested 3 times, and the average value was taken.
[0066] Step 3: Thermogravimetric Analysis (TGA) Turn on the thermogravimetric analyzer and introduce N2 atmosphere at a flow rate of 40 mL / min; Weigh 15 mg of each sample and place it in an alumina crucible; Set the heating program: increase the temperature from 50℃ to 800℃ at a rate of 20℃ / min; Record the thermogravimetric curves and statistically analyze the 5% thermogravimetric temperature (Td5%) and the residual carbon rate at 800℃. Each group of samples was tested 3 times, and the average value was taken.
[0067] Step 4: Tensile strength test The 2mm thick film sample was cut into dumbbell-shaped standard specimens; Turn on the universal testing machine and set the tensile rate to 5 mm / min; Clamp the specimen in the fixture, ensuring that the specimen axis is parallel to the tensile direction; Start the test until the specimen breaks, and record the maximum tensile strength. Five parallel samples were tested for each group of samples, and the average value was taken.
[0068] Step 5: Double bond conversion rate test Turn on the infrared spectrometer and configure the ATR accessories; Before curing, a small amount of casting solution was taken and subjected to infrared scanning, recording the result at 1635 cm⁻¹. -1 The area of the characteristic peak at C=C is A0; Immediately after light irradiation, the cured sample was taken for infrared scanning, and the value at 1635 cm⁻¹ was recorded. -1 The area of the remaining C=C characteristic peak is A1; Normalization was performed using the benzene ring skeletal vibration peak as an internal standard peak. Calculate double bond conversion rate: Conversion rate (%) = (1 - A1 / A0) × 100%; Each group of samples was tested 3 times, and the average value was taken.
[0069] Step 6: Deep curing effect test Take a 5mm thick sample and cut it along the center line to obtain a fresh cross-section; Using a microhardness tester, the Shore D hardness is tested every 0.5 mm, starting from the sample surface. Five points were tested at each depth location, and the average value was taken. Plot the hardness as a function of depth to assess the uniformity of deep curing. Step 7: High-Temperature Aging Performance Test Place the sample in a high-temperature aging chamber and set the temperature to 300℃. Aging in air for 24 hours; Weigh the samples before and after aging, and calculate the mass loss rate. At the same time, observe whether there are cracks, discoloration, deformation or other phenomena on the sample surface; Three parallel samples were tested for each group of samples, and the average value was taken.
[0070] The final test results are shown in Table 1 below.
[0071] Table 1 Experimental Results As shown in Table 1, the samples in Examples 1-2 exhibited higher Tg values, indicating that the molecular chains of the materials maintained strong confinement and stability at high temperatures. This result is mainly attributed to the introduction of rigid heterocyclic structures such as benzoxazinone or benzoxazole in the main chain of the polyarylene ether copolymer, which endows the matrix with natural high thermal stability. Simultaneously, the vinyl end groups of the hyperbranched polysiloxane form a three-dimensional cross-linked network through free radical initiators, further enhancing intermolecular binding and thus suppressing the free movement of chain segments at high temperatures. In contrast, the comparative samples, lacking some key components or having replaced conventional free radical initiators, showed a decrease in Tg values, indicating that the molecular chains were more prone to movement at high temperatures, resulting in relatively lower thermal stability.
[0072] In thermogravimetric analysis, the 5% thermogravimetric temperature (Td5%) of the example samples was significantly higher than that of the comparative samples, and the residual carbon content at 800℃ was also higher. This indicates that the materials of the examples are more resistant to decomposition under high-temperature oxidation conditions and have stronger resistance to thermal degradation. This performance advantage mainly stems from the introduction of two-dimensional nanomaterials, such as strontium titanate and barium titanate nanosheets, which are uniformly dispersed in the polymer matrix, increasing the thermal conductivity of the material, promoting uniform heat distribution, and reducing local overheating. At the same time, their high specific surface area and surface organosilanes modification can strengthen the interfacial bonding force, thereby delaying the diffusion of pyrolysis products and the chain breakage process.
[0073] Tensile strength tests showed that the maximum tensile strength of the example sample was significantly higher than that of the comparative sample, exhibiting higher strength and toughness. This performance improvement is mainly attributed to the rigid-flexible design of the material structure: the polyarylether copolymer provides a rigid framework, while the flexible end segments of the hyperbranched polysiloxane and the two-dimensional nanomaterials form stress dispersion centers, enabling efficient dissipation of external stress. Simultaneously, the two-dimensional structure of the nanosheets can induce crack deflection, achieving a toughening mechanism. This synergistic effect not only improves the insufficient toughness of traditional polyarylether materials but also ensures the structural integrity and mechanical stability of the material in thick film or sheet states.
[0074] Deep curing tests showed that the hardness inside the thick sheet of the example sample changed little with depth, indicating a uniform light irradiation curing effect. In contrast, the comparative sample showed a significant hardness gradient, indicating that its curing reaction was limited by the light penetration depth or insufficient initiator activity. High-temperature aging tests further verified that the material of the example had an extremely low mass loss rate after 24 hours at 300°C, with no cracks, discoloration, or obvious deformation on the surface. In contrast, the comparative sample showed slight discoloration and partial shrinkage, indicating that the material of the example can maintain good structural stability and heat resistance under long-term high-temperature conditions.
[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the technical solutions of the embodiments of the present invention.
Claims
1. A high-temperature resistant polymerizable material composition, characterized in that, These include polyarylene ether copolymers containing reactive heterocyclic structures, hyperbranched polysiloxanes containing unsaturated end groups, two-dimensional nanomaterials modified with organosilane surfaces, and free radical initiators; The mass ratio of the polyarylene ether copolymer containing reactive heterocyclic structures to the hyperbranched polysiloxane containing unsaturated end groups is 1:(0.3-0.8), the amount of the two-dimensional nanomaterial modified with organosilane surface is 1%-5% of the total mass of the polyarylene ether copolymer and the hyperbranched polysiloxane, and the amount of the free radical initiator is 0.5%-5% of the total mass of the polyarylene ether copolymer and the hyperbranched polysiloxane. Wherein, the reactive heterocyclic structure is at least one of benzoxazinone, benzoxazole, or benzimidazole; the number-average molecular weight of the hyperbranched polysiloxane is 2000-5000 g / mol; the unsaturated end group is vinyl or allyl; and the two-dimensional nanomaterial is any one of layered metal oxide nanosheets, layered bimetallic hydroxide nanosheets, or MXene nanosheets.
2. The composition according to claim 1, characterized in that, The polyarylene ether copolymer is a polyarylene ether nitrile copolymer containing a benzoxazinone structure, and the molar percentage of the benzoxazinone structure in the main chain of the polyarylene ether copolymer is 10%-30%.
3. The composition according to claim 1, characterized in that, The hyperbranched polysiloxane is a hyperbranched structure prepared by hydrolysis-condensation polymerization of vinyltrimethoxysilane and tetramethyltetravinylcyclotetrasiloxane.
4. The composition according to claim 1, characterized in that, The two-dimensional nanomaterial is strontium titanate or barium titanate nanosheets with a thickness of 1-5 nm.
5. The composition according to claim 1, characterized in that, The free radical initiator is a binary photoinitiation system composed of metal nanoclusters and sulfur- or nitrogen-containing hydrogen donor compounds.
6. The composition according to claim 5, characterized in that, The metal nanoclusters are gold or silver nanoclusters with a particle size of 1-3 nm, the sulfur-containing hydrogen donor compound is a thiol compound, and the nitrogen-containing hydrogen donor compound is an amine compound.
7. A method for preparing a high-temperature resistant polymerizable material composition as described in any one of claims 1-6, characterized in that, Includes the following steps: S1: Hyperbranched polysiloxanes containing unsaturated end groups and two-dimensional nanomaterials modified with organosilane surfaces are dispersed in an organic solvent and premixed under ultrasonic assistance to form a uniform hybrid dispersion. S2: Dissolve a polyarylene ether copolymer containing a reactive heterocyclic structure in an aprotic polar solvent to prepare a solution; S3: Under shear conditions, the hybrid dispersion is added to the solution obtained in S2 and mixed evenly to form a casting solution; S4: Add a free radical initiator to the casting solution and cure it by light irradiation.
8. The preparation method according to claim 7, characterized in that, In S1, the organic solvent is a mixed solvent prepared by mixing tetrahydrofuran and N,N-dimethylformamide in a volume ratio of 1:(2-4).
9. The preparation method according to claim 7, characterized in that, The ultrasonic power is 300-500W, and the ultrasonic time is 30-60min.
10. The preparation method according to claim 8, characterized in that, In step S4, the curing process uses an LED light source with a wavelength of 365-405nm for light irradiation curing, with an irradiation intensity of 50-100 mW / cm². 2 The irradiation time is 10-30 minutes.