CN109232890B - Preparation method of prepolymer for low-dielectric bismaleimide resin system - Google Patents
Preparation method of prepolymer for low-dielectric bismaleimide resin system Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08K7/00—Use of ingredients characterised by shape
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Abstract
The invention discloses a preparation method of a prepolymer for a low-dielectric bismaleimide resin system, which takes bismaleimide, an allyl compound, mesoporous silica and polyphenylene oxide as raw materials, and prepares the low-dielectric high-performance bismaleimide resin system by preparing the polyphenylene oxide to coat the mesoporous silica and applying the mesoporous silica to the bismaleimide resin system; the method disclosed by the invention has the characteristics of simple process, wide applicability and the like, and the prepared material has wide application potential in the fields of aviation, aerospace and electronics.
Description
The invention relates to a low dielectric bismaleimide resin system and a preparation method thereof, belonging to the technical preparation part of products, and the invention is a divisional application with application date of 2016, 12 and 9, and application number of 2016111327196.
Technical Field
The invention belongs to the technical field of high-performance resin matrix, relates to a low-dielectric high-performance resin matrix composite material, and particularly relates to a preparation method of a prepolymer for a low-dielectric bismaleimide resin system.
Background
The bismaleimide resin system is a typical high-performance thermosetting resin, has excellent mechanical property, thermal property, electrical property and the like, and has outstanding application potential in the fields of aviation and aerospace electronic materials. With the rapid development of microelectronic technology, the performance of the existing bismaleimide resin system material cannot meet the development of high integration level, lower power consumption and high performance electronic products, so that the development of a low dielectric and high performance bismaleimide resin system with more excellent performance is required. The modification of bismaleimide by inorganic particles is easy to improve the mechanical property and the thermal property of the bismaleimide resin, but the dielectric property of the material cannot be obviously reduced. The mesoporous silica is an inorganic material with a pore structure, has a very large specific surface area, a large number of Si-O-Si chain segments and abundant silicon hydroxyl groups, and therefore, the mesoporous silica provides favorable conditions for designing a material with outstanding mechanical property, heat resistance and dielectric property (dielectric constant of about 1.5-1.7). Unfortunately, although the mesoporous silica material can significantly improve the mechanical properties and even the thermal properties of resin-based composite materials, the advantage of low dielectric properties is not fully developed, because small molecular substances can permeate into the mesopores of the silica during the material forming process, and thus the low dielectric properties of the resin-based composite materials cannot be fully utilized. In addition, since mesoporous silica has a high specific surface area, its addition significantly increases the viscosity of the resin system, resulting in deterioration of resin molding manufacturability. Therefore, how to effectively seal the mesopores of the mesoporous silica has positive significance for promoting the application of the low dielectric property of the mesoporous silica under the conditions of not obviously affecting the low dielectric property and a resin forming process. Polyphenylene Oxide (PPO) is an important high-performance thermoplastic resin, which has a high glass transition temperature (Tg =210 ℃), good heat resistance and dimensional stability, high toughness, and low moisture absorption rate, and although the addition of PPO can reduce the dielectric properties of a thermosetting resin system to some extent, the addition of PPO with a higher content can reduce the crosslinking density or other properties of the resin system such as strength, heat resistance and the like, and the use of PPO alone can reduce the dielectric properties of the thermosetting resin system less effectively.
Disclosure of Invention
The invention aims to provide a low dielectric bismaleimide resin system and a preparation method thereof, which seal mesoporous of mesoporous silica by a material with low dielectric constant, are beneficial to maintaining the low dielectric property of the mesoporous silica, and thus promote the application of the mesoporous silica in the field of developing low dielectric materials.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a low dielectric bismaleimide resin system comprises the following steps: heating bismaleimide and an allyl compound to a transparent solution, then adding polyphenyl ether to coat mesoporous silica particles, and stirring to obtain a prepolymer; then pouring the prepolymer into a mold, and vacuumizing for 30-40 min at 130-150 ℃; and then curing at the temperature of 150-230 ℃ to obtain the low dielectric bismaleimide resin system.
In the technical scheme, the raw material components and the mass ratio are 100 parts of bismaleimide; 50-100 parts of an allyl compound; 2-8 parts of polyphenylene oxide coated mesoporous silica.
In the technical scheme, bismaleimide and an allyl compound are stirred and heated at 130-140 ℃ to form a transparent solution; and naturally cooling after curing for 7-9 hours to obtain a cured substance, namely the low dielectric bismaleimide resin system.
In the above technical solution, the bismaleimide is bismaleimide diphenylmethane or bismaleimide anisole.
In the above technical scheme, the allyl compound is diallyl bisphenol A, diallyl bisphenol S, allyl aralkyl phenol, polyallyl ether ketone, allyl phenol epoxy resin, and N-allyl arylamine.
In the technical scheme, the prepolymer is obtained by stirring at 130-150 ℃ for 30-50 min.
In the technical scheme, the preparation method of the polyphenylene oxide coated mesoporous silica particles comprises the following steps: dissolving polyphenyl ether in a benzene solvent, adding mesoporous silica, stirring, adding the mixture into a water solution containing a surfactant to form an oil-in-water system, and stirring for 4-6 hours to obtain polyphenyl ether-coated mesoporous silica particles; the mass ratio of the polyphenyl ether to the mesoporous silica is (1-3.3) to 1.
In the technical scheme, the benzene solvent is preferably toluene, and the mass ratio of the polyphenyl ether to the benzene solvent is 1: 10-18; the surfactant is sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, potassium monododecyl phosphate and the like, and the mass concentration of the surfactant in the water solution containing the surfactant is 0.1-0.3%; polyphenylene ethers are polyphenylene ether resins, including polyphenylene ether resins of different molecular weights and modified polyphenylene ether resins thereof (e.g., polyphenylene ether (PPO. multidot.630) having a number average molecular weight (Mn) of 17300, vinyl terminated polyphenylene ether (PPO. multidot.MX 9000-111) having Mn of 1100, and vinyl terminated polyphenylene ether (Noryl. multidot.SA 9000) having Mn of 2200). The polyphenyl ether is insoluble in water, and the polyphenyl ether is precipitated at a water-oil phase interface and deposited or adsorbed on the surface of mesoporous silica along with gradual volatilization of a benzene solvent, and a mesopore is sealed.
In the technical scheme, the aperture of the mesoporous silica is 2-9 nm, and the particle size is 20-100 nm. For example, the specific surface area is 500 to 800m2(iv) mesoporous silica (UC-S-1) with a pore diameter of 7-9 nm in each of a two-dimensional pore channel and a hexagonal mesopore; the specific surface area is 700m2(UC-S-3) mesoporous silica having a pore size of 6nm in a three-dimensional pore channel and a cubic mesopore; the specific surface area is 1300m2(UC-S-6) with the pore diameter of 2nm of two-dimensional pore canal and hexagonal mesopores.
Preferably, the curing process is 150 ℃/2h +180 ℃/2h +200 ℃/2h + 220-230 ℃/2 h. On one hand, the preparation method successfully solves the problem that the viscosity of the thermosetting material is increased by the existing inorganic material, so that the thermosetting resin maintains good manufacturability; on the other hand, under the curing process of the invention, the components in the BMI prepolymer react gradually to form excellent interface adhesion, thereby solving the problem of poor compatibility of the existing organic and inorganic phases; therefore, the prepared low dielectric bismaleimide resin material has good mechanical property and keeps good thermal property.
The invention also discloses a low dielectric bismaleimide resin system prepared by the method, the normal temperature dielectric constant is as low as 2.6, the dielectric loss is as low as 0.012, and the low dielectric bismaleimide resin system has obvious application potential in the field of electronic materials.
Further, the invention also discloses a preparation method of the prepolymer, which comprises the following steps of heating bismaleimide and an allyl compound to a transparent solution, adding polyphenyl ether to coat mesoporous silica particles, and stirring at 130-150 ℃ for 30-50 min to obtain the prepolymer; the preparation method of the polyphenylene oxide-coated mesoporous silica particles comprises the steps of dissolving polyphenylene oxide in a benzene solvent, adding mesoporous silica, stirring, adding the mixture into a water solution containing a surfactant to form an oil-in-water system, and stirring for 4-6 hours to obtain the polyphenylene oxide-coated mesoporous silica particles; the mass ratio of the polyphenyl ether to the mesoporous silica is (1-3.3) to 1.
The invention also discloses the prepolymer prepared by the method and application of the prepolymer in preparing a low dielectric material.
Compared with the prior art, the invention has the beneficial effects that:
1. the bismaleimide resin system material prepared by the invention not only has excellent mechanical property and thermal property, but also has obviously low dielectric property; compared with a system in which mesoporous silica and polyphenyl ether are independently added, the material adopting the double-horse system of mesoporous silica coated with the same amount of polyphenyl ether has lower and more stable dielectric property, and shows obvious application potential in the field of electronic materials;
2. according to the invention, polyphenyl ether is creatively adsorbed on the surface of mesoporous silica, the mesopores are effectively sealed, and after the polyphenyl ether is added into a bismaleimide and allyl compound solution, resin is prevented from entering the mesopores, so that the low dielectric property of the product is guaranteed;
3. the preparation method of the low dielectric bismaleimide resin system disclosed by the invention has the advantages of wide applicability and simple operation process; the prepared prepolymer is suitable for the preparation process of composite materials such as casting, mould pressing and the like, and is suitable for industrial application.
Drawings
FIG. 1 is a scanning electron microscope image of mesoporous silica and polyphenylene ether-coated mesoporous silica of example 1;
FIG. 2 is an infrared spectrum of mesoporous silica, polyphenylene ether and polyphenylene ether coated mesoporous silica of example 1;
FIG. 3 is an SEM image of impact cross-section of the materials of comparative example 1 and example 1;
FIG. 4 is an SEM image of a polyphenylene ether-coated mesoporous silica of example 2;
fig. 5 is an SEM image of impact cross-section of the materials of comparative example 2 and example 2.
Detailed Description
The technical solution of the present invention is further described with reference to the following examples.
Example 1
2g of polyphenylene ether (vinyl-terminated polyphenylene ether (PPO. MX9000-111) having a number average molecular weight of 1100) was completely dissolved in 25ml of toluene to obtain a polyphenylene ether solution, and then 0.6g of mesoporous silica (UC-S-1) was added thereto, followed by stirring and dispersing, and then added to 500ml of an aqueous solution of a sodium lauryl sulfate surfactant having a mass concentration of 0.15% to form an oil-in-water system. Because the polyphenyl ether is insoluble in water, the separated polyphenyl ether can be deposited or adsorbed on the surface of the mesoporous silicon dioxide along with the gradual volatilization of the toluene solvent, and the mesopores are sealed. And after stirring for 4 hours, washing and filtering the precipitate, and drying the precipitate for 4 hours in vacuum at 120 ℃ to obtain the polyphenylene ether filled and coated mesoporous silica material, wherein the mass ratio of the polyphenylene ether to the mesoporous silica is 3.3: 1. FIG. 1 is a Scanning Electron Microscope (SEM) photograph of mesoporous silica (left) and polyphenylene ether-coated mesoporous silica (right); FIG. 2 shows an infrared (FTIR) spectrum of mesoporous silica, polyphenylene oxide and polyphenylene oxide-coated mesoporous silica.
Stirring and heating 50g of bismaleimide diphenylmethane and 50g of diallyl bisphenol A compound at 130 ℃ to obtain a transparent solution, then adding 1g of polyphenylene ether coated mesoporous silica particles, carrying out prepolymerization at 140 ℃ for 50min under the stirring condition, then pouring the prepolymer solution into a flat plate mold, vacuumizing at 140 ℃ for about 30min, then carrying out curing at 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h according to a temperature program, and taking out the cured material from the flat plate mold after natural cooling, thereby obtaining the product.
Comparative example 1
Stirring and heating 50g of bismaleimide diphenylmethane and 50g of diallyl bisphenol A compound at 130 ℃ to obtain a transparent solution, carrying out prepolymerization at 140 ℃ for 50min under the stirring condition, pouring the prepolymer solution into a flat plate mold, vacuumizing at 140 ℃ for about 30min, then carrying out curing at 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h according to a temperature program, and taking out the cured material from the flat plate mold after natural cooling. FIG. 3 is an SEM image of impact fracture sections of the materials prepared in comparative example 1 (left) and example 1 (right), and Table 1 shows the performance parameters of the cured material of example 1 and the cured material of comparative example 1.
As can be seen from fig. 1 (left), the surface of the mesoporous silica can find tiny pores, but the pore structure of the mesoporous silica is not obviously observed on the surface of the polyphenylene ether-coated mesoporous silica (right) due to the deposition of the polyphenylene ether; as can be seen from fig. 2, the polyphenylene ether-coated mesoporous silica contains polyphenylene ether and characteristic absorption peaks of the mesoporous silica, which demonstrate that polyphenylene ether is deposited on the mesoporous silica; FIG. 3 is an SEM picture of the impact fracture section of the prepared material, and the right picture shows that the section of the material added with the polyphenylene oxide coated mesoporous silica is coarser than that of a pure resin system, which indicates that the material has excellent mechanical properties; it can be seen from table 1 that, after the polyphenylene ether-coated mesoporous silica particles are added, the mechanical properties of the material are superior to those of a pure resin system, and particularly, the dielectric properties of the material added with the polyphenylene ether-coated mesoporous silica are obviously reduced, which is mainly caused by the low dielectric properties of the polyphenylene ether and the mesoporous silica.
TABLE 1 Property parameters of the materials
| Performance of | Comparative example 1 | Example 1 |
| Impact Strength (KJ/m)2) | 9.9 | 10.9 |
| Fracture toughness (K)IC)/MPa·m1/2 | 1.2 | 1.39 |
| Flexural Strength/MPa | 111 | 137 |
| 5wt% weight loss thermal decomposition temperature/° C (TGA method) | 416 | 418 |
| Dielectric constant (Normal temperature, 10)2～106Hz） | 4.4～4.0 | 3.6～3.5 |
| Dielectric loss (Normal temperature, 10)2～106Hz） | 0.014～0.08 | 0.013～0.019 |
Example 2
2g of polyphenylene ether (vinyl-terminated polyphenylene ether (PPO. MX9000-111) having a number average molecular weight of 1100) was completely dissolved in 25ml of toluene to obtain a polyphenylene ether solution, and then 1.0g of mesoporous silica (UC-S-1) was added thereto, followed by stirring and dispersing, and then added to 500ml of an aqueous solution of a sodium lauryl sulfate surfactant having a mass concentration of 0.2% to form an oil-in-water system. Because the polyphenyl ether is insoluble in water, the separated polyphenyl ether can be deposited or adsorbed on the surface of the mesoporous silicon dioxide along with the gradual volatilization of the toluene solvent, and the mesopores are sealed. And after stirring for 5 hours, washing and filtering the precipitate, and drying the precipitate for 5 hours in vacuum at 120 ℃ to obtain the polyphenylene ether filled and coated mesoporous silica material, wherein the mass fraction ratio of the polyphenylene ether to the mesoporous silica is 2: 1. FIG. 4 is an SEM photograph of polyphenylene ether-coated mesoporous silica.
Stirring and heating 50g of bismaleimide diphenylmethane and 50g of diallyl bisphenol A compound at 130 ℃ to obtain a transparent solution, adding 4g of polyphenylene ether coated mesoporous silica particles, carrying out prepolymerization at 140 ℃ for 50min under the stirring condition, pouring the prepolymer solution into a flat plate mold, vacuumizing at 140 ℃ for 30min, curing at 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h according to a temperature program, and taking out the cured material from the flat plate mold after natural cooling.
Comparative example 2
Stirring and heating 50g of bismaleimide diphenylmethane and 50g of diallyl bisphenol A compound at 130 ℃ to obtain a transparent solution, adding 2.7g of polyphenyl ether and 1.3g of mesoporous silica (which are respectively equivalent to the contents of the polyphenyl ether and the mesoporous silica in 4g of polyphenyl ether coated mesoporous silica) under the stirring condition, pre-polymerizing for 50min at 140 ℃, pouring the prepolymer solution into a flat plate mold, vacuumizing for 30min at 140 ℃, then curing at 150 ℃/2h +180 ℃/2h +200 ℃/2h +220 ℃/2h according to the temperature program, and taking out the cured material from the flat plate mold after natural cooling. Fig. 5 is an SEM image of the fracture cross-section of the impact fracture of the materials prepared in comparative example 2 (left) and example 2 (right), and table 2 is the performance parameters of the materials of example 2 and comparative example 2.
As can be seen from fig. 4, due to the deposition of polyphenylene ether, the morphology of the polyphenylene ether-coated mesoporous silica is significantly different from that of the mesoporous silica (fig. 1, left); comparing the left side and the right side of fig. 5, it can be found that when the mesoporous silica (left) is directly added into the resin system, the resin monomer can permeate into the pores of the mesoporous silica, and when the polyphenylene ether-coated mesoporous silica (right) is added, it can be found that the fractured mesoporous silica still has pores, which obviously contributes to fully exerting the low dielectric property of the mesoporous silica; the data in table 2 show that, in addition to very low dielectric constant and dielectric loss, the product of the invention has better mechanical properties than a material prepared by separately adding equivalent amounts of polyphenylene ether and mesoporous silica, which may be due to the good dispersibility of the polyphenylene ether-coated modified mesoporous silica in the resin system, and the small degree of damage to the cross-linked network structure of the matrix because the interfacial contact area between the polyphenylene ether-coated modified mesoporous silica particles and the resin system is smaller than that between the polyphenylene ether-coated mesoporous silica particles and the resin system.
TABLE 2 Property parameters of the materials
| Performance of | Comparative example 2 | Example 2 |
| Impact Strength (KJ/m)2) | 10 | 12.5 |
| Fracture toughness (K)IC)/MPa·m1/2 | 1.7 | 1.9 |
| Flexural Strength/MPa | 165 | 177 |
| 5wt% weight loss thermal decomposition temperature/° C (TGA method) | 416 | 419 |
| Dielectric constant (Normal temperature, 10)2～106Hz） | 3.6～3.5 | 2.9～3.2 |
| Dielectric loss (Normal temperature, 10)2～106Hz） | 0.012～0.016 | 0.011～0.014 |
Example 3
2g of polyphenylene ether (vinyl-terminated polyphenylene ether (Noryl SA9000) having a number average molecular weight of 2200) was completely dissolved in 30ml of toluene to obtain a polyphenylene ether solution, and then 1.4g of mesoporous silica (UC-S-3) was added thereto, followed by stirring and dispersing, and then added to 500ml of an aqueous solution of potassium monododecyl phosphate surfactant having a mass concentration of 0.3%, to form an oil-in-water system. Because the polyphenyl ether is insoluble in water, the separated polyphenyl ether can be deposited or adsorbed on the surface of the mesoporous silicon dioxide along with the gradual volatilization of the toluene solvent, and the mesopores are filled or sealed. And after stirring for 6 hours, washing and filtering the precipitate, and drying the precipitate for 6 hours in vacuum at 120 ℃ to obtain the polyphenylene ether filled and coated mesoporous silica material, wherein the mass fraction ratio of the polyphenylene ether to the mesoporous silica is 1.43: 1.
Stirring and heating 50g of bismaleimide diphenyl ether and 30g of diallyl bisphenol S at 130 ℃ to obtain a transparent solution, adding 1.8g of polyphenylene ether coated mesoporous silica particles, carrying out prepolymerization at 140 ℃ for 50min under the stirring condition, pouring the prepolymer solution into a flat plate mold, vacuumizing at 140 ℃ for 30min, curing at 150 ℃/2h +180 ℃/2h +200 ℃/2h +230 ℃/2h according to a temperature program, and taking out the cured material from the flat plate mold after natural cooling.
Comparative example 3
Stirring and heating 50g of bismaleimide diphenyl ether and 30g of diallyl bisphenol S compound at 130 ℃ to obtain a transparent solution, carrying out prepolymerization at 140 ℃ for 50min under the stirring condition, pouring the prepolymer solution into a flat plate mold, vacuumizing at 140 ℃ for about 30min, then carrying out curing at 150 ℃/2h +180 ℃/2h +200 ℃/2h +230 ℃/2h according to a temperature program, and taking out the cured material from the flat plate mold after natural cooling. Table 3 shows the performance parameters of the materials of example 3 and comparative example 3, and it can be seen from Table 3 that the mechanical properties of the materials are better than those of the pure resin system after the polyphenylene ether is added to coat the mesoporous silica particles. In particular, the dielectric property of the material added with the polyphenylene oxide-coated mesoporous silica is obviously reduced, which is mainly caused by the excellent mechanical property, thermal property and low dielectric property of the polyphenylene oxide-coated mesoporous silica.
TABLE 3 Property parameters of the materials
| Performance of | Comparative example 3 | Example 3 |
| Impact Strength (KJ/m)2) | 13.5 | 15.7 |
| Fracture toughness (K)IC)/MPa·m1/2 | 1.3 | 2.1 |
| Flexural Strength/MPa | 116 | 165 |
| 5wt% weight loss thermal decomposition temperature/° C (TGA method) | 443 | 446 |
| Dielectric constant (Normal temperature, 10)2～106Hz） | 4.2～4.0 | 2.7～3.1 |
| Dielectric loss (Normal temperature, 10)2～106Hz） | 0.011～0.06 | 0.011～0.013 |
Example 4
Completely dissolving 2g of polyphenylene oxide (PPO 630) with the number average molecular weight of 17300) in 40ml of toluene to obtain a polyphenylene oxide solution, then adding 2g of mesoporous silica (UC-S-6), stirring and dispersing, then adding into 600ml of aqueous solution of sodium dodecyl sulfate surfactant with the mass concentration of 0.2% to form an oil-in-water system, wherein the polyphenylene oxide is insoluble in water, the precipitated polyphenylene oxide can be deposited or adsorbed on the surface of the mesoporous silica along with the gradual volatilization of a toluene solvent, filling or sealing mesopores, washing, filtering and drying the precipitate in vacuum at 120 ℃ for 5 hours after stirring, thus obtaining the polyphenylene oxide filled and coated mesoporous silica material, wherein the mass fraction ratio of the polyphenylene oxide to the mesoporous silica is 1: 1.
Stirring and heating 50g of bismaleimide diphenylmethane and 25g of allyl phenol epoxy resin at 130 ℃ to obtain a transparent solution, then adding 3g of polyphenylene ether coated mesoporous silica particles, carrying out prepolymerization at 140 ℃ for 50min under the stirring condition, then pouring the prepolymer solution into a flat plate mold, vacuumizing at 140 ℃ for about 30min, then carrying out curing at 150 ℃/2h +180 ℃/2h +200 ℃/2h +230 ℃/2h according to a temperature program, and taking out the cured material from the flat plate mold after natural cooling.
Comparative example 4
Stirring and heating 50g of bismaleimide diphenylmethane and 25g of allyl phenol epoxy resin at 130 ℃ to obtain a transparent solution, carrying out prepolymerization for 50min at 140 ℃ under the stirring condition, pouring the prepolymer solution into a flat plate mold, vacuumizing for about 30min at 140 ℃, then curing at 150 ℃/2h +180 ℃/2h +200 ℃/2h +230 ℃/2h according to a temperature program, and taking out the cured material from the flat plate mold after natural cooling.
TABLE 4 Property parameters of the materials
| Performance of | Comparative example 4 | Example 4 |
| Impact Strength (KJ/m)2) | 11.3 | 14.7 |
| Fracture toughness (K)IC)/MPa·m1/2 | 1.15 | 1.76 |
| Flexural Strength/MPa | 123 | 171 |
| 5wt% weight loss thermal decompositionTemperature/° C (TGA method) | 452 | 460 |
| Dielectric constant (Normal temperature, 10)2～106Hz） | 4.3～4.7 | 2.6～3.0 |
| Dielectric loss (Normal temperature, 10)2～106Hz） | 0.018～0.09 | 0.012～0.013 |
Table 4 shows the performance parameters of the materials of example 4 and comparative example 4. from Table 4, it can be seen that the mechanical properties of the materials are better than those of the pure resin system after the polyphenylene ether is added to coat the mesoporous silica particles. In particular, the dielectric property of the material added with the polyphenylene oxide-coated mesoporous silica is obviously reduced, which is mainly caused by the excellent mechanical property, thermal property and low dielectric property of the polyphenylene oxide-coated mesoporous silica.
Claims (2)
1. A preparation method of a prepolymer for a low dielectric bismaleimide resin system is characterized by comprising the following steps: heating bismaleimide and an allyl compound to a transparent solution, adding polyphenylene oxide to coat mesoporous silica particles, and stirring at 130-150 ℃ for 30-50 min to obtain a prepolymer; the preparation method of the polyphenylene oxide coated mesoporous silica particles comprises the following steps: dissolving polyphenyl ether in a benzene solvent, adding mesoporous silica, stirring, adding the mixture into a water solution containing a surfactant, and stirring for 4-6 hours to obtain polyphenyl ether-coated mesoporous silica particles; the mass ratio of the polyphenyl ether to the mesoporous silica is (1-3.3) to 1; the mass ratio of the bismaleimide to the allyl compound to the polyphenylene oxide coated mesoporous silica particles is 100 to (50-100) to (2-8); the bismaleimide is bismaleimide diphenylmethane and/or bismaleimide diphenyl methyl ether; the allyl compound is diallyl bisphenol A, diallyl bisphenol S, allyl aralkyl phenol, polyallyl ether ketone, allyl phenol epoxy resin or N-allyl arylamine; the molecular weight of the polyphenyl ether is 1100-20000; the aperture of the mesoporous silica is 2 nm-9 nm, and the particle size is 20-100 nm; the surfactant is sodium dodecyl benzene sulfonate, sodium dodecyl sulfate or potassium monododecyl phosphate.
2. The method for preparing the prepolymer for the low dielectric bismaleimide resin system as claimed in claim 1, wherein the prepolymer is prepared by the following steps: the mass ratio of the polyphenyl ether to the benzene solvent is 1: 10-18; the mass concentration of the surfactant in the surfactant-containing aqueous solution is 0.1-0.3%; stirring for 4-6 hours, washing the mixed solution with water, performing suction filtration, and performing vacuum drying at 100-120 ℃ for 4-6 hours to obtain the polyphenylene oxide-coated mesoporous silica particles.
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| CN101775139B (en) * | 2009-12-31 | 2012-02-01 | 苏州大学 | Method for preparing modified bismaleimide resin |
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| CN102631884B (en) * | 2012-04-12 | 2013-12-04 | 苏州大学 | Closed mesoporous silicon oxide and preparation method of same |
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| CN102161829A (en) * | 2011-03-12 | 2011-08-24 | 苏州大学 | Bismaleimide resin system and preparation method thereof |
| CN102627857A (en) * | 2012-04-20 | 2012-08-08 | 苏州大学 | Modified thermosetting resin and preparation method thereof |
| CN103965606A (en) * | 2013-02-04 | 2014-08-06 | 联茂电子股份有限公司 | Low dielectric material |
| CN105968808A (en) * | 2016-07-05 | 2016-09-28 | 苏州大学 | Self-repair resin-based composite material and preparation method thereof |
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| CN109232891B (en) | 2020-11-17 |
| CN109021235B (en) | 2020-07-21 |
| CN109021235A (en) | 2018-12-18 |
| CN109232891A (en) | 2019-01-18 |
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