Polyimide fiber and basalt fiber composite board and preparation method thereof

Abstract

The invention relates to the technical field of composite boards, in particular to a polyimide fiber and basalt fiber composite board and a preparation method thereof. The composite material comprises a base plate formed by a plurality of layers of blended fabrics which are tiled, overlapped and bonded together, warp yarns of adjacent blended fabrics are perpendicular to each other, and the blended fabrics are blended fabrics of polyimide fibers and basalt fibers which are subjected to oxidation modification; the upper and lower surfaces of the substrate have polyamide-imide resin layers. The H2O2 solution is used for oxidizing the fabric, so that carbon-carbon bonds of polyimide are oxidized and broken, amido bonds are kept stable, the specific surface area of fibers is increased, the adhesion of the surfaces of the fibers is improved, the binding force of the fibers and resin is enhanced, and the strength and toughness of the composite board are enhanced. The polyamide-imide resin layers are formed on the upper surface and the lower surface of the base plate, so that the crack resistance and the impact resistance of the composite board are greatly enhanced, and meanwhile, the heat preservation property and the attractive degree of the composite board are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of composite boards, and in particular to a composite board of polyimide fiber and basalt fiber and a preparation method thereof. Background Art

[0002] Composite panels are a new generation of high-performance building partitions produced industrially. They are usually made of two or more materials and have the advantages of environmental protection and energy saving, light weight and earthquake resistance, fire resistance, moisture resistance, heat preservation and sound insulation. Most of the current composite panels use wood, rock wool and ceramics as the matrix. However, composite panels with wood, rock wool and ceramics as the matrix have low strength, low compression and tensile properties, poor fire resistance and poor thermal insulation. At present, we need to develop high-performance composite panels that are lightweight, high-strength, high temperature resistant, fire retardant, and soundproof and heat-insulating. Summary of the invention

[0003] The purpose of the present invention is to address the above-mentioned deficiencies in the prior art and to provide a polyimide fiber and basalt fiber composite board and a preparation method thereof.

[0004] The present invention discloses a polyimide fiber and basalt fiber composite board, comprising multiple layers of blended fabrics which are laid flat, overlapped and bonded together, wherein the warp yarns of adjacent blended fabrics are perpendicular to each other, and the blended fabric is a blended fabric of polyimide fiber and basalt fiber which has been oxidatively modified, and the upper and lower surfaces of the polyimide fiber and basalt fiber composite substrate have polyamide-imide resin layers.

[0005] Furthermore, the oxidatively modified treatment agent is a H2O2 solution.

[0006] Furthermore, the adhesive used for bonding is a mixture of resin, curing agent and accelerator.

[0007] Furthermore, the resin is MFE 701-01 styrene-free epoxy vinyl ester resin, with a viscosity of 700±100 mPa.s, a tensile strength of 68 MPa, a tensile modulus of 3200 MPa, an elongation at break of 2.5%, a flexural strength of 120 MPa, and a flexural modulus of 3200 MPa.

[0008] Furthermore, the curing agent is BUTANOX M-50 curing agent, and the curing agent density is 1.180 g / cm 3 , the curing agent viscosity is 24mPa.s; the accelerator is P001 accelerator C 14 H 22 CoO4 is a purple liquid with a molecular weight of 313.25, a flash point of 48.9°C and a melting point of 140°C.

[0009] Furthermore, the number of layers of the blended fabric is 5-7.

[0010] Furthermore, the blended fabric has a gram weight of 350-400 g / m 2 , board density weight 2-4kg / m 2 .

[0011] A method for preparing the above-mentioned polyimide fiber and basalt fiber composite board comprises the following steps:

[0012] Step S1: soak the blended fabric in H2O2 solution for 2-4 hours, then take it out, wash it and dry it;

[0013] Step S2: spraying a release agent inside the upper and lower molds, and laying the cut mixed-woven fabric into the mold in sequence by laying it flat and overlapping; the spraying release agent is 0.1-0.5 mm, and the volatilization time is 5-10 minutes.

[0014] Step S3: coating the prepared adhesive layer by layer on the flat polyimide fiber and basalt fiber blended fabric, and using a molding machine to heat and cure the polyimide fiber and basalt fiber blended fabric bonded into one, to obtain a polyimide fiber and basalt fiber composite substrate;

[0015] Step S4: evenly apply the polyamide-imide resin on the upper and lower surfaces of the polyimide fiber and basalt fiber composite substrate, and heat and cure to obtain a polyimide fiber and basalt fiber composite board.

[0016] Furthermore, the adhesive is prepared by the following method: adding the accelerator to the resin in proportion and stirring in a storage tank to make the resin and the accelerator dispersed evenly, and defoaming the resin and the accelerator in the storage tank by vacuuming;

[0017] Add the curing agent to the stirred resin and accelerator in proportion and stir in the storage tank to make the curing agent, resin and accelerator evenly dispersed, and defoam the mixture of resin, curing agent and accelerator in the storage tank by vacuuming;

[0018] The mass ratio of resin, accelerator and curing agent is 200:1-3:1-3;

[0019] The resin and accelerator are stirred in the storage tank for 5-10 minutes, the stirring speed is 200-300 rpm, and the negative pressure value of vacuum is -0.1Mpa. The resin and curing agent are stirred in the storage tank for 5-10 minutes, the stirring speed is 200-300 rpm, and the negative pressure value of vacuum is -0.1Mpa.

[0020] Furthermore, in step S3, the mold closing speed is 3-8s, the temperature is raised to 100°C at 4-6°C / min and kept at that temperature for 15-25min, and then cooled and cured; the mold opening speed is the same as the mold closing speed.

[0021] The present invention uses H2O2 solution to perform oxidation treatment on a blended fabric of polyimide fiber and basalt fiber, so that the carbon-carbon bonds of the polyimide are oxidatively broken while the amide bonds are kept stable. The structure and performance of the fibers remain basically unchanged while increasing the specific surface area of ​​the fibers, improving the adhesion of the fiber surface, enhancing the bonding force between the fibers and the resin, and enhancing the strength and toughness of the composite board.

[0022] The warp yarns of the adjacent blended fabrics are perpendicular to each other and are light in weight, making the composite board lighter, with a board surface density of 2-4 kg / m 2 , which improves the ease of use of composite panels.

[0023] The polyimide fiber and basalt fiber composite board of the present application uses polyimide material and basalt material as the main materials, which increases the heat resistance, flame retardancy, thermal insulation and insulation of the composite board. By making the warp yarns of adjacent blended fabrics perpendicular to each other, the tensile strength of the composite board is 10-15 times that of the composite board with ordinary wood, rock wool and ceramic as the matrix, thereby improving the safety of the composite board and also enhancing the service life of the composite board.

[0024] A polyimide fiber and basalt fiber composite board of the present application uses MFE 701-01 styrene-free epoxy vinyl ester resin as the bonding material between the substrate layers, and by adding a curing agent and an accelerator to the resin, the bonding strength and toughness between the layers are enhanced, thereby improving the tensile strength and compressive strength of the composite board.

[0025] The polyimide fiber and basalt fiber blended fabric is light in weight, so the resin can fully infiltrate the fabric, and the layers are firmly bonded, stable and impact resistant. A polyamide-imide resin layer (PAI) is formed on the upper and lower surfaces of the substrate, which greatly enhances the crack resistance and impact resistance of the polyimide fiber and basalt fiber composite board, while improving the thermal insulation and aesthetics of the composite board.

[0026] The preparation method of the polyimide fiber and basalt fiber composite plate of the present application is simple, safe and environmentally friendly, has low preparation cost, stable and excellent performance of the finished product, and good use effect. DETAILED DESCRIPTION

[0027] The following are specific embodiments of the present invention, which further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.

[0028] Example 1

[0029] (1) The polyimide fiber and basalt fiber blended fabric is immersed in a H2O2 solution for 2-4 hours, then taken out, washed, and dried to obtain the polyimide fiber and basalt fiber fabric after oxidation treatment.

[0030] (2) Spraying a release agent on the inside of the upper and lower molds, with a thickness of 0.1-0.5 mm and a volatilization time of 5-10 min, manually cutting the polyimide fiber and basalt fiber blended fabric into 5 sheets of 1000 mm × 1000 mm, and laying the first layer of the cut polyimide fiber and basalt fiber blended fabric on the lower mold at 0°;

[0031] (3) Take 2000g of MFE 701-01 styrene-free epoxy vinyl ester resin, take 10g of accelerator with a pipette and add it to the resin and stir in a storage tank. The stirring time is 5 minutes and the stirring speed is 200 rpm to make the resin and accelerator evenly dispersed. The resin and accelerator in the storage tank are defoamed by vacuuming. The negative pressure value of vacuuming is -0.1Mpa;

[0032] (4) Use a pipette to take 20 g of curing agent and add it to the stirred resin and accelerator in the storage tank and stir to make the curing agent, resin and accelerator evenly dispersed. The stirring time is 5 min and the stirring speed is 200 rpm. The resin, curing agent and accelerator mixture in the storage tank is defoamed by vacuuming. The negative pressure value of vacuuming is -0.1 MPa.

[0033] (5) using a hand lay-up process to apply the mixed resin to the first layer of polyimide fiber and basalt fiber blended fabric laid flat on the lower composite film, so that the resin fully impregnates the first layer of polyimide fiber and basalt fiber blended fabric, and then lays a second layer of polyimide fiber and basalt fiber blended fabric of 1000mm×1000mm on the first layer of polyimide fiber and basalt fiber blended fabric at 90°, and applies the mixed resin to the second layer of polyimide fiber and basalt fiber blended fabric, so that the resin fully impregnates the second layer of polyimide fiber and basalt fiber blended fabric, repeating the above process to lay the third, fourth, and fifth layers of polyimide fiber and basalt fiber blended fabric flat and overlapped at 0° and 90° in turn, fully impregnating them with resin, and bonding the polyimide fiber and basalt fiber blended fabric into one;

[0034] (6) The polyimide fiber and basalt fiber blended fabric bonded together is heated and cured by a molding machine, the pressure is set to 60 kg, the mold closing speed is 3-8 s, the temperature is increased to 100 ° C at 4-6 ° C / min, the temperature is kept for 15 min, and then the temperature is lowered and cured, and the mold is opened, and the mold opening speed is the same as the mold closing speed. A polyimide fiber and basalt fiber composite board substrate is obtained.

[0035] (7) Pour the PAI polyamide-imide resin on the upper and lower surfaces of the cooled substrate, spread it evenly with a scraper, turn on the flat vulcanizer, open the mold, put a polytetrafluoroethylene film on the lower mold, place the substrate on the polytetrafluoroethylene film, manually close the film so that the substrate and the upper mold of the vulcanizer are 10 cm apart, set the temperature to 100°C, raise the temperature of the flat vulcanizer to 100°C, cure for 30 minutes, set the temperature of the vulcanizer to 120°C, raise the temperature to 120°C, cure for 20 minutes, open the mold and take out the substrate, so that the PAI polyamide-imide resin is cured to form a film on the substrate, and obtain a polyimide fiber and basalt fiber composite sheet.

[0036] Example 2

[0037] (1) The polyimide fiber and basalt fiber blended fabric is immersed in a H2O2 solution for 2-4 hours, then taken out, washed, and dried to obtain the polyimide fiber and basalt fiber fabric after oxidation treatment.

[0038] (2) Spraying a release agent on the inside of the upper and lower molds, with a thickness of 0.1-0.5 mm and a volatilization time of 5-10 min, manually cutting the polyimide fiber and basalt fiber blended fabric into 6 sheets of 1000 mm × 1000 mm, and laying the first layer of the cut polyimide fiber and basalt fiber blended fabric on the lower mold at 0°;

[0039] (3) Take 2000g of MFE 701-01 styrene-free epoxy vinyl ester resin, take 10g of accelerator with a pipette and add it to the resin and stir in a storage tank. The stirring time is 5 minutes and the stirring speed is 250 rpm to make the resin and accelerator evenly dispersed. The resin and accelerator in the storage tank are defoamed by vacuuming. The negative pressure value of vacuuming is -0.1 MPa.

[0040] (4) Use a pipette to take 20 g of curing agent and add it to the stirred resin and accelerator in the storage tank and stir to make the curing agent, resin and accelerator evenly dispersed. The stirring time is 5 min and the stirring speed is 250 rpm. The resin, curing agent and accelerator mixture in the storage tank is defoamed by vacuuming. The negative pressure value of vacuuming is -0.1 MPa.

[0041] (5) using a hand lay-up process to apply the mixed resin to the first layer of polyimide fiber and basalt fiber blended fabric laid flat on the lower composite film, so that the resin fully impregnates the first layer of polyimide fiber and basalt fiber blended fabric, and then lays a second layer of polyimide fiber and basalt fiber blended fabric of 1000mm×1000mm on the first layer of polyimide fiber and basalt fiber blended fabric at 90°, and applies the mixed resin to the second layer of polyimide fiber and basalt fiber blended fabric, so that the resin fully impregnates the second layer of polyimide fiber and basalt fiber blended fabric, repeating the above process to lay the third, fourth, fifth, and sixth layers of polyimide fiber and basalt fiber blended fabric flat and overlapped at 0° and 90° in turn, fully impregnating them with resin, and bonding the polyimide fiber and basalt fiber blended fabric into one;

[0042] (6) The polyimide fiber and basalt fiber blended fabric bonded together is heated and cured by a molding machine, the pressure is set to 60 kg, the mold closing speed is 3-8 s, the temperature is increased to 100 ° C at 4-6 ° C / min, the temperature is kept for 20 min, and then the temperature is lowered and cured, and the mold is opened, and the mold opening speed is the same as the mold closing speed. A polyimide fiber and basalt fiber composite board substrate is obtained.

[0043] (7) Pour the PAI polyamide-imide resin on the upper and lower surfaces of the cooled substrate, spread it evenly with a scraper, turn on the flat vulcanizer, open the mold, put a polytetrafluoroethylene film on the lower mold, place the substrate on the polytetrafluoroethylene film, manually close the film so that the substrate and the upper mold of the vulcanizer are 10 cm apart, set the temperature to 100°C, raise the temperature of the flat vulcanizer to 100°C, cure for 30 minutes, set the temperature of the vulcanizer to 120°C, raise the temperature to 120°C, cure for 20 minutes, open the mold and take out the substrate, so that the PAI polyamide-imide resin is cured to form a film on the substrate, and obtain a polyimide fiber and basalt fiber composite sheet.

[0044] Example 3

[0045] (1) The polyimide fiber and basalt fiber blended fabric is immersed in a H2O2 solution for 2-4 hours, then taken out, washed, and dried to obtain the polyimide fiber and basalt fiber fabric after oxidation treatment.

[0046] (2) Spraying a release agent on the inside of the upper and lower molds, with a thickness of 0.1-0.5 mm and a volatilization time of 5-10 min, manually cutting the polyimide fiber and basalt fiber blended fabric into 7 sheets of 1000 mm × 1000 mm, and laying the first layer of the cut polyimide fiber and basalt fiber blended fabric on the lower mold at 0°;

[0047] (3) Take 2000g of MFE 701-01 styrene-free epoxy vinyl ester resin, take 10g of accelerator with a pipette and add it to the resin and stir in a storage tank. The stirring time is 10min and the stirring speed is 300 rpm to make the resin and accelerator evenly dispersed. The resin and accelerator in the storage tank are defoamed by vacuuming. The negative pressure value of vacuuming is -0.1Mpa.

[0048] (4) Take 20g of curing agent with a pipette and add it to the stirred resin and accelerator in the storage tank and stir until the curing agent, resin and accelerator are evenly dispersed. The stirring time is 10min and the stirring speed is 300 rpm. The resin, curing agent and accelerator mixture in the storage tank is defoamed by vacuuming. The negative pressure value of vacuuming is -0.1Mpa.

[0049] (5) using a hand lay-up process to apply the mixed resin to the first layer of polyimide fiber and basalt fiber blended fabric laid flat on the lower composite film, so that the resin fully infiltrates the first layer of polyimide fiber and basalt fiber blended fabric, and then laying a second layer of polyimide fiber and basalt fiber blended fabric of 1000mm×1000mm at 90° on the first layer of polyimide fiber and basalt fiber blended fabric, and applying the mixed resin to the second layer of polyimide fiber and basalt fiber blended fabric, so that the resin fully infiltrates the second layer of polyimide fiber and basalt fiber blended fabric, repeating the above process to lay the third, fourth, fifth, sixth, and seventh layers of polyimide fiber and basalt fiber blended fabric flat at 0° and 90° in turn, fully infiltrating them with resin, and bonding the polyimide fiber and basalt fiber blended fabric into one;

[0050] (6) The polyimide fiber and basalt fiber blended fabric bonded together is heated and cured by a molding machine, the pressure is set to 60 kg, the mold closing speed is 3-8 s, the temperature is increased to 100 ° C at 4-6 ° C / min, the temperature is kept for 25 min, and then the temperature is lowered and cured, and the mold is opened, and the mold opening speed is the same as the mold closing speed. A polyimide fiber and basalt fiber composite board substrate is obtained.

[0051] (7) Pour the PAI polyamide-imide resin on the upper and lower surfaces of the cooled substrate, spread it evenly with a scraper, turn on the flat vulcanizer, open the mold, put a polytetrafluoroethylene film on the lower mold, place the substrate on the polytetrafluoroethylene film, manually close the film so that the substrate and the upper mold of the vulcanizer are 10 cm apart, set the temperature to 100°C, raise the temperature of the flat vulcanizer to 100°C, cure for 30 minutes, set the temperature of the vulcanizer to 120°C, raise the temperature to 120°C, cure for 20 minutes, open the mold and take out the substrate, so that the PAI polyamide-imide resin is cured to form a film on the substrate, and obtain a polyimide fiber and basalt fiber composite sheet.

[0052] Comparative Example 1

[0053] Excluding step (1), that is, the polyimide fiber and basalt fiber blended fabric is not subjected to oxidation treatment, the other steps are the same as those in the embodiment.

[0054] Comparative Example 2

[0055] Step (7) is not included, that is, the polyimide fiber and basalt fiber composite sheet is not used to make an exterior decorative layer, and the other steps are the same as those in the embodiment.

[0056] The physical property parameters of the polyimide fiber and basalt fiber composite plates prepared in Examples 1 to 3 of the present application were tested, and the test results are shown in the following table.

[0057]

[0058]

[0059] From the above table, we can see that the polyimide fiber and basalt fiber composite board prepared in the embodiment of the present application has a surface density of 2-4 kg / m 2 , smaller than the current conventional composite panels, lighter and more convenient to use.

[0060] The present application forms a polyamide-imide resin layer on the upper and lower surfaces of the substrate, which greatly enhances the crack resistance and impact resistance of the polyimide fiber and basalt fiber composite board, while improving the thermal insulation and aesthetics of the composite board.

[0061] In addition, the tensile strength of the polyimide fiber and basalt fiber composite board prepared in the embodiment of the present application is above 330 GPa, the flexural strength is above 370 GPa, the tensile modulus is above 14 GPa, and the flexural modulus is above 18 GPa, indicating that the performance of the polyimide fiber and basalt fiber composite board prepared in the embodiment of the present application is better than that of the composite board prepared in Comparative Example 1.

[0062] For matters not mentioned above, the prior art applies.

[0063] Although some specific embodiments of the present invention have been described in detail through examples, those skilled in the art should understand that the above examples are for illustration only and are not intended to limit the scope of the present invention. Those skilled in the art to which the present invention belongs may make various modifications or supplements to the specific embodiments described or replace them in a similar manner, but they will not deviate from the direction of the present invention or exceed the scope defined by the attached claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc. made to the above embodiments based on the technical essence of the present invention should be included in the protection scope of the present invention.

Claims

1. A polyimide fiber and basalt fiber composite sheet, characterized in that: The invention relates to a polyimide fiber and basalt fiber composite substrate which is composed of multiple layers of blended fabrics which are laid flat, overlapped and bonded together, wherein the warp yarns of adjacent blended fabrics are perpendicular to each other, and the blended fabrics are blended fabrics of polyimide fiber and basalt fiber which have been oxidatively modified; the upper and lower surfaces of the polyimide fiber and basalt fiber composite substrate are provided with polyamide-imide resin layers.

2. The polyimide fiber and basalt fiber composite sheet according to claim 1, characterized in that: The oxidatively modified treatment agent is a H2O2 solution.

3. The polyimide fiber and basalt fiber composite sheet according to claim 1, characterized in that: The adhesive used for bonding is a mixture of resin, curing agent and accelerator.

4. The polyimide fiber and basalt fiber composite sheet according to claim 3, characterized in that: The resin is MFE 701-01 styrene-free epoxy vinyl ester resin.

5. The polyimide fiber and basalt fiber composite sheet according to claim 3, characterized in that: The curing agent is BUTANOX M-50 curing agent; the accelerator is P001 accelerator C 14 H 22 CoO4.

6. The polyimide fiber and basalt fiber composite sheet according to claim 1, characterized in that: The mixed fabric has 5 to 7 layers.

7. The polyimide fiber and basalt fiber composite sheet according to claim 1, characterized in that: The gram weight of the blended fabric is 350-400g / m 2 , board density weight 2-4kg / m 2 .

8. A method for preparing a composite sheet of polyimide fiber and basalt fiber according to any one of claims 1 to 7, characterized in that: The steps include: Step S1: soak the blended fabric in H2O2 solution for 2-4 hours, then take it out, wash it and dry it; Step S2: spraying a mold release agent inside the upper and lower molds, and laying the cut blended fabrics flat into the mold in sequence by flatly laying and stacking; Step S3: coating the prepared adhesive layer by layer on the flat polyimide fiber and basalt fiber blended fabric, and using a molding machine to heat and cure the polyimide fiber and basalt fiber blended fabric bonded into one, to obtain a polyimide fiber and basalt fiber composite substrate; Step S4: evenly apply the polyamide-imide resin on the upper and lower surfaces of the polyimide fiber and basalt fiber composite substrate, and heat and cure to obtain a polyimide fiber and basalt fiber composite board.

9. The preparation method according to claim 8, characterized in that: The adhesive is prepared by the following method: adding the accelerator to the resin in proportion and stirring in a storage tank to make the resin and the accelerator dispersed evenly, and defoaming the resin and the accelerator in the storage tank by vacuuming; Add the curing agent to the stirred resin and accelerator in proportion and stir in the storage tank to make the curing agent, resin and accelerator evenly dispersed, and defoam the mixture of resin, curing agent and accelerator in the storage tank by vacuuming; The mass ratio of resin, accelerator and curing agent is 200:1-3:1-3.

10. The preparation method according to claim 8, characterized in that: In step S3, the mold closing speed is 3-8s, the temperature is raised to 100°C at 4-6°C / min, kept at that temperature for 15-25min, and then cooled and solidified; the mold opening speed is the same as the mold closing speed.

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