Corrosion-resistant and high-temperature-resistant fiber composite material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of composite materials, and discloses a corrosion-resistant and high-temperature-resistant fiber composite material as well as a preparation method and application thereof. The fiber composite material comprises glass fiber cloth and a coating coated on the surface of the glass fiber cloth, the coating comprises the following raw material components: a component A and a component B, the component A is prepared by mixing bismaleimide resin, dihydroxyl-terminated polydimethylsiloxane and pentaerythritol, and then adding a modified filler, an auxiliary agent and a solvent; the component B is prepared from isocyanate, methyl-5-norbornene-2, 3-dicarboxylic anhydride and a catalyst; the preparation process of the modified filler comprises the following steps: mixing graphene oxide, nano zirconium oxide, boron nitride, sodium dodecyl benzene sulfonate, ethanol and water, then adding a silane coupling agent and octadecanoic acid-2, 2-dimethylolpropane-1, 3-diol ester, carrying out ultrasonic dispersion, and drying. The fiber composite material has good high temperature resistance and corrosion resistance at the same time.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and in particular relates to a corrosion-resistant and high-temperature-resistant fiber composite material and a preparation method and application thereof. Background Art

[0002] Glass fiber has a wide range of applications, including in construction, transportation, energy and environmental protection, and the electrical and electronic fields. When used in the electrical and electronic fields, glass fiber is often used in the manufacture of copper-clad laminates, which require excellent high-temperature and corrosion resistance.

[0003] In the prior art, the high temperature resistance and corrosion resistance of glass fibers are often improved by modifying the glass fibers or applying a coating on the surface of the glass fibers. However, the existing high temperature resistance is generally below 330°C.

[0004] Therefore, there is an urgent need to provide a new glass fiber product that can simultaneously meet good high temperature resistance and corrosion resistance. Summary of the Invention

[0005] The present invention aims to address at least one of the technical problems existing in the aforementioned prior art. To this end, the present invention provides a corrosion-resistant and high-temperature-resistant fiber composite material, as well as its preparation method and application. The fiber composite material of the present invention exhibits both excellent high-temperature resistance and corrosion resistance.

[0006] The fiber composite material of this invention achieves high-temperature and corrosion resistance through the synergistic effect of the cross-linked resin network and the uniform dispersion of modified fillers. Specifically, the bismaleimide resin is cured with methyl-5-norbornene-2,3-dicarboxylic anhydride to form a high-crosslink density structure, imparting thermal stability to the material. The tetrahydroxyl groups of the bishydroxy-terminated polydimethylsiloxane and pentaerythritol react with isocyanates, not only increasing the crosslink density but also interpenetrating with the resin network to form a stable three-dimensional network, enhancing the heat resistance of the fiber composite. The carboxyl groups of the graphene oxide (GO) in the modified filler condense with the hydrolysis products of the silane coupling agent, forming covalent bonds that anchor it to the resin network. Boron nitride (BN) sheets are uniformly dispersed by octadecanoic acid-2,2-dimethylolpropane-1,3-diol ester, providing a thermal conductivity path that relieves localized thermal stress. Nano-zirconium oxide is compatible with the polydimethylsiloxane segments, achieving directional alignment to block penetration of corrosive media. By modifying graphene oxide, nano-zirconium oxide, and boron nitride, the modified fillers are uniformly dispersed within the three-dimensional network structure formed by the resin system, significantly enhancing the fiber composite's high-temperature resistance and corrosion resistance. Specifically, the present invention utilizes the precise crosslinking of hydroxyl-isocyanate / bismaleimide resin-methyl-5-norbornene-2,3-dicarboxylic anhydride with the modified fillers to achieve molecular-level resin-filler bonding, significantly improving the fiber composite's overall performance in terms of high-temperature and corrosion resistance.

[0007] A first aspect of the present invention provides a corrosion-resistant and high-temperature-resistant fiber composite material.

[0008] A corrosion-resistant and high-temperature-resistant fiber composite material, comprising a glass fiber cloth and a coating coated on the surface of the glass fiber cloth; The raw material components of the coating include: component A and component B; The component A comprises bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, additives, and solvent; The B component includes isocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and a catalyst; The preparation process of the modified filler includes: mixing graphene oxide, nano zirconium oxide, boron nitride, sodium dodecylbenzenesulfonate, ethanol and water, then adding a silane coupling agent and octadecanoic acid-2,2-dihydroxymethylpropane-1,3-diol ester, ultrasonically dispersing, and drying to obtain the modified filler.

[0009] Preferably, the weight ratio of the graphene oxide, nano zirconium oxide, boron nitride, sodium dodecylbenzenesulfonate, ethanol and water is 1: (0.5-1.5): (0.1-2.0): (0.1-0.8): (3-10): (5-20), and more preferably 1: (0.8-1.2): (1-2): (0.2-0.7): (4-10): (10-20).

[0010] Preferably, the weight ratio of the graphene oxide, the silane coupling agent and octadecanoic acid-2,2-dihydroxymethylpropane-1,3-diol ester is 1:(0.8-2):(0.1-1.0), and more preferably 1:(1-1.8):(0.3-0.8).

[0011] Preferably, during the preparation of the modified filler, nano yttrium oxide is also added when graphene oxide is added.

[0012] Preferably, the ultrasonic dispersion time is 20-40 minutes, more preferably 25-35 minutes.

[0013] Preferably, the isocyanate is selected from at least one of m-xylylenediisocyanate and hexamethylene diisocyanate.

[0014] Preferably, the catalyst comprises an organic tin, such as dibutyltin dilaurate.

[0015] Preferably, the solvent includes at least one of toluene, tetrahydrofuran, ethyl acetate and acetone.

[0016] Preferably, the drying temperature is 80-100° C., and the drying time is 1-3 hours.

[0017] Preferably, the auxiliary agent includes a defoaming agent.

[0018] Preferably, the defoaming agent is polydimethylsiloxane.

[0019] Preferably, the silane coupling agent includes at least one of KH550, KH560 or KH570.

[0020] Preferably, the boron nitride has a hexagonal crystal structure.

[0021] Preferably, in the component A, the weight ratio of bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, additive, and solvent is 30: (5-15): (3-12): (12-35): (1-8): (20-50), and more preferably 30: (8-12): (5-10): (15-30): (1-5): (30-50).

[0022] Preferably, in the component B, the weight ratio of isocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and catalyst is 1:(0.5-1.8):(0.2-0.7), more preferably 1:(1.1-1.8):(0.3-0.6).

[0023] Preferably, the weight ratio of component A to component B is 10:(0.5-1.6), more preferably 10:(0.8-1.1).

[0024] A second aspect of the present invention provides a method for preparing a corrosion-resistant and high-temperature-resistant fiber composite material.

[0025] A method for preparing a corrosion-resistant and high-temperature-resistant fiber composite material comprises the following steps: (1) Taking glass fiber cloth, soaking it in alkali solution, and then drying it to obtain treated glass fiber cloth; (2) The component A and the component B are mixed to obtain a mixture, and then the treated glass fiber cloth is immersed in the mixture. The treated glass fiber cloth is taken out and subjected to heat treatment to obtain the fiber composite material.

[0026] Preferably, the glass fiber cloth is electronic grade and is a conventional product with models such as 106, 1080, and 2116.

[0027] Preferably, the alkali solution includes sodium hydroxide solution or potassium hydroxide solution.

[0028] Preferably, the concentration of the alkali solution is 0.5-2 mol / L.

[0029] Preferably, the soaking temperature is 25-45° C., and the soaking time is 0.5-2 hours.

[0030] Preferably, the drying temperature is 60-100° C. and the drying time is 0.5-2 hours.

[0031] Preferably, the heating treatment process is to first keep the temperature at 70-120° C. for 50-110 minutes, then keep the temperature at 120-150° C. for 50-120 minutes, and then keep the temperature at 190-210° C. for 1-2 hours.

[0032] A third aspect of the present invention provides an application of a corrosion-resistant and high-temperature-resistant fiber composite material.

[0033] Application of the above fiber composite materials in the electronic and electrical fields.

[0034] Preferably, the application includes application in a circuit board.

[0035] Compared with the prior art, the present invention has the following beneficial effects: By modifying graphene oxide, nano-zirconium oxide, and boron nitride, the modified filler is uniformly dispersed within the three-dimensional network structure formed by the resin system, significantly enhancing the fiber composite's high-temperature resistance and corrosion resistance. Specifically, the present invention utilizes the precise crosslinking of hydroxyl-isocyanate / methyl-5-norbornene-2,3-dicarboxylic anhydride and the interaction of the modified filler to achieve molecular-level resin-filler bonding, significantly improving the fiber composite's overall performance and resistance to high temperatures and corrosion. DETAILED DESCRIPTION

[0036] In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the following examples are given for illustration. It should be noted that the following examples do not limit the scope of protection claimed by the present invention.

[0037] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0038] The glass fiber cloth used below is electronic grade, a conventional product, model 1080.

[0039] Example 1 A corrosion-resistant and high-temperature-resistant fiber composite material, comprising a glass fiber cloth and a coating wrapped on the surface of the glass fiber cloth; The raw material components of the coating include: component A and component B, and the weight ratio of component A to component B is 10:1.2; Component A includes bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, polydimethylsiloxane, and acetone, wherein the weight ratio of bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, polydimethylsiloxane, and acetone is 30:10:5:30:4:30; Component B includes m-xylylenediisocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and dibutyltin dilaurate, wherein the weight ratio of m-xylylenediisocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and dibutyltin dilaurate is 1:1.8:0.2; The modified filler was prepared by mixing graphene oxide, nano-zirconium oxide, boron nitride (particle size of 80±5 nm), sodium dodecylbenzenesulfonate, ethanol, and water for 20 minutes, then adding a silane coupling agent KH560 and 1,3-diol octadecanoate, ultrasonically dispersing the mixture for 40 minutes, and drying the mixture at 100°C for 1 hour to obtain the modified filler. The weight ratio of graphene oxide, nano zirconium oxide, boron nitride, sodium dodecylbenzenesulfonate, ethanol and water is 1:1:1.5:0.4:4:10; The weight ratio of graphene oxide, silane coupling agent KH560 and octadecanoic acid-2,2-dihydroxymethylpropane-1,3-diol ester is 1:1.1:0.5.

[0040] A method for preparing a corrosion-resistant and high-temperature-resistant fiber composite material comprises the following steps: (1) Take glass fiber cloth, soak it in 0.1 mol / L sodium hydroxide solution at 25°C for 0.2 hours, and then dry it at 100°C for 1 hour to obtain treated glass fiber cloth; (2) The raw material components of component A are mixed to obtain component A, the raw material components of component B are mixed to obtain component B, and then component A and component B are mixed to obtain a mixture, and then the treated glass fiber cloth is immersed in the mixture. After 20 minutes, the treated glass fiber cloth is taken out, treated at 80°C for 60 minutes, then treated at 150°C for 60 minutes, and then kept warm at 200°C for 2 hours to obtain a fiber composite material.

[0041] Example 2 A corrosion-resistant and high-temperature-resistant fiber composite material, comprising a glass fiber cloth and a coating wrapped on the surface of the glass fiber cloth; The raw material components of the coating include: component A and component B, and the weight ratio of component A to component B is 10:1.0; Component A includes bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, polydimethylsiloxane, and acetone, wherein the weight ratio of bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, polydimethylsiloxane, and acetone is 30:8:6:28:5:35; Component B includes m-xylylenediisocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and dibutyltin dilaurate, wherein the weight ratio of m-xylylenediisocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and dibutyltin dilaurate is 1:1.6:0.2; The modified filler was prepared by mixing graphene oxide, nano-zirconium oxide (300 mesh), boron nitride (particle size of 80±5 nm), sodium dodecylbenzenesulfonate, ethanol, and water for 30 minutes, then adding a silane coupling agent KH570 and 1,3-diol octadecanoate, ultrasonically dispersing the mixture for 40 minutes, and drying the mixture at 100°C for 1 hour to obtain the modified filler. The weight ratio of graphene oxide, nano zirconium oxide, boron nitride, sodium dodecylbenzenesulfonate, ethanol and water is 1:1.2:1.6:0.5:5:12; The weight ratio of graphene oxide, silane coupling agent KH560 and octadecanoic acid-2,2-dihydroxymethylpropane-1,3-diol ester is 1:1.1:0.6.

[0042] A method for preparing a corrosion-resistant and high-temperature-resistant fiber composite material comprises the following steps: (1) Take glass fiber cloth, soak it in 0.1 mol / L sodium hydroxide solution at 25°C for 0.2 hours, and then dry it at 100°C for 1 hour to obtain treated glass fiber cloth; (2) The raw material components of component A are mixed to obtain component A, the raw material components of component B are mixed to obtain component B, and then component A and component B are mixed to obtain a mixture, and then the treated glass fiber cloth is immersed in the mixture. After 25 minutes, the treated glass fiber cloth is taken out, treated at 80°C for 60 minutes, then treated at 150°C for 60 minutes, and then kept warm at 200°C for 2 hours to obtain a fiber composite material.

[0043] Example 3 A corrosion-resistant and high-temperature-resistant fiber composite material, comprising a glass fiber cloth and a coating wrapped on the surface of the glass fiber cloth; The raw material components of the coating include: component A and component B, and the weight ratio of component A to component B is 10:1.2; Component A includes bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, polydimethylsiloxane, and acetone, wherein the weight ratio of bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, polydimethylsiloxane, and acetone is 30:10:5:30:4:30; Component B includes m-xylylenediisocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and dibutyltin dilaurate, wherein the weight ratio of m-xylylenediisocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and dibutyltin dilaurate is 1:1.8:0.2; The modified filler was prepared by mixing graphene oxide, nano-yttrium oxide, nano-zirconium oxide (300 mesh), boron nitride (particle size of 80±5 nm), sodium dodecylbenzenesulfonate, ethanol, and water for 20 minutes, then adding a silane coupling agent KH560 and 1,3-diol octadecanoate, ultrasonically dispersing the mixture for 40 minutes, and drying the mixture at 100°C for 1 hour to obtain the modified filler. The weight ratio of graphene oxide, nano zirconium oxide, boron nitride, sodium dodecylbenzenesulfonate, ethanol and water is 1:1:1.5:0.4:4:10; The weight ratio of graphene oxide, silane coupling agent KH560 and octadecanoic acid-2,2-dihydroxymethylpropane-1,3-diol ester is 1:1.1:0.5; The weight ratio of graphene oxide to nano-yttrium oxide is 1:0.9.

[0044] A method for preparing a corrosion-resistant and high-temperature-resistant fiber composite material comprises the following steps: (1) Take glass fiber cloth, soak it in 0.1 mol / L sodium hydroxide solution at 25°C for 0.2 hours, and then dry it at 100°C for 1 hour to obtain treated glass fiber cloth; (2) The raw material components of component A are mixed to obtain component A, the raw material components of component B are mixed to obtain component B, and then component A and component B are mixed to obtain a mixture, and then the treated glass fiber cloth is immersed in the mixture. After 20 minutes, the treated glass fiber cloth is taken out, treated at 80°C for 60 minutes, then treated at 150°C for 60 minutes, and then kept warm at 200°C for 2 hours to obtain a fiber composite material.

[0045] Comparative Example 1 Compared with Example 1, the only difference of Comparative Example 1 is that an equal amount of dihydroxy-terminated polydimethylsiloxane is used instead of pentaerythritol, and other components and preparation process are the same as those of Example 1.

[0046] Comparative Example 2 Compared with Example 1, the only difference of Comparative Example 2 is that an equal amount of sodium dodecylbenzenesulfonate is used instead of 2,2-dihydroxymethylpropane-1,3-diol octadecanoate, and other components and preparation process are the same as those of Example 1.

[0047] Comparative Example 3 Compared with Example 1, the only difference of Comparative Example 3 is that an equal amount of graphene oxide is used instead of boron nitride, and the other components and preparation process are the same as those of Example 1.

[0048] Comparative Example 4 Compared with Example 1, the only difference of Comparative Example 4 is that an equal amount of graphene oxide is used instead of nano zirconium oxide, and the other components and preparation process are the same as those of Example 1.

[0049] Product effect testing 1. High temperature resistance test The fiber composite materials prepared in Examples 1-3 and Comparative Examples 1-4 were applied to printed circuit boards, and heat resistance tests were performed according to GB / T4677.11-1984 “Test Method for Thermal Shock Resistance of Printed Circuit Boards”. The results are shown in Table 1.

[0050] Table 1

[0051] As can be seen from Table 1, the fiber composite materials prepared in Examples exhibit significantly better heat resistance than those in Comparative Examples. As can be seen from Example 1 and Comparative Example 1, the lack of pentaerythritol in Comparative Example 1 results in a decrease in the density of the resin after cross-linking and hinders the uniform dispersion of the modified filler, resulting in a decrease in the heat resistance of the fiber composite material prepared in Comparative Example 1.

[0052] It can be seen from Example 1 and Comparative Example 2 that Comparative Example 2 lacks 2,2-dimethylolpropane-1,3-diol octadecanoate, resulting in uneven dispersion of boron nitride, thereby reducing the heat resistance of the fiber composite material.

[0053] It can be seen from Example 1 and Comparative Examples 3-4 that the present invention uses graphene oxide, nano zirconium oxide and boron nitride to prepare the modified filler in a coordinated manner, so that the heat resistance of the prepared fiber composite material can be significantly enhanced.

[0054] The fiber composite material prepared in Example 3 was first immersed in a 0.5 mol / L sodium hydroxide solution at 60°C for 96 hours, and then immersed in 0.5 mol / L hydrochloric acid at 60°C for 96 hours. Heat resistance testing was then conducted in accordance with GB / T4677.11-1984, "Test Method for Thermal Shock Resistance of Printed Circuit Boards." The heat resistance temperature of the fiber composite material prepared in Example 3 was measured to be 353°C. This shows that even after acid and alkali corrosion treatment, the fiber composite material prepared in Example 3 still maintains good heat resistance, demonstrating that the fiber composite material prepared in the present invention has excellent corrosion resistance.

[0055] 2. Corrosion resistance test The fiber composite materials prepared in Example 1, Example 3, Comparative Example 1, and Comparative Example 4 were tested for radial breaking strength (recorded as the radial breaking strength without acid or alkali treatment) in accordance with GB / T 7689.5-2013 "Test methods for reinforced fabrics - Part 5: Determination of tensile strength and elongation at break of glass fibers". The fibers were then immersed in a 0.5 mol / L sodium hydroxide solution at 60°C for 96 hours, and then immersed in 0.5 mol / L hydrochloric acid at 60°C for 96 hours. The strength of the fiber composite materials was then tested (recorded as the radial breaking strength without acid or alkali treatment). The results are shown in Table 2.

[0056] Table 2

[0057] Among them, radial breaking strength retention rate (%) = radial breaking strength after acid and alkali treatment / radial breaking strength without acid and alkali treatment*100%.

[0058] As can be seen from Table 2, the examples have better corrosion resistance than the comparative examples. As can be seen from Example 1, Comparative Examples 1 and 4, pentaerythritol and nano-zirconium oxide have a significant effect on constructing the corrosion-resistant coating.

Claims

1. A fiber composite material, characterized in that It includes glass fiber cloth and a coating wrapped on the surface of the glass fiber cloth; The raw material components of the coating include: component A and component B; The component A comprises bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, additives, and solvent; The B component includes isocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and a catalyst; The preparation process of the modified filler includes: mixing graphene oxide, nano zirconium oxide, boron nitride, sodium dodecylbenzenesulfonate, ethanol and water, then adding a silane coupling agent and octadecanoic acid-2,2-dihydroxymethylpropane-1,3-diol ester, ultrasonically dispersing, and drying to obtain the modified filler.

2. The fiber composite material according to claim 1, characterized in that The weight ratio of the graphene oxide, nano zirconium oxide, boron nitride, sodium dodecylbenzenesulfonate, ethanol and water is 1: (0.5-1.5): (0.1-2.0): (0.1-0.8): (3-10): (5-20).

3. The fiber composite material according to claim 1, characterized in that The weight ratio of the graphene oxide, the silane coupling agent and octadecanoic acid-2,2-dihydroxymethylpropane-1,3-diol ester is 1: (0.8-2): (0.1-1.0).

4. The fiber composite material according to claim 1, characterized in that The isocyanate is selected from at least one of m-xylylenediisocyanate and hexamethylene diisocyanate; and / or the catalyst includes organic tin; and / or the auxiliary agent includes a defoaming agent.

5. The fiber composite material according to claim 1, characterized in that The silane coupling agent includes at least one of KH550, KH560 or KH570.

6. The fiber composite material according to claim 1, characterized in that In the component A, the weight ratio of bismaleimide resin, bishydroxy-terminated polydimethylsiloxane, pentaerythritol, modified filler, additive and solvent is 30: (5-15): (3-12): (12-35): (1-8): (20-50).

7. The fiber composite material according to claim 1, characterized in that In the B component, the weight ratio of isocyanate, methyl-5-norbornene-2,3-dicarboxylic anhydride, and catalyst is 1:(0.5-1.8):(0.2-0.7); and / or the weight ratio of the A component to the B component is 10:(0.5-1.6).

8. The method for preparing the fiber composite material according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Taking glass fiber cloth, soaking it in alkali solution, and then drying it to obtain treated glass fiber cloth; (2) The component A and the component B are mixed to obtain a mixture, and then the treated glass fiber cloth is immersed in the mixture. The treated glass fiber cloth is taken out and subjected to heat treatment to obtain the fiber composite material.

9. The preparation method according to claim 8, characterized in that The alkali solution includes sodium hydroxide solution or potassium hydroxide solution; and / or, the heat treatment process is first keeping warm at 70-120°C for 50-110 minutes, then keeping warm at 120-150°C for 50-120 minutes, and then keeping warm at 180-210°C for 1-2 hours.

10. Use of the fiber composite material according to any one of claims 1 to 7 in the field of electronics and electrical equipment.

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