High-temperature-resistant polyhedral oligomeric silsesquioxane modified epoxy resin and curing method thereof

Abstract

The invention discloses high-temperature-resistant polyhedral oligomeric silsesquioxane modified epoxy resin and a curing method thereof, and relates to the technical field of epoxy resin. The water-based epoxy resin paint comprises the following components in percentage by weight: 48%-52% of bisphenol A epoxy resin, 38%-42% of methylhexahydrophthalic anhydride, 7%-9% of epoxy group or amino modified cage type polysilsesquioxane, 0.8%-1.2% of benzyl dimethylamine or 2-ethyl-4-methylimidazole, 0.8%-1.2% of a defoaming agent BYK-066N, a flatting agent BYK-307 and the balance of water. The preparation method comprises the following steps: proportionally mixing bisphenol A epoxy resin and epoxy group / amino modified cage type polysilsesquioxane, and stirring in a constant-temperature environment of 60 DEG C for 30 minutes; adding the balance of water, and adjusting the viscosity of the system to 60 mPa.s to obtain a mixture; then treating the mixture for 35 minutes at the frequency of 30kHz by using ultrasonic equipment to obtain premixed resin; by introducing high-temperature-resistant polysilsesquioxane, the performance bottleneck of a traditional modification method is broken through, and collaborative optimization of heat resistance, mechanical properties, processing efficiency and functional characteristics in the field of coatings is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resins, and more specifically, to a high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin and a curing method thereof. Background Art

[0002] Epoxy resin refers to a resin compound containing at least two reactive epoxy groups in its molecule. After curing, epoxy resin has many outstanding excellent properties, such as strong adhesion to various materials, especially metals, strong chemical corrosion resistance, high mechanical strength, good electrical insulation, corrosion resistance, etc. Chinese Patent with application number CN 118108925 A proposes a waterborne modified epoxy resin and its preparation method, which is characterized in that it is prepared according to the following steps: 1) Condensing bisphenol A epoxy resin with alkoxy or hydroxyl group-containing siloxane to obtain an organosilicon modified epoxy resin connected by SiOC bonds; 2) Reacting the organosilicon modified epoxy resin with dextran under alkaline conditions to obtain the product. It provides another new idea for the waterborne property, toughening and water resistance of epoxy resin during film formation by curing. However, in the specific use process, there is a contradiction between toughening and heat resistance. Rubber toughening (such as nitrile rubber) will cause a significant decrease in the glass transition temperature (Tg) of epoxy resin (20 - 40 °C), while thermoplastic resin toughening (such as polyetherimide) can maintain Tg, but it will cause processing coking problems due to a sharp increase in viscosity (>10000 mPa·s). Moreover, the modification with long-chain fatty acids requires a high temperature (>120 °C) reaction, with high energy consumption and a product viscosity >5000 mPa·s, and it cannot be used in low-VOCs coatings. Core-shell polymer toughening requires multiple solvent exchanges (200 - 300 L of solvent per ton of resin), increasing the energy consumption of distillation and accounting for the total cost. Summary of the Invention

[0003] To solve the above problems, the present invention provides a high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin and a curing method thereof.

[0004] The present invention provides a high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin, and the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition comprises the following components: 48% to 52% of bisphenol A epoxy resin, 38% to 42% of methylhexahydrophthalic anhydride, 7% to 9% of epoxy group or amino group modified cage-shaped polyhedral oligomeric silsesquioxane, 0.8% to 1.2% of benzyldimethylamine or 2-ethyl-4-methylimidazole, a total of 0.8% to 1.2% of defoaming agent BYK-066N and leveling agent BYK-307, and the balance of water.

[0005] The present invention also proposes a curing method for the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin, comprising the following steps: Step 1: Mix bisphenol A epoxy resin and epoxy group / amino modified cage-like polyhedral oligomeric silsesquioxane in proportion, and place them in a constant temperature environment of 60°C and stir for 30 minutes; Add the remaining water, adjust the viscosity of the system to 60 mPa·s to obtain a mixture; Then use ultrasonic equipment to process the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin; Step 2: Add methylhexahydrophthalic anhydride to the premixed resin, keep the temperature at 60°C, stir mechanically for 1 hour, add a promoter in proportion, and stir for 20 minutes; Add defoaming agent BYK-066N and leveling agent BYK-307, and stir for 10 minutes to obtain a mixture; Step 3: Transfer the mixture to a vacuum degassing machine, degas at a vacuum degree of -0.095 MPa for 20 minutes to complete the preparation.

[0006] Inject the degassed resin into the mold and let it stand for 10 minutes to allow the leveling agent to take effect; Step 4: Raise the temperature to 100°C and keep it warm for 2 hours; Raise the temperature to 140°C and keep it warm for 4 hours; Gradually raise the temperature to 160°C and keep it warm for 3 hours to complete curing; Step 5: Age the cured material in an environment of 85°C / 85%RH for 1000 hours and anneal it at 200°C for 2 hours.

[0007] Preferably, the specific steps of Step 1 are as follows: During the process of adding the remaining water and adjusting the viscosity of the system to 60 mPa·s, every other cycle, use a rheometer to detect the viscosity of the current mixture; Every other cycle, automatically adjust the water addition amount according to the viscosity of the current mixture. The specific method is: According to the formula , calculate and obtain the adjusted water addition amount , where is the current volume of the mixture, is the viscosity of the current mixture detected by the rheometer, is the target viscosity, that is, 60 mPa·s.

[0008] Preferably, the specific steps of Step 1 further include the following: During the process of using ultrasonic equipment to process the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin, every other cycle, according to the formula , calculate and obtain the adjustment value of the ultrasonic equipment frequency , where is the reference frequency, that is, 30 kHz.

[0009] Preferably, the specific steps of the first step further include the following. During the process of using an ultrasonic device to treat the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin, a nitrogen blowing process is added. While using the ultrasonic device for ultrasonic treatment, nitrogen is purged. The gas flow rate of nitrogen is adjusted according to the frequency of the ultrasonic device, and the specific method is as follows; According to the formula , the real-time gas flow rate of nitrogen is calculated and obtained , where is the initial gas flow rate of nitrogen.

[0010] Preferably, during the fourth step, the dynamic immobilization curve of the epoxy resin / poly(silsesquioxane) system is tested by DSC, and the activation energy , frequency factor A, and reaction order m / n are obtained by fitting. The DSC heat release data is collected in real time , if is greater than a preset threshold value, a cooling instruction is triggered; The upper limit of the cooling rate is set to -5 °C / min, and the cooling is carried out at the upper limit of the cooling rate until is less than or equal to the preset threshold value.

[0011] Preferably, the specific calculation steps for the real-time collection of DSC heat release data are as follows: According to the formula , the DSC heat release data is calculated and obtained , where R is the gas constant, T is the absolute temperature, is the conversion rate, reflects the Arrhenius relationship of temperature on the reaction rate, is the conversion rate term, describing the rate change in different stages of the reaction.

[0012] Preferably, during the fourth step, during the process of heating to 100 °C and holding for 2 hours, the heating rate is 2 °C / min. During the process of heating to 140 °C and holding for 4 hours, the heating rate is reduced to 1 °C / min. During the process of stepwise heating to 160 °C and holding for 3 hours, the heating rate is reduced to 0.5 °C / min.

[0013] Preferably, the specific steps of the third step further include: For transferring the mixture to a vacuum degassing machine and degassing for 20 minutes under a vacuum degree of -0.095 MPa, a three-stage gradient degassing is carried out. The first stage is -0.08 MPa / 5 min: to break the large air bubbles with a diameter > 100 μm in the resin, and the bubbles are expanded and broken by a sudden drop in pressure; Second stage: -0.095 MPa for 10 minutes: Remove 1–100 μm bubbles, combine with constant temperature control to reduce the resin viscosity, and accelerate the migration of bubbles to the surface; Third stage: -0.1 MPa for 5 minutes: Superimpose 20 Hz low-frequency vibration, and use mechanical wave perturbation to destroy the surface tension balance of nanoscale bubbles; For injecting the degassed resin into the mold and standing for 10 minutes, process a honeycomb-shaped flow channel on the mold surface, and drive the resin to fill quickly through capillary action.

[0014] Preferably, the specific steps of step five further include; For the process of annealing at 200 °C for 2 hours, adopt a three-step gradient annealing process to optimize the release of residual stress: The first stage: 200 °C for 30 minutes: The second stage: 180 °C for 60 minutes: Lower the temperature to extend the stress relaxation time constant τ, and use the medium temperature section to promote grain boundary slip and dislocation recombination; The third stage: 160 °C for 90 minutes.

[0015] Beneficial effects: By introducing epoxy group / amino group modified cage-like polyhedral oligomeric silsesquioxane (POSS), the contradiction between traditional toughening and heat resistance is solved. The rigid inorganic cage-like skeleton of POSS (Si-O-Si bond angle 109.5°) is embedded in the epoxy network through chemical bonding to form an "organic-inorganic interpenetrating structure", which maintains high heat resistance while improving toughness; Adopt ultrasonic dispersion combined with a three-stage gradient degassing process, directly disperse POSS through a water-based system, and avoid the high-temperature reaction (>120 °C) and solvent exchange required for long-chain fatty acid modification; By adjusting the ultrasonic frequency, when the viscosity increases, the ultrasonic frequency is automatically increased (, enhancing the cavitation force, ensuring that the dispersed particle size of POSS <100 nm, avoiding the risk of microcracks, the frequency is dynamically adjusted with the viscosity, and the energy consumption is reduced compared with traditional fixed-frequency ultrasonic treatment. Brief Description of the Drawings

[0016] Figure 1 is the method flow chart of the present invention. Detailed Embodiments

[0017] As Figure 1 shown: A heat-resistant cage-like polyhedral oligomeric silsesquioxane modified epoxy resin, and the heat-resistant cage-like polyhedral oligomeric silsesquioxane modified epoxy resin composition comprises the following components: 48% to 52% of bisphenol A epoxy resin, 38% to 42% of methylhexahydrophthalic anhydride, 7% to 9% of epoxy or amino modified cage-like polyhedral oligomeric silsesquioxane, 0.8% to 1.2% of benzyldimethylamine or 2-ethyl-4-methylimidazole, a total of 0.8% to 1.2% of defoamer BYK-066N and leveling agent BYK-307, and the balance of water.

[0018] It should be noted that bisphenol A epoxy resin, as the matrix material, provides high rigidity, chemical corrosion resistance and adhesion strength through benzene rings, ether bonds and hydroxyl groups. Its low viscosity (characteristics suitable for impregnation and potting processes); it is formulated with methylhexahydrophthalic anhydride in an approximate 1:1 equivalent ratio to form a three-dimensional crosslinked network, endowing the cured material with a glass transition temperature of 110 - 130 °C and excellent electrical properties; Adding 7% to 9% of epoxy or amino modified cage-like polyhedral oligomeric silsesquioxane, its Si-O-Si cage structure significantly enhances the thermal stability by restricting the movement of molecular chains. At the same time, the nano-dispersed polyhedral oligomeric silsesquioxane particles can terminate the propagation of microcracks, increasing the impact toughness to over 15 kJ / m². Benzyldimethylamine or 2-ethyl-4-methylimidazole, as accelerators, achieve stepwise curing at 120 - 180 °C by reducing the curing activation energy, avoiding local accumulation; The defoamer BYK-066N and the leveling agent BYK-307 synergistically optimize the processing performance, supplemented with a small amount of water to adjust the viscosity. Finally, the system exhibits the characteristics of low viscosity and long pot life. The cured material has a Tg ≥ 200 °C, a flexural strength ≥ 130 MPa, and a performance retention rate > 90% after 1000 hours of damp heat aging, suitable for waterborne high-activity ink coatings.

[0019] The present invention also proposes a curing method for a high-temperature resistant cage-like polyhedral oligomeric silsesquioxane modified epoxy resin, comprising the following steps: Step 1: Mix bisphenol A epoxy resin with epoxy / amino modified cage-like polyhedral oligomeric silsesquioxane in proportion, and place it in a constant temperature environment of 60 °C and stir for 30 minutes; make the polyhedral oligomeric silsesquioxane nanoparticles fully wet the resin matrix; Add the balance of water to adjust the viscosity of the system to 60 mPa·s to obtain a mixture; assist in the dispersion of polyhedral oligomeric silsesquioxane and inhibit agglomeration; Then use an ultrasonic device to treat the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin; ensure that the polyhedral oligomeric silsesquioxane is uniformly dispersed and there are no nano-scale aggregates; Step 2: Add methylhexahydrophthalic anhydride to the premixed resin, keep the temperature at 60 °C, mechanically stir for 1 hour, add the accelerator in proportion, and stir for 20 minutes; to reduce the curing activation energy and extend the pot life; Add the defoamer BYK-066N and the leveling agent BYK-307, and stir for 10 minutes to obtain a mixed material; stir at a low speed to reduce bubbles and optimize the coating flatness; Step 3: Transfer the mixture to a vacuum degassing machine and degas it for 20 minutes under a vacuum of -0.095 MPa; eliminate the influence of microbubbles on the curing network; Inject the degassed resin into the mold and let it stand for 10 minutes to allow the leveling agent to take effect; form a uniform preformed structure; Step 4: Raise the temperature to 100 °C and keep it warm for 2 hours; allow methylhexahydrophthalic anhydride to react with epoxy groups to initially form a prepolymer and avoid local agglomeration; Raise the temperature to 140 °C and keep it warm for 4 hours; promote the covalent bonding of the Si-O-Si cage structure of polyhedral oligomeric silsesquioxane with the epoxy network and enhance the crosslinking density.

[0020] Raise the temperature step by step to 160 °C and keep it warm for 3 hours to complete curing; complete the construction of the three-dimensional network and make the glass transition temperature (Tg) ≥ 200 °C; Step 5: Age the cured material in an environment of 85 °C / 85% RH for 1000 hours and anneal it at 200 °C for 2 hours. It should be noted that eliminate residual stress and further stabilize the crosslinked structure, and increase the flexural strength to ≥ 130 MPa As an optional embodiment; the specific steps of Step 1 are as follows: It should be noted that it is difficult to maintain stability when manually adjusting the system viscosity to 60 mPa·s, and excessive addition of water will dilute the resin, resulting in a decrease in the crosslinking density after curing; During the process of adding the remaining water and adjusting the system viscosity to 60 mPa·s, every other cycle, use a rheometer to detect the viscosity of the current mixture; Implement the process of adding the remaining water through a faucet equipped with a valve. Every other cycle, automatically adjust the water addition amount according to the viscosity of the current mixture. The specific method is as follows: According to the formula , calculate and obtain the adjusted water addition amount , where is the current volume of the mixture, is the viscosity of the current mixture detected by the rheometer, is the target viscosity, that is, 60 mPa·s. It should be noted that the rheometer can sensitively capture the influence of factors such as shear rate and temperature on viscosity. Through periodic detection and formula calculation, the system can dynamically compensate for environmental fluctuations or process parameter offsets, maintain viscosity stability. The viscosity data generated by periodic detection can be used to optimize the calculation coefficients in the water addition algorithm, reduce the trial-and-error cost. Precise control of the water addition amount avoids waste of excessive water and improves resource utilization efficiency. The rheometer can detect microstructural changes and combine with automatic water addition to inhibit local agglomeration or delamination caused by sudden viscosity changes. In the epoxy resin system, undispersed fillers may form defects due to abnormal increase in viscosity. Real-time adjustment can avoid such problems and ensure material uniformity.

[0021] As an alternative embodiment; the specific steps of step one further include the following: During the process of using an ultrasonic device to process the mixture for 35 minutes at a frequency of 30 kHz to obtain the premixed resin, every other cycle, according to the formula , calculate and obtain the adjustment value of the ultrasonic device frequency , where is the reference frequency, that is, 30 kHz. It should be noted that to avoid the frequency deviation of manual adjustment, ensure batch - to - batch consistency, meet the mixing requirements of high - viscosity resins and shear - sensitive materials (such as collagen solution), reduce the energy consumption and noise pollution of traditional mechanical stirring, and through dynamic frequency adjustment, the advantages of ultrasonic devices in mixing, dispersion, and stability control are further amplified.

[0022] As an alternative embodiment; the specific steps of step one further include the following. During the process of using an ultrasonic device to process the mixture for 35 minutes at a frequency of 30 kHz to obtain the premixed resin, a process of adding nitrogen blowing is included. While using the ultrasonic device for ultrasonic treatment, nitrogen is purged; The gas flow rate of nitrogen is adjusted depending on the frequency of the ultrasonic device, and the specific method is as follows; According to the formula , calculate and obtain the real - time gas flow rate of nitrogen , where is the initial gas flow rate of nitrogen. It should be noted that purging nitrogen can form an inert atmosphere to prevent side oxidation reactions caused by the contact of resin with oxygen during ultrasonic treatment, and dynamically adjusting the flow rate can match the required nitrogen coverage in real - time according to the ultrasonic energy input intensity.

[0023] As an alternative embodiment; during the process of step four, the dynamic immobilization curve of the epoxy resin / poly(silsesquioxane) system is tested by DSC, and the activation energy , frequency factor A, and reaction order m / n are obtained by fitting. The DSC heat release data is collected in real - time . If is greater than the preset threshold value, then a cooling instruction is triggered; it should be noted that the preset threshold value is 10 mW / g, and it can be adjusted according to needs; Set the upper limit of the cooling rate to - 5℃ / min, and cool at the upper limit of the cooling rate until is less than or equal to the preset threshold value.

[0024] As an alternative embodiment; the specific calculation steps for the real - time collection of DSC heat release data are as follows: According to the formula , calculate and obtain the DSC heat release data , where R is the gas constant, T is the absolute temperature, is the conversion rate, Arrhenius relation of temperature to reaction rate. is the conversion term, which describes the rate change at different stages of the reaction.

[0025] As an optional embodiment; during the process of step four, when the temperature is raised to 100°C and kept warm for 2 hours, the heating rate is 2°C / min, when the temperature is raised to 140°C and kept warm for 4 hours, the heating rate is reduced to 1°C / min, and when the temperature is stepped up to 160°C and kept warm for 3 hours, the heating rate is reduced to 0.5°C / min.

[0026] As an optional embodiment, the specific steps of step three also include: The mixed material is transferred to the vacuum degassing machine and degassing is performed at a vacuum degree of -0.095MPa for 20 minutes. The first stage is -0.08MPa / 5 minutes: large bubbles with a diameter of >100μm in the resin are broken, and the bubbles are expanded and broken by the sudden drop in pressure. Second stage - 0.095MPa / 10 minutes: remove 1-100μm bubbles, combine with constant temperature control to reduce resin viscosity, and accelerate bubble migration to the surface; Level 3 - 0.1MPa / 5 minutes: superimposed with 20Hz low-frequency vibration, using mechanical wave disturbance to destroy the surface tension balance of nano-scale bubbles; When the degassed resin is injected into the mold, it is left to stand for 10 minutes, and a honeycomb flow channel is processed on the mold surface to drive the resin to fill quickly through capillary force. It should be noted that the three-stage gradient degassing is 33% more efficient than the traditional single-stage degassing, while energy consumption is reduced by 25%. The honeycomb mold reduces resin waste and increases the filling rate from 85% to 98%.

[0027] As an optional embodiment; the specific steps of step five also include: For the process of annealing at 200 °C for 2 hours, a three-step gradient annealing process was used to optimize the residual stress release: the first stage was 200 °C / 30 minutes: the atomic diffusion inside the material was quickly activated by high temperature to initially release the stress in the high-energy dislocation area; The second stage is 180℃ / 60 minutes: lower the temperature to extend the stress relaxation time constant τ, and use the medium temperature stage to promote grain boundary sliding and dislocation recombination; avoid abnormal grain growth due to excessively high temperature; The third stage is 160℃ / 90 minutes. The low temperature stage is combined with a longer holding time to achieve deep release of residual stress through viscoelastic rheology, reducing the final stress to less than 5% of the initial value.

[0028] The following is a further description according to specific embodiments: Example 1: The mass percentages of the components of the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition are as follows: bisphenol A epoxy resin 48%, methylhexahydrophthalic anhydride 38%, epoxy group or amino group modified cage-shaped polyhedral oligomeric silsesquioxane 7%, benzyldimethylamine or 2-ethyl-4-methylimidazole 0.8%, defoaming agent BYK-066N and leveling agent BYK-307 in total 0.8%, and the balance water; The preparation method of the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition is as follows: Step 1: Mix bisphenol A epoxy resin and epoxy group / amino group modified cage-shaped polyhedral oligomeric silsesquioxane in proportion, and place them in a constant temperature environment of 60°C and stir for 30 minutes; Add the balance water, adjust the viscosity of the system to 60 mPa·s to obtain a mixture; Then use an ultrasonic device to treat the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin; Step 2: Add methylhexahydrophthalic anhydride to the premixed resin, keep the temperature at 60°C, mechanically stir for 1 hour, add the accelerator in proportion, and stir for 20 minutes; Add defoaming agent BYK-066N and leveling agent BYK-307, and stir for 10 minutes to obtain a mixed material; Step 3: Transfer the mixed material to a vacuum degassing machine and degas at a vacuum degree of -0.095 MPa for 20 minutes; Inject the degassed resin into a mold and let it stand for 10 minutes to allow the leveling agent to take effect; Step 4: Raise the temperature to 100°C and keep it warm for 2 hours; Raise the temperature to 140°C and keep it warm for 4 hours; Gradually raise the temperature to 160°C and keep it warm for 3 hours to complete curing; Step 5: Age the cured material in an environment of 85°C / 85%RH for 1000 hours and anneal at 200°C for 2 hours.

[0029] Example 2: The mass percentages of the components of the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition are as follows: bisphenol A epoxy resin 50%, methylhexahydrophthalic anhydride 40%, epoxy group or amino group modified cage-shaped polyhedral oligomeric silsesquioxane 8%, benzyldimethylamine or 2-ethyl-4-methylimidazole 1%, defoaming agent BYK-066N and leveling agent BYK-307 in total 1%, and the balance water; The preparation method of the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition is as follows: Step 1: Mix bisphenol A epoxy resin and epoxy group / amino group modified cage-shaped polyhedral oligomeric silsesquioxane in proportion, and place them in a constant temperature environment of 60°C and stir for 30 minutes; Add surplus water and adjust the viscosity of the system to 60 mPa·s to obtain a mixture; Then use an ultrasonic device to process the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin; Step Two: Add methylhexahydrophthalic anhydride to the premixed resin, maintain the temperature at 60°C, mechanically stir for 1 hour, add a promoter in proportion, and stir for 20 minutes; Add defoamer BYK-066N and leveling agent BYK-307, and stir for 10 minutes to obtain a mixed material; Step Three: Transfer the mixed material to a vacuum degassing machine and degas it at a vacuum degree of -0.095 MPa for 20 minutes; Inject the degassed resin into a mold and let it stand for 10 minutes to allow the leveling agent to take effect; Step Four: Raise the temperature to 100°C and keep it warm for 2 hours; Raise the temperature to 140°C and keep it warm for 4 hours; Gradually raise the temperature to 160°C and keep it warm for 3 hours to complete curing; Step Five: Age the cured material in an environment of 85°C / 85%RH for 1000 hours and anneal it at 200°C for 2 hours; Example Three: The mass percentages of the components of the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition are as follows: bisphenol A epoxy resin 52%, methylhexahydrophthalic anhydride 42%, epoxy group or amino group modified cage-shaped polyhedral oligomeric silsesquioxane 9%, benzyl dimethylamine or 2-ethyl-4-methylimidazole 1.2%, defoamer BYK-066N and leveling agent BYK-307 in total 1.2% and the remaining water; The preparation method of the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition is as follows: Step One: Mix bisphenol A epoxy resin and epoxy group / amino group modified cage-shaped polyhedral oligomeric silsesquioxane in proportion, place them in a constant temperature environment of 60°C and stir for 30 minutes; Add surplus water and adjust the viscosity of the system to 60 mPa·s to obtain a mixture; Then use an ultrasonic device to process the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin; Step Two: Add methylhexahydrophthalic anhydride to the premixed resin, maintain the temperature at 60°C, mechanically stir for 1 hour, add a promoter in proportion, and stir for 20 minutes; Add defoamer BYK-066N and leveling agent BYK-307, and stir for 10 minutes to obtain a mixed material; Step Three: Transfer the mixed material to a vacuum degassing machine and degas it at a vacuum degree of -0.095 MPa for 20 minutes; Inject the degassed resin into a mold and let it stand for 10 minutes to allow the leveling agent to take effect; Step 4: Heat up to 100 °C and keep the temperature for 2 hours; Heat up to 140 °C and keep the temperature for 4 hours; Gradually heat up to 160 °C and keep the temperature for 3 hours to complete curing; Step 5: Age the cured material in an environment of 85 °C / 85% RH for 1000 hours and anneal it at 200 °C for 2 hours; Example 4: The mass percentages of the components of the high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin composition are as follows: bisphenol A epoxy resin 50%, methylhexahydrophthalic anhydride 40%, epoxy group or amino group modified cage-type polyhedral oligomeric silsesquioxane 8%, benzyldimethylamine or 2-ethyl-4-methylimidazole 1%, defoamer BYK-066N and leveling agent BYK-307 in total 1% and the balance water; The preparation method of the high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin composition is as follows: Step 1: Mix bisphenol A epoxy resin and epoxy group / amino group modified cage-type polyhedral oligomeric silsesquioxane in proportion, place them in a constant temperature environment of 60 °C and stir for 30 minutes; Add the balance water, adjust the viscosity of the system to 60 mPa·s to obtain a mixture; Then use an ultrasonic device to treat the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin; Step 2: Add methylhexahydrophthalic anhydride to the premixed resin, keep the temperature at 60 °C, mechanically stir for 1 hour, add the accelerator in proportion and stir for 20 minutes; Add defoamer BYK-066N and leveling agent BYK-307 and stir for 10 minutes to obtain a mixed material; Step 3: Transfer the mixed material to a vacuum degassing machine and degas it at a vacuum degree of -0.095 MPa for 20 minutes; Inject the degassed resin into a mold and let it stand for 10 minutes to allow the leveling agent to take effect; Step 4: Heat up to 100 °C and keep the temperature for 2 hours; Heat up to 140 °C and keep the temperature for 4 hours; Gradually heat up to 160 °C and keep the temperature for 3 hours to complete curing; Step 5: Age the cured material in an environment of 85 °C / 85% RH for 1000 hours and anneal it at 200 °C for 2 hours; On the basis of Step 1, during the process of using an ultrasonic device to treat the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin, every other cycle, according to the formula , calculate and obtain the adjustment value of the ultrasonic device frequency , where is the reference frequency, that is, 30 kHz; Example 5: The mass percentage of the components of the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition is as follows: bisphenol A epoxy resin 50%, methylhexahydrophthalic anhydride 40%, epoxy group or amino group modified cage-shaped polyhedral oligomeric silsesquioxane 8%, benzyldimethylamine or 2-ethyl-4-methylimidazole 1%, defoaming agent BYK-066N and leveling agent BYK-307 in total 1%, and the balance is water; The preparation method of the high-temperature resistant cage-shaped polyhedral oligomeric silsesquioxane modified epoxy resin composition is as follows: Step 1: Mix bisphenol A epoxy resin and epoxy group / amino group modified cage-shaped polyhedral oligomeric silsesquioxane in proportion, and place them in a constant temperature environment of 60°C and stir for 30 minutes; Add the remaining water, adjust the viscosity of the system to 60 mPa·s to obtain a mixture; Then use an ultrasonic device to treat the mixture at a frequency of 30 kHz for 35 minutes to obtain a premixed resin; Step 2: Add methylhexahydrophthalic anhydride to the premixed resin, keep the temperature at 60°C, mechanically stir for 1 hour, add the accelerator in proportion, and stir for 20 minutes; Add defoaming agent BYK-066N and leveling agent BYK-307, and stir for 10 minutes to obtain a mixed material; Step 3: Transfer the mixed material to a vacuum degassing machine and degas at a vacuum degree of -0.095 MPa for 20 minutes; Inject the degassed resin into a mold and let it stand for 10 minutes to allow the leveling agent to take effect; Step 4: Raise the temperature to 100°C and keep it warm for 2 hours; Raise the temperature to 140°C and keep it warm for 4 hours; Gradually raise the temperature to 160°C and keep it warm for 3 hours to complete curing; Step 5: Age the cured material in an environment of 85°C / 85%RH for 1000 hours and anneal at 200°C for 2 hours; Based on Step 3, during the process of transferring the mixed material to a vacuum degassing machine and degassing at a vacuum degree of -0.095 MPa for 20 minutes, perform three-stage gradient degassing. The first stage is -0.08 MPa / 5 minutes: break the large air bubbles with a diameter > 100 μm in the resin, and promote the bubbles to expand and rupture through a sudden drop in pressure; The second stage is -0.095 MPa / 10 minutes: remove 1–100 μm bubbles, combine with constant temperature control to reduce the viscosity of the resin, and accelerate the migration of bubbles to the surface; The third stage is -0.1 MPa / 5 minutes: superimpose a 20 Hz low-frequency vibration, and use mechanical wave disturbance to destroy the surface tension balance of nanoscale bubbles; During the process of injecting the degassed resin into the mold and allowing it to stand for 10 minutes, a honeycomb-shaped flow channel is machined on the surface of the mold, and the resin is driven to fill quickly by capillary action.

[0030] Among them, Example 1, Example 2, and Example 3 are roughly the same, the difference lies in the different formula percentages of the high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin composition. Based on the comparison of Example 1, Example 2, and Example 3, the percentage range of the component mass of the high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin composition that can meet the requirements can be obtained. The high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin composition prepared based on the component mass of this high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin combination has the advantages of strong attraction to mosquitoes and flies and a long effective time. Example 4 and Example 3 are roughly the same, the difference lies in that Example 4 adds steps on the basis of Example 3. By comparison, the performance of the high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin prepared under different environments can be obtained. Example 5 and Example 3 are also roughly the same, the difference lies in that an additional process step is added in Example 5. Perform performance tests on the high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin composition prepared in the above examples. The specific test method is to place the high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin composition produced in different examples at the same position and the same height for testing, record the number of mosquitoes and flies attracted per hour, use this value as the attraction, and use the time from the start of the test to when the attraction is lower than 20% of the average attraction as the duration. The test results are shown in the following table:

[0031] Analyze the multiple high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin compositions prepared according to the above Examples 1 to 5. Among them, the high-temperature resistant cage-type polyhedral oligomeric silsesquioxane modified epoxy resin compositions prepared in Examples 1 to 3 can meet the specific use performance requirements.

[0032] The above is only the preferred implementation mode of the present invention. The protection scope of the present invention is not limited to the above examples. All technical solutions falling within the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those of ordinary skill in the art, several improvements and retouches made without departing from the principle of the present invention should also be regarded as within the protection scope of this template.

Claims

1. A high temperature resistant cage-type polysilsesquioxane modified epoxy resin, characterized in that: The high temperature resistant cage-type polysilsesquioxane modified epoxy resin composition comprises the following components: Bisphenol A epoxy resin 48% to 52%, methyl hexahydrophthalic anhydride 38% to 42%, epoxy or amino modified cage polysilsesquioxane 7% to 9%, benzyldimethylamine or 2-ethyl-4-methylimidazole 0.8% to 1.2%, defoamer BYK-066N and leveling agent BYK-307 0.8% to 1.2% in total and the balance water.

2. A method for curing a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 1, characterized in that: The following steps are involved: Step 1: Mix bisphenol A epoxy resin and epoxy / amino modified cage polysilsesquioxane in proportion, place in a constant temperature environment of 60°C and stir for 30 minutes; Adding the remaining amount of water to adjust the system viscosity to 60 mPa·s, to obtain a mixture; Then, the mixture was treated with an ultrasonic device at a frequency of 30 kHz for 35 minutes to obtain a premixed resin; Step 2: Add methyl hexahydrophthalic anhydride to the premixed resin, maintain the temperature at 60°C, mechanically stir for 1 hour, add accelerator in proportion, and stir for 20 minutes; Add defoamer BYK-066N and leveling agent BYK-307, stir for 10 minutes to obtain a mixture; Step 3: Transfer the mixture to a vacuum degassing machine and degas for 20 minutes at a vacuum degree of -0.095 MPa to complete the preparation; Inject the degassed resin into the mold and let it sit for 10 minutes to allow the leveling agent to take effect; Step 4: Heat to 100°C and keep warm for 2 hours; Raise the temperature to 140°C and keep warm for 4 hours; Stepwise heating to 160℃, keeping warm for 3 hours to complete curing; Step 5: After curing, the material is aged in an 85°C / 85%RH environment for 1000 hours and annealed at 200°C for 2 hours.

3. A method for curing a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 2, characterized in that: The specific steps of step one are as follows: During the process of adding the remaining water and adjusting the system viscosity to 60 mPa·s, the viscosity of the current mixture was measured by a rheometer every other cycle; Every other cycle, the amount of water added is automatically adjusted according to the viscosity of the current mixture. The specific method is as follows: According to the formula , calculate and obtain the adjusted water addition amount ,in is the current volume of the mixture, The viscosity of the current mixture is obtained by rheometer testing. is the target viscosity, i.e. 60 mPa·s.

4. A method for curing a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 3, characterized in that: The specific steps of step one also include the following: The mixture was treated with ultrasonic equipment at a frequency of 30 kHz for 35 minutes to obtain a premixed resin. Every other cycle, according to the formula , calculate and obtain the adjustment value of the ultrasonic equipment frequency ,in is the reference frequency, i.e. 30kHz.

5. A method for curing a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 3, characterized in that: The specific steps of step 1 also include the following: using an ultrasonic device to treat the mixture at a frequency of 30kHz for 35 minutes to obtain a premixed resin, adding a nitrogen blowing process, while using the ultrasonic device to perform ultrasound and blowing nitrogen; The nitrogen gas flow rate is adjusted by the frequency of the ultrasonic device, as follows; According to the formula , calculate and obtain the real-time gas flow rate of nitrogen ,in is the initial gas flow rate of nitrogen.

6. The curing method of a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 1, characterized in that: In the process of step 4, the dynamic immobilization curve of the epoxy resin / polysilsesquioxane system is tested by DSC, and the activation energy is obtained by fitting. , frequency factor A and reaction order m / n, real-time collection of DSC heat release data ,like If it is greater than the preset threshold, a cooling command is triggered; Set the upper limit of the cooling rate to -5℃ / min, and cool down according to the upper limit of the cooling rate until Less than or equal to a preset threshold.

7. A method for curing a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 6, characterized in that: The real-time collection of DSC heat release data The specific calculation steps are as follows: According to the formula , calculate and obtain the DSC heat release data , where R is the gas constant, T is the absolute temperature, is the conversion rate, Arrhenius relation of temperature to reaction rate. is the conversion term, which describes the rate change at different stages of the reaction.

8. The curing method of a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 1, characterized in that: During the process of step four, the heating rate is 2°C / min when the temperature is raised to 100°C and kept warm for 2 hours, the heating rate is reduced to 1°C / min when the temperature is raised to 140°C and kept warm for 4 hours, and the heating rate is reduced to 0.5°C / min when the temperature is stepped up to 160°C and kept warm for 3 hours.

9. The curing method of a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 1, characterized in that: The specific steps of step three also include: The mixed material is transferred to the vacuum degassing machine and degassing is performed at a vacuum degree of -0.095MPa for 20 minutes. The first stage is -0.08MPa / 5 minutes: large bubbles with a diameter of >100μm in the resin are broken, and the bubbles are expanded and broken by the sudden drop in pressure. Second stage - 0.095MPa / 10 minutes: remove 1-100μm bubbles, combine with constant temperature control to reduce resin viscosity, and accelerate bubble migration to the surface; Level 3 - 0.1MPa / 5 minutes: superimposed with 20Hz low-frequency vibration, using mechanical wave disturbance to destroy the surface tension balance of nano-scale bubbles; The degassed resin is injected into the mold and allowed to stand for 10 minutes. A honeycomb flow channel is then processed on the mold surface to drive the resin to fill quickly through capillary force.

10. The curing method of a high temperature resistant cage-type polysilsesquioxane modified epoxy resin according to claim 6, characterized in that: The specific steps of step five also include: For the annealing process at 200°C for 2 hours, a three-step gradient annealing process was used to optimize the residual stress release: The first stage was 200°C / 30 minutes: The second stage is 180℃ / 60 minutes: lower the temperature to extend the stress relaxation time constant τ, and use the medium temperature stage to promote grain boundary sliding and dislocation recombination; The third stage is 160℃ / 90 minutes.

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