Continuous fiber reinforced modified polyphenyl ether thermoplastic composite material laminated plate and continuous automatic preparation method thereof

Abstract

The invention discloses a continuous fiber reinforced modified polyphenyl ether thermoplastic composite material laminated plate and a continuous automatic preparation method thereof, and the laminated plate is composed of a continuous fiber fabric as a reinforcement and a modified polyphenyl ether thermoplastic resin as a matrix, the dosage of the continuous fiber fabric and the modified polyphenyl ether thermoplastic resin is 30-70 parts by weight, and the modified polyphenyl ether thermoplastic resin is formed by polymerizing a mixed resin material. The preparation method comprises the following steps: mixing polyphenyl ether powder, vinyl modified polyphenyl ether, a styrene monomer, a flame retardant and an assistant until the mixture is in a daub shape, alternately paving the mixture and continuous fiber fabric through an online gluing system, then carrying out high-temperature hot press molding, and carrying out in-situ polymerization reaction on sheets under high-temperature and pressurized conditions, and meanwhile, infiltrating and infiltrating the continuous fiber fabric, cooling to room temperature, and demolding. The resin and fiber interface bonding property is good, the mechanical property of the composite material is good, and the lightweight requirements in the fields of aviation, automobiles, photovoltaics, new energy and the like are met.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials, and in particular relates to a continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate and a continuous automated preparation method thereof. Background Art

[0002] In the prior art, continuous fiber reinforced thermoplastic composite laminates are usually prepared by heating and melting thermoplastic resins and then pressing them with fibers or fiber fabrics into sheets or plates; or the molten thermoplastic resin is film-formed and then rolled and compounded with fibers or fiber fabrics into sheets or plates. However, when preparing composite laminates by the above hot melt method, the contact between the thermoplastic resin and the fiber interface is only physical wrapping, and there is no reaction with the fiber interface, and the bonding force is poor. Moreover, due to the high processing temperature and poor fluidity of polyphenylene ether resin, it is difficult to effectively infiltrate the fibers, and the degree to which the mechanical properties of the fibers used as reinforcements in the composite material are exerted depends on the effectiveness of the load transfer at the interface between the resin and the fiber. Therefore, the composite industry generally recognizes that the mechanical properties of thermoplastic composites are generally much lower than those of thermosetting composites.

[0003] For thermoplastic composites, one way to overcome the above fiber interface problem is in-situ polymerization, that is, preparing composite materials by in-situ polymerization. Since the polymer has wrapped the fiber and made its interface participate in the reaction process when the polymerization reaction occurs, the interfacial bonding force is improved, and the mechanical properties of the thermoplastic composite are greatly improved. However, the market application maturity of the above method is relatively low, especially for continuous fiber reinforced thermoplastic composites, there are still the following problems: 1) The difficulty of impregnation of the fiber surface makes it impossible to use the in-situ polymerization method for most thermoplastic resins; 2) The sensitivity of the material to water during the polymerization process leads to a low process yield, high investment in special equipment, and high requirements for the moisture content of the fiber surface; 3) A full polymerization reaction takes a long time, which is difficult to meet mass production needs. Summary of the invention

[0004] The main purpose of the present invention is to provide a continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, whose comprehensive performance meets the demand for lightweight composite materials in the fields of aviation, automobiles, photovoltaics, new energy, etc., and the recyclable and reusable properties of the material meet environmental protection requirements.

[0005] Another object of the present invention is to provide a continuous automated preparation method for the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, which has a simple process and can be mass-produced.

[0006] To achieve the above object, the present invention adopts the following technical solution:

[0007] The first aspect of the present invention is a continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, characterized in that it includes 30 to 70 parts by weight of continuous fiber fabric as a reinforcement and 30 to 70 parts by weight of modified polyphenylene ether thermoplastic resin as a matrix; the modified polyphenylene ether thermoplastic resin is polymerized from a mixed resin material, and includes, by weight: 30 to 70 parts by weight of polyphenylene ether, 30 to 70 parts by weight of styrene, 5 to 20 parts by weight of vinyl modified polyphenylene ether, 0.5 to 2 parts by weight of initiator, 1 to 3 parts by weight of silane coupling agent, 3 to 16 parts by weight of flame retardant, 0.2 to 0.6 parts by weight of antioxidant, 0.3 to 1 parts by weight of heat stabilizer, 0.2 to 0.4 parts by weight of light stabilizer, and 0.05 to 0.3 parts by weight of ultraviolet light absorber.

[0008] Preferably, the vinyl-modified polyphenylene ether comprises, by weight, 30 to 70 parts by weight of polyphenylene ether, 1 to 3 parts by weight of acrylic monomer and 0.5 to 1 part by weight of catalyst; the preparation method comprises: dissolving polyphenylene ether and acrylic monomer in a solvent and mixing evenly, passing nitrogen gas for protection, slowly dropping the catalyst, heating and stirring in an oil bath for esterification reaction, the reaction temperature is 60 to 120° C., the reaction time is 2 to 10 hours, and cooling, filtering and removing the solvent after the reaction is completed to obtain the product.

[0009] Preferably, the structural thickness of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate is 0.2 to 5 mm. In theory, a thicker structure no longer has the lightweight advantage of high-performance continuous fiber reinforced composite materials.

[0010] Preferably, the material of the continuous fiber fabric is selected from one or more of carbon fiber, glass fiber, and polymer fiber, and the continuous fiber fabric includes woven fabric and / or warp knitted axial fabric.

[0011] Preferably, the modified polyphenylene ether thermoplastic resin comprises, by weight: 60 parts by weight of polyphenylene ether, 10 parts by weight of vinyl modified polyphenylene ether, 30 parts by weight of styrene, 2 parts by weight of initiator, 3 parts by weight of silane coupling agent, 7 parts by weight of flame retardant, 0.5 parts by weight of antioxidant, 0.7 parts by weight of heat stabilizer, 0.3 parts by weight of light stabilizer, and 0.2 parts by weight of ultraviolet light absorber.

[0012] In a second aspect of the present invention, the method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate comprises the following steps:

[0013] (i) mixing polyphenylene ether, vinyl modified polyphenylene ether, styrene, initiator, silane coupling agent, flame retardant, antioxidant, heat stabilizer, light stabilizer and ultraviolet light absorber in an automated mixing device until the mixture is in a paste state, and then alternately coating the mixture with continuous fiber fabric in an online glue coating system to obtain a mixed resin sheet;

[0014] (ii) preheating a flat plate press, placing the mixed resin sheet on the continuous fiber fabric for high-temperature hot pressing, wherein the mixed resin sheet undergoes in-situ polymerization under high temperature and pressure conditions and simultaneously penetrates and soaks the continuous fiber fabric, and then cools to room temperature and demolds to obtain the product.

[0015] Preferably, the temperature of the high-temperature hot pressing molding is 140-210° C., the pressure is 0.5-20 MPa, and the hot pressing time is 0.5-3 h.

[0016] Preferably, the method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate comprises:

[0017] (1) A release agent is applied to the upper surface of the lower steel plate of the flat press in advance or an isolation film is placed thereon, and the cut continuous fiber fabric is placed at a predetermined position above the lower steel plate;

[0018] (2) using an automated mixing device to mix the materials into a paste-like state, and then alternately coating the materials with continuous fiber fabrics through an online glue coating system to obtain a mixed resin sheet;

[0019] (3) A release agent is applied to the lower surface of the upper steel plate of the flat press in advance or an isolation film is placed thereon, and the upper steel plate is covered on the continuous fiber fabric on which the mixed resin sheet is finally laid, and aligned with the lower steel plate below;

[0020] (4) The assembled lower steel plate, continuous fiber fabric, mixed resin sheet and upper steel plate are respectively moved into a flat plate press with a preheating temperature of 140-210°C, and the outer door of the press is closed and the mold is closed for high-temperature pressing. The pressing time is 0.5-3h and the pressing pressure is 0.5-20MPa. The process is assisted by vacuuming. After the pressing is completed, the pressure is maintained and the temperature is lowered to below 130°C, the vacuum is released, and the door is opened to remove the mold.

[0021] More preferably, in step (4), a multi-layer flat plate press with six openings is used, and the above steps (1)-(4) are repeated until all openings of the multi-layer flat plate press are filled.

[0022] More preferably, in step (4), the vacuum is released and the door is opened to demould, and the lower steel plate, product and upper steel plate combination of each layer in the multi-layer flat press are transferred to a separate multi-layer cold press and cold pressed together to below 80°C, and the number of open layers of the multi-layer cold press is consistent with the number of multi-layer flat presses.

[0023] During the preparation process of the above-mentioned continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, the mixed resin sheet undergoes an in-situ polymerization reaction, and reacts with the fiber interface during the polymerization process, so it has higher mechanical properties. At the same time, the mixed resin sheet has uniform thickness and is easy to penetrate and infiltrate the continuous fiber fabric under the action of high temperature and pressure, and can easily achieve a composite fiber volume content greater than 50%. According to actual product requirements, a higher fiber content is pursued, and excellent mechanical properties are possessed at the same thickness of the composite laminate. In addition, due to the easy operation and thickness uniformity of the mixed resin sheet state, the preparation method is easy to realize automated production, and can be matched with a multi-layer flat press to increase the number of pieces produced per unit time without shortening the polymerization time and ensuring a high degree of polymerization. The method can greatly increase production capacity, thereby matching mass production needs.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. The present invention uses modified polyphenylene ether thermoplastic resin to prepare continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminates, maintaining the environmentally friendly characteristics of recyclable and reusable thermoplastic composites. At the same time, an in-situ polymerization method is adopted, and the resin and fiber interface bonding is good, thereby ensuring higher mechanical properties of the composite material and meeting the lightweight requirements in the fields of aviation, automobiles, photovoltaics, and new energy.

[0026] 2. The mixed resin sheet used in the present invention is used as a raw material before the polymerization reaction. It is easy to operate and has uniform thickness. It is easy to penetrate and infiltrate the fiber fabric under heating and pressurization conditions, thereby achieving a high fiber volume content of more than 50% to achieve higher mechanical properties. It is suitable for product application needs with higher mechanical requirements. In addition, the mixed resin sheet is insensitive to moisture, and does not require equipment modification, special customization or special fiber treatment.

[0027] 3. The mixed resin is in a clay-like state and can be made into uniformly thick sheets, which are easy to operate. On the one hand, it is highly compatible with automated production. On the other hand, the sheets are highly compatible with multi-layer flat presses. Under the condition of maintaining full polymerization, the number of products produced per unit time can be increased or decreased by using multi-layer open pressing, thereby shortening the average production time of a single piece, and achieving the effect of improving production efficiency and product stability to match large-scale mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Schematic diagram of the structure of the six-layer opening press used in the embodiment. DETAILED DESCRIPTION

[0029] In order to more fully understand and demonstrate the technical solutions, purposes and advantages of the present invention, the technical effects produced by the present invention are further described in detail and completely in conjunction with the accompanying drawings and specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all. It should be pointed out that for ordinary technicians in this field, other embodiments obtained without departing from the concept of the present invention all belong to the protection scope of the present invention.

[0030] The continuous automated preparation method of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate in the following embodiment comprises the following steps:

[0031] Step 1: Place the cut continuous fiber fabric on the set position above the lower steel plate. The upper surface of the lower steel plate is coated with a release agent (for low-cost products without high surface requirements) or a separation film (for products with higher surface requirements). This step can use a positioning auxiliary device to ensure the accurate placement of the fabric; automatic operation can be selected to place the lower steel plate on an operating table with a conveyor belt, and automatically grab and place it.

[0032] Step 2: Use an automated mixing device to mix the materials into a paste-like state, and then alternately coat them with the continuous fiber fabric through an online glue coating system to obtain a mixed resin sheet. The weight of the sheet is calculated in advance based on the actual needs of the product. This step can be automated, and the lower steel plate carrying the continuous fiber fabric is transported to the sheet laying robot operation area via a conveyor belt, and the robot lays the mixed resin sheet. For thicker products or products with more layers, repeat the above steps to make the mixed resin sheet more evenly distributed between different layers of continuous fiber fabric to improve the product effect.

[0033] Step 3: Cover the upper steel plate on the continuous fiber fabric with the final laid material pieces and align it with the lower steel plate below. Coat the lower surface of the upper steel plate with a release agent or place an isolation film in advance. This step can be automated. The lower steel plate carrying the laid continuous fiber fabric and the material pieces is transported to the upper steel plate storage area via a conveyor belt, and the upper steel plate is automatically grabbed and placed.

[0034] Step 4: Move the combination of the lower steel plate, continuous fiber fabric, mixed resin sheet and upper steel plate into a flat plate press with a preheating temperature of 140-210°C. This step can be automated, and the combination of the lower steel plate, fabric, mixed resin sheet and upper steel plate is transported to the flat plate press via a conveyor belt. Since the polymerization time of the mixed resin material needs to be at least 30 minutes or more, and the production time of a single piece needs to be shortened for mass production applications, but at the same time, the polymerization time should not be reduced to ensure a high degree of polymerization, and a multi-layer flat plate press is used for pressing. For example, a 6-layer open flat plate press ( Figure 1), repeat the above operation for 6 times until all the openings of the multi-layer flat press are filled. In the cycle operation of the integrated automated production line, the theoretically shortest production time of a single piece after average production is 5 minutes. If more layers of openings are added, the average production time of a single piece can be further shortened to achieve higher production efficiency.

[0035] Step 5: After all the combinations of lower steel plates, continuous fiber fabrics, mixed resin sheets, and upper steel plates enter the preheated flat press, the outer door of the press is closed and the mold is pressed. The pressing time is 0.5 to 3 hours (depending on the product performance requirements and production efficiency), and the pressing pressure is 0.5 to 20 MPa. The process can be assisted by vacuuming to improve product quality. The continuous fiber fabric and the mixed resin sheet are pressed and polymerized at high temperature in this step to form a product. After the pressing is completed, the pressure can be maintained and the temperature can be lowered to below 130°C, and then the vacuum can be removed and the door can be opened to eject the mold. For mass production applications, the multi-layer flat press should be kept at a constant temperature at a preheating temperature of 140 to 210°C. After the pressing is completed, the vacuum can be directly removed and the door can be opened to eject the mold, and the combination of the lower steel plate, product, and upper steel plate of each layer in the multi-layer flat press is transferred to a separate multi-layer cold press and cold pressed together to below 80°C. The number of opening layers of the multi-layer cold press is consistent with the number of multi-layer flat presses.

[0036] Step 6: After the pressing is completed, the combination of the lower steel plate, the product, and the upper steel plate is transferred to the operating table, the upper steel plate is removed, and then the product is taken out. This step can be operated automatically, and the combination of the lower steel plate, the product, and the upper steel plate is transported to the upper steel plate storage area by a conveyor belt, and the upper steel plate is automatically unloaded and re-placed for storage, and then the product is automatically unloaded and transferred for storage, and finally the lower steel plate is transported back to the starting position of the lower steel plate in step 1 by a conveyor belt to wait for the next round of automatic cycle operation.

[0037] Example 1

[0038] The present embodiment provides a continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, which is composed of a continuous fiber fabric as a reinforcement and a modified polyphenylene ether thermoplastic resin as a matrix, wherein the modified polyphenylene ether thermoplastic resin is polymerized from a mixed resin material, including: 60 parts by weight of polyphenylene ether, 10 parts by weight of vinyl modified polyphenylene ether, 30 parts by weight of styrene, 2 parts by weight of an initiator, 3 parts by weight of a silane coupling agent, 7 parts by weight of a flame retardant, 0.5 parts by weight of an antioxidant, 0.7 parts by weight of a heat stabilizer, 0.3 parts by weight of a light stabilizer, and 0.2 parts by weight of an ultraviolet light absorber.

[0039] Among them, the initiator is BPO; the silane coupling agent is KH-570; the flame retardant is aluminum hypophosphite; the antioxidant is 3,5-di-tert-butyl-hydroxyphenylpropionate octadecyl ester; the heat stabilizer is triphenyl phosphite; the light stabilizer is 2-(2-hydroxy-5-methylphenyl)benzotriazole; and the ultraviolet light absorber is zinc oxide.

[0040] The preparation steps are as follows: the above materials are mixed by an automated mixing device until they are in a clay state, and then alternately coated with a continuous fiber fabric through an online glue coating system to obtain a mixed resin sheet, wherein the continuous fiber fabric is made of glass fiber and the fabric form is a warp knitted axial fabric; the structural thickness of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate is 5 mm. Then, high-temperature hot pressing is performed at a temperature of 210°C, a pressure of 15MPa, and a hot pressing time of 2h. In-situ polymerization is performed at high temperature, and the continuous fiber fabric is infiltrated and infiltrated under the action of pressure, and a composite material is formed after the polymerization is completed. Specifically, it can also be prepared by the continuous automated preparation method of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate as above.

[0041] Example 2

[0042] The present embodiment provides a continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, which is composed of a continuous fiber fabric as a reinforcement and a modified polyphenylene ether thermoplastic resin as a matrix, wherein the modified polyphenylene ether thermoplastic resin is polymerized from a mixed resin material and includes, by weight: 60 parts by weight of polyphenylene ether, 5 parts by weight of vinyl modified polyphenylene ether, 30 parts by weight of styrene, 2 parts by weight of initiator, 3 parts by weight of silane coupling agent, 7 parts by weight of flame retardant, 0.5 parts by weight of antioxidant, 0.7 parts by weight of heat stabilizer, 0.3 parts by weight of light stabilizer, and 0.2 parts by weight of ultraviolet light absorber.

[0043] Among them, the initiator is BPO; the silane coupling agent is KH-570; the flame retardant is aluminum hypophosphite; the antioxidant is 3,5-di-tert-butyl-hydroxyphenylpropionate octadecyl ester; the heat stabilizer is triphenyl phosphite; the light stabilizer is 2-(2-hydroxy-5-methylphenyl)benzotriazole; and the ultraviolet light absorber is zinc oxide.

[0044] The preparation steps are as follows: the above materials are mixed by an automated mixing device until they are in a clay state, and then alternately coated with a continuous fiber fabric through an online glue coating system to obtain a mixed resin sheet, wherein the continuous fiber fabric is made of glass fiber and the fabric form is a warp knitted axial fabric; the structural thickness of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate is 5 mm. Then, high-temperature hot pressing is performed at a temperature of 210°C, a pressure of 15MPa, and a hot pressing time of 2h. In-situ polymerization is performed at high temperature, and the continuous fiber fabric is infiltrated and infiltrated under the action of pressure, and a composite material is formed after the polymerization is completed. Specifically, it can also be prepared by the continuous automated preparation method of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate as above.

[0045] Example 3

[0046] The present embodiment provides a continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, which is composed of a continuous fiber fabric as a reinforcement and a modified polyphenylene ether thermoplastic resin as a matrix, wherein the modified polyphenylene ether thermoplastic resin is polymerized from a mixed resin material and includes, by weight: 60 parts by weight of polyphenylene ether, 20 parts by weight of vinyl modified polyphenylene ether, 30 parts by weight of styrene, 2 parts by weight of an initiator, 3 parts by weight of a silane coupling agent, 7 parts by weight of a flame retardant, 0.5 parts by weight of an antioxidant, 0.7 parts by weight of a heat stabilizer, 0.3 parts by weight of a light stabilizer, and 0.2 parts by weight of an ultraviolet light absorber.

[0047] Among them, the initiator is BPO; the silane coupling agent is KH-570; the flame retardant is aluminum hypophosphite; the antioxidant is 3,5-di-tert-butyl-hydroxyphenylpropionate octadecyl ester; the heat stabilizer is triphenyl phosphite; the light stabilizer is 2-(2-hydroxy-5-methylphenyl)benzotriazole; and the ultraviolet light absorber is zinc oxide.

[0048] The preparation steps are as follows: the above materials are mixed by an automated mixing device until they are in a clay state, and then alternately coated with a continuous fiber fabric through an online glue coating system to obtain a mixed resin sheet, wherein the continuous fiber fabric is made of glass fiber and the fabric form is a warp knitted axial fabric; the structural thickness of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate is 5 mm. Then, high-temperature hot pressing is performed at a temperature of 210°C, a pressure of 15MPa, and a hot pressing time of 2h. In-situ polymerization is performed at high temperature, and the continuous fiber fabric is infiltrated and infiltrated under the action of pressure, and a composite material is formed after the polymerization is completed. Specifically, it can also be prepared by the continuous automated preparation method of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate as above.

[0049] Example 4

[0050] The present embodiment provides a continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, which is composed of a continuous fiber fabric as a reinforcement and a modified polyphenylene ether thermoplastic resin as a matrix, wherein the modified polyphenylene ether thermoplastic resin is polymerized from a mixed resin material and includes, by weight: 60 parts by weight of polyphenylene ether, 10 parts by weight of vinyl modified polyphenylene ether, 30 parts by weight of styrene, 2 parts by weight of initiator, 3 parts by weight of silane coupling agent, 7 parts by weight of flame retardant, 0.5 parts by weight of antioxidant, 0.7 parts by weight of heat stabilizer, 0.3 parts by weight of light stabilizer, and 0.2 parts by weight of ultraviolet light absorber.

[0051] Among them, the initiator is BPO; the silane coupling agent is KH-570; the flame retardant is aluminum hypophosphite; the antioxidant is 3,5-di-tert-butyl-hydroxyphenylpropionate octadecyl ester; the heat stabilizer is triphenyl phosphite; the light stabilizer is 2-(2-hydroxy-5-methylphenyl)benzotriazole; and the ultraviolet light absorber is zinc oxide.

[0052] The preparation steps are as follows: the above materials are mixed by an automated mixing device until they are in a clay state, and then alternately coated with a continuous fiber fabric through an online glue coating system to obtain a mixed resin sheet, wherein the continuous fiber fabric is made of glass fiber, the fabric form is a warp knitted axial fabric, and the structural thickness of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate is 5 mm. Then, high-temperature hot pressing is performed at a temperature of 160°C, a pressure of 15MPa, and a hot pressing time of 2h. In-situ polymerization is performed at high temperature, and the continuous fiber fabric is infiltrated and infiltrated under the action of pressure, and a composite material is formed after the polymerization is completed. Specifically, it can also be prepared by the continuous automated preparation method of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate as above.

[0053] Example 5

[0054] The present embodiment provides a continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, which is composed of a continuous fiber fabric as a reinforcement and a modified polyphenylene ether thermoplastic resin as a matrix, wherein the modified polyphenylene ether thermoplastic resin is polymerized from a mixed resin material and includes, by weight: 60 parts by weight of polyphenylene ether, 10 parts by weight of vinyl modified polyphenylene ether, 30 parts by weight of styrene, 2 parts by weight of initiator, 3 parts by weight of silane coupling agent, 7 parts by weight of flame retardant, 0.5 parts by weight of antioxidant, 0.7 parts by weight of heat stabilizer, 0.3 parts by weight of light stabilizer, and 0.2 parts by weight of ultraviolet light absorber.

[0055] Among them, the initiator is BPO; the silane coupling agent is KH-570; the flame retardant is aluminum hypophosphite; the antioxidant is 3,5-di-tert-butyl-hydroxyphenylpropionate octadecyl ester; the heat stabilizer is triphenyl phosphite; the light stabilizer is 2-(2-hydroxy-5-methylphenyl)benzotriazole; and the ultraviolet light absorber is zinc oxide.

[0056] The preparation steps are as follows: the above materials are mixed by an automated mixing device until they are in a clay state, and then alternately coated with a continuous fiber fabric through an online glue coating system to obtain a mixed resin sheet, wherein the continuous fiber fabric is made of glass fiber, the fabric form is a warp knitted axial fabric, and the structural thickness of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate is 1 mm. Then, high-temperature hot pressing is performed at a temperature of 210°C, a pressure of 15MPa, and a hot pressing time of 2h. In-situ polymerization is performed at high temperature, and the continuous fiber fabric is infiltrated and infiltrated under the action of pressure, and a composite material is formed after the polymerization is completed. Specifically, it can also be prepared by the continuous automated preparation method of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate as above.

[0057] Comparative Example

[0058] Compared with Example 1, this comparative example does not adopt the in-situ polymerization method to produce continuous fiber modified polyphenylene ether composite materials, and contains 60 weight parts of polyphenylene ether, 40 weight parts of polystyrene, 3 weight parts of silane coupling agent, 7 weight parts of flame retardant, 0.5 weight part of antioxidant, 0.7 weight part of heat stabilizer, 0.3 weight part of light stabilizer, and 0.2 weight part of ultraviolet light absorber.

[0059] Among them, the initiator is BPO; the silane coupling agent is KH-570; the flame retardant is aluminum hypophosphite; the antioxidant is 3,5-di-tert-butyl-hydroxyphenylpropionate octadecyl ester; the heat stabilizer is triphenyl phosphite; the light stabilizer is 2-(2-hydroxy-5-methylphenyl)benzotriazole; and the ultraviolet light absorber is zinc oxide.

[0060] The preparation steps are as follows: the above materials are pressed into sheets by a flat vulcanizer, alternately covered with continuous fiber fabrics, and then hot-pressed at high temperature. The temperature is 210°C, the pressure is 15 MPa, and the hot pressing time is 15 minutes. The structural thickness of the composite laminate is 5 mm.

[0061] Table 1

[0062]

[0063] In summary, the preparation method of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate of the present invention belongs to the in-situ polymerization method, and there is also a reaction with the fiber interface during the polymerization process, and it has high mechanical properties. In addition, the thickness of the mixed resin sheet is uniform, and it is easy to penetrate and infiltrate the continuous fiber fabric under the action of high temperature and pressure, and the composite fiber volume content greater than 50% can be easily achieved. According to the actual product requirements, a higher fiber content is pursued, so that excellent mechanical properties are obtained at the same thickness of the composite laminate.

[0064] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate, characterized in that: The invention comprises, by weight, 30 to 70 parts by weight of continuous fiber fabric as a reinforcement and 30 to 70 parts by weight of modified polyphenylene ether thermoplastic resin as a matrix; The modified polyphenylene ether thermoplastic resin is polymerized from a mixed resin material, and includes, by weight: 30-70 parts by weight of polyphenylene ether, 30-70 parts by weight of styrene, 5-20 parts by weight of vinyl-modified polyphenylene ether, 0.5-2 parts by weight of initiator, 1-3 parts by weight of silane coupling agent, 3-16 parts by weight of flame retardant, 0.2-0.6 parts by weight of antioxidant, 0.3-1 parts by weight of heat stabilizer, 0.2-0.4 parts by weight of light stabilizer, and 0.05-0.3 parts by weight of ultraviolet light absorber.

2. The continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to claim 1, characterized in that: The structural thickness of the continuous fiber reinforced modified polyphenylene ether thermoplastic composite material laminate is 0.2-5 mm.

3. The continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to claim 1, characterized in that: The material of the continuous fiber fabric is selected from one or more of carbon fiber, glass fiber, and polymer fiber, and the form of the continuous fiber fabric includes woven fabric and / or warp knitted axial fabric.

4. The method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to claim 1, characterized in that: The vinyl modified polyphenylene ether comprises, by weight, 30 to 70 parts by weight of polyphenylene ether, 1 to 3 parts by weight of acrylic monomer and 0.5 to 1 part by weight of catalyst. The preparation method comprises: dissolving polyphenylene ether and acrylic monomer in a solvent and mixing them evenly, passing nitrogen gas for protection, slowly dropping the catalyst, heating and stirring in an oil bath for esterification reaction, the reaction temperature is 60 to 120° C., the reaction time is 2 to 10 hours, and cooling, filtering and removing the solvent after the reaction is completed to obtain the vinyl modified polyphenylene ether.

5. The method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to claim 1, characterized in that: The modified polyphenylene ether thermoplastic resin includes, by weight: 60 parts by weight of polyphenylene ether, 10 parts by weight of vinyl modified polyphenylene ether, 30 parts by weight of styrene, 2 parts by weight of initiator, 3 parts by weight of silane coupling agent, 7 parts by weight of flame retardant, 0.5 parts by weight of antioxidant, 0.7 parts by weight of heat stabilizer, 0.3 parts by weight of light stabilizer and 0.2 parts by weight of ultraviolet light absorber.

6. The method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to any one of claims 1 to 5, characterized in that: The following steps are involved: (i) mixing polyphenylene ether, vinyl modified polyphenylene ether, styrene, initiator, silane coupling agent, flame retardant, antioxidant, heat stabilizer, light stabilizer and ultraviolet light absorber in an automated mixing device until the mixture is in a paste state, and then alternately coating the mixture with continuous fiber fabric in an online glue coating system to obtain a mixed resin sheet; (ii) preheating a flat plate press, placing the mixed resin sheet on the continuous fiber fabric for high-temperature hot pressing, wherein the mixed resin sheet undergoes in-situ polymerization under high temperature and pressure conditions and simultaneously penetrates and soaks the continuous fiber fabric, and then cools to room temperature and demolds to obtain the product.

7. The method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to claim 6, characterized in that: The temperature of the high-temperature hot pressing molding is 140-210° C., the pressure is 0.5-20 MPa, and the hot pressing time is 0.5-3 hours.

8. The method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to claim 6, characterized in that: The method for preparing the laminate comprises: (1) A release agent is applied to the upper surface of the lower steel plate of the flat press in advance or an isolation film is placed thereon, and the cut continuous fiber fabric is placed at a predetermined position above the lower steel plate; (2) using an automated mixing device to mix the materials into a paste-like state, and then alternately coating the materials with continuous fiber fabrics through an online glue coating system to obtain a mixed resin sheet; (3) A release agent is applied to the lower surface of the upper steel plate of the flat press in advance or an isolation film is placed thereon, and the upper steel plate is covered on the continuous fiber fabric on which the mixed resin sheet is finally laid, and aligned with the lower steel plate below; (4) The assembled lower steel plate, continuous fiber fabric, mixed resin sheet and upper steel plate are respectively moved into a flat plate press with a preheating temperature of 140-210°C, and the outer door of the press is closed and the mold is closed for high-temperature pressing. The pressing time is 0.5-3h and the pressing pressure is 0.5-20MPa. The process is assisted by vacuuming. After the pressing is completed, the pressure is maintained and the temperature is lowered to below 130°C, the vacuum is released, and the door is opened to remove the mold.

9. The method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to claim 8, characterized in that: In step (4), a multi-layer flat plate press with six openings is used, and the above steps (1)-(4) are repeated until all openings of the multi-layer flat plate press are filled.

10. The method for preparing the continuous fiber reinforced modified polyphenylene ether thermoplastic composite laminate according to claim 8, characterized in that: In step (4), the vacuum is released and the door is opened to release the mold, and the lower steel plate, product and upper steel plate combination of each layer in the multi-layer flat plate press are transferred to a separate multi-layer cold press and cold pressed together to below 80°C. The number of opening layers of the multi-layer cold press is consistent with the number of multi-layer flat plate presses.

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