Continuous fiber reinforced thermoplastic resin-based composite material and preparation method thereof

Abstract

The invention relates to a continuous fiber reinforced thermoplastic resin-based composite material and a preparation method thereof. The composite material comprises a thermoplastic resin and a continuous fiber material. Wherein the weight-average molecular weight Mw of the thermoplastic resin is greater than or equal to 500kg / mol, and the content of the thermoplastic resin in the composite material is 5wt%-90wt%. The preparation method comprises the following steps: (1) adding a photoinitiator G or a thermal initiator R into a monomer D, and uniformly mixing to obtain a polymerization system J; (2) dipping a continuous fiber material in the polymerization system J to obtain a pre-dipping system Y; and (3) initiating in-situ polymerization of the prepreg system Y through ultraviolet radiation or heating to obtain the continuous fiber reinforced thermoplastic resin-based composite material. The composite material is excellent in performance, the preparation method is simple and easy to implement, and the composite material has wide application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials and relates to a continuous fiber reinforced thermoplastic resin-based composite material and a preparation method thereof. Background Art

[0002] In recent years, with the increasingly severe energy and environmental problems, continuous fiber reinforced resin-based composite materials with lightweight and high-strength characteristics have received extensive attention from technicians from all over the world. People are eager to expect that this composite material can be applied on a large scale in the fields of transportation, wind power generation, power equipment, etc., hoping to reduce consumption and emissions through lightweight materials, alleviate energy shortages and control environmental pollution. At present, continuous fiber reinforced resin-based composite materials are divided into two categories: continuous fiber reinforced thermosetting resin-based composite materials and continuous fiber reinforced thermoplastic resin-based composite materials. Since thermosetting resin prepolymers are usually liquid at room temperature, have good fluidity, are easy to impregnate continuous fibers, and the resin performance after cross-linking and curing is stable, the mainstream continuous fiber reinforced resin-based composite materials on the market are continuous fiber reinforced thermosetting resin-based composite materials.

[0003] However, continuous fiber reinforced thermosetting resin-based composite materials have the disadvantages of long processing cycle and high cost, low processing efficiency, difficult repair and recycling, and poor toughness of composite materials. In contrast, continuous fiber reinforced thermoplastic resin-based composite materials have the advantages of short processing cycle, low processing cost, easy recycling and repair. In view of this, continuous fiber reinforced thermoplastic resin-based composite materials have gradually entered people's field of vision. For example, patents CN113150546B, CN117124671A, and CN116674221A respectively report a PBO fiber reinforced thermoplastic resin-based bulletproof composite material, a highly conductive thermoplastic resin-based continuous carbon fiber composite material, and a high-temperature resistant continuous fiber reinforced thermoplastic resin-based composite honeycomb.

[0004] However, there is a technical difficulty in the processing and molding of continuous fiber reinforced thermoplastic resin-based composite materials: thermoplastic resins are generally solid at room temperature and cannot wet continuous fibers. Even after heating and melting, the melt still exhibits high viscosity and poor fluidity, and it is still difficult to effectively wet continuous fibers. In order to overcome this technical difficulty, technicians from various countries have proposed and implemented a variety of methods for compounding thermoplastic resins with continuous fibers: such as solution impregnation, film lamination, powder impregnation, melt impregnation, melt pultrusion, and continuous fiber blending. However, the above methods all have their limitations.

[0005] In order to overcome the limitations of the above methods, a new method for preparing continuous fiber reinforced thermoplastic resin-based composite materials, the in-situ polymerization method, has emerged in the past decade. The in-situ polymerization method uses low-viscosity thermoplastic resin monomers or prepolymers to complete the impregnation and compounding of continuous fibers. It can effectively overcome the technical difficulty that thermoplastic resins are difficult to impregnate continuous fibers, and has the advantages of being solvent-free, simple and easy to implement. So far, many patents have reported this method, but the prior art has the shortcomings of improper preparation of the polymerization system and the lack of precise control of the in-situ polymerization process. The thermoplastic resins currently obtained by the in-situ polymerization method usually do not have high molecular weight (≥500kg / mol) or ultra-high molecular weight (≥1000kg / mol), so the composite material obtained is difficult to be a high-performance composite material. For example, patent CN106995533A prepares a polymerization system with a high photoinitiator dosage (0.1% to 10% of the mass of the resin monomer), which results in a large number of free radicals generated during the polymerization process and a high probability of double radical termination between free radicals, so that the obtained thermoplastic resin usually has a low molecular weight; patent CN117447802A dissolves the polymer corresponding to the resin monomer in a monomer solution to obtain a polymerization system, but the molecular weight of the polymer used is usually low, and a part of low molecular weight polymer exists in the thermoplastic resin obtained by polymerization; patent CN109467884 has a wide range of in-situ polymerization temperature (15°C to 200°C). If in-situ polymerization is carried out at high temperature, the high-speed moving free radicals will cause the probability of chain termination to increase significantly, making it difficult to obtain a high molecular weight thermoplastic resin. Summary of the invention

[0006] The purpose of the present invention is to solve the shortcomings of the existing in-situ polymerization technology and provide a continuous fiber reinforced thermoplastic resin-based composite material and a preparation method thereof.

[0007] The present invention first provides a continuous fiber reinforced thermoplastic resin-based composite material, which comprises a thermoplastic resin and a continuous fiber material; wherein the weight average molecular weight M of the thermoplastic resin is w Generally, it is better to be greater than or equal to 500kg / mol, and more preferably greater than or equal to 1000kg / mol. The present invention has no particular restriction on the content of thermoplastic resin, but considering that too high resin content leads to a sharp weakening of the reinforcement effect of the continuous fibers, and too low resin content leads to insufficient bonding between the continuous fibers, its content is generally 5wt% to 90wt%, more preferably 5wt% to 50wt%, and optimally 20wt% to 50wt%.

[0008] The continuous fiber material in the present invention refers to a fiber that exists in a continuous form in a composite material, usually with a longer length and a smaller diameter, as opposed to short-cut fibers. Considering the production cost of the continuous fiber material, the continuous fiber material is one or more of continuous carbon fiber, glass fiber, polyester fiber, nylon fiber, ultra-high molecular weight polyethylene fiber, aramid fiber, polyarylate fiber and basalt fiber.

[0009] The various compound components in the raw material monomer D of the thermoplastic resin need to be easily available. Therefore, the raw material monomer D of the thermoplastic resin is one or more of methacrylate, acrylate, styrene, acrylonitrile and vinyl acetate.

[0010] By adjusting the refractive index of the thermoplastic resin to be close to the refractive index of the continuous fiber material, the continuous fiber reinforced thermoplastic resin-based composite material of the present invention can have high transparency, and its light transmittance T in the spectral range of 500nm to 800nm ​​is greater than 80%.

[0011] The present invention also provides a method for preparing a continuous fiber reinforced thermoplastic resin-based composite material, comprising the following steps:

[0012] S1: Add photoinitiator G or thermal initiator R to monomer D, mix well and obtain polymerization system J;

[0013] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y;

[0014] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation or heating to obtain a continuous fiber reinforced thermoplastic resin-based composite material.

[0015] The monomer D as described above needs to be a liquid with low viscosity and good fluidity at room temperature so as to better wet the continuous fiber material. In addition, the refractive index of the thermoplastic resin obtained after polymerization of the monomer D can be close to the refractive index of the continuous fiber material. Therefore, in the present invention, the monomer D is one or more of methacrylate, acrylate, styrene, acrylonitrile and vinyl acetate.

[0016] The present invention has no particular restrictions on the type of photoinitiator G, but considering that the polymerization rate of the cleavage-type free radical photoinitiator is faster than that of the hydrogen abstraction-type initiator, the present invention selects a cleavage-type photoinitiator to initiate polymerization. Preferably, the photoinitiator G is one or more of benzoin ethyl ether, α,α-dimethylbenzil ketal, 1-hydroxy-cyclohexyl benzophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0017] The present invention has no particular restrictions on the amount of photoinitiator G added, but considering that too much photoinitiator added results in a large number of free radicals, free radicals are easily terminated by double radicals, and thus the molecular weight of the synthesized thermoplastic resin is low; too little photoinitiator added results in the free radical chain growth rate being much lower than the chain termination rate of oxygen inhibition during polymerization, so that the polymerization rate is extremely slow, or even no polymerization occurs. The amount of photoinitiator G added is generally 50ppm to 500ppm of the weight of the monomer D, more preferably 50ppm to 200ppm of the weight of the monomer D, and most preferably 50ppm to 100ppm of the weight of the monomer D.

[0018] Based on the consideration of polymerization temperature range and initiation efficiency, the present invention selects organic peroxide compounds, azo compounds and persulfate thermal initiators to initiate polymerization. Preferably, the thermal initiator R is one or more of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, tetramethylbutyl peroxyneodecanoate, and diisopropyl peroxydicarbonate.

[0019] The present invention has no particular restriction on the amount of thermal initiator R added, but considering that too much thermal initiator added results in too many free radicals, free radicals are easily terminated by double radicals, and thus the molecular weight of the resulting thermoplastic resin is low; too low a thermal initiator added results in the free radical chain growth rate during the polymerization process being much lower than the chain termination rate of oxygen inhibition, resulting in low polymerization efficiency, or even no polymerization. The amount of thermal initiator R added is generally 50ppm to 500ppm of the weight of the monomer D, more preferably 50ppm to 200ppm of the weight of the monomer D, and most preferably 50ppm to 100ppm of the weight of the monomer D.

[0020] Since the continuous fiber material needs to be easily wetted by the polymer system Y, and its refractive index can be close to the refractive index of the thermoplastic resin, the continuous fiber material is one or more of continuous carbon fiber, glass fiber, polyester fiber, nylon fiber, ultra-high molecular weight polyethylene fiber, aramid fiber, polyarylate fiber and basalt fiber; preferably, the continuous fiber material is one or more of continuous glass fiber, polyester fiber, nylon fiber and ultra-high molecular weight polyethylene fiber.

[0021] The wavelength of the ultraviolet radiation in the present invention is consistent with the wavelength range of the ultraviolet light source. Therefore, the wavelength of the ultraviolet radiation is 270nm to 400nm.

[0022] The present invention has no particular restrictions on the intensity of ultraviolet radiation, but considering that too low light intensity makes the photoinitiator absorb less light energy, so the time (induction period) for the photoinitiator to cleave and generate primary free radicals is longer, and the in-situ polymerization efficiency is low; too high light intensity will cause side reactions such as polymer main chain breakage, so it is difficult for thermoplastic resin to have a high molecular weight. The intensity of ultraviolet radiation is generally 100mW / cm2 ~1500mW / cm 2 More preferably, 100 mW / cm 2 ~500mW / cm 2 , most preferably 200mW / cm 2 ~400mW / cm 2 .

[0023] The present invention has no particular limitation on the time of ultraviolet irradiation, but it is considered that too short an irradiation time leads to incomplete polymerization reaction and low conversion rate of monomer D, and too long an irradiation time leads to a lengthy preparation cycle of the composite material. The time of ultraviolet irradiation is generally preferably 5 min to 180 min, more preferably 5 min to 120 min, and most preferably 10 min to 90 min.

[0024] The present invention has no particular restrictions on the heating temperature, but the polymerization rate and the molecular weight of the thermoplastic resin are related to the heating temperature: a higher reaction temperature makes the free radical movement rate faster, thereby a higher polymerization rate, but the high-speed moving free radicals are easy to terminate with double radicals, and the molecular weight of the obtained thermoplastic resin is low; on the contrary, a lower reaction temperature makes the free radical movement rate slower, and the free radicals are not easy to terminate with double radicals, and a thermoplastic resin with a higher molecular weight can be obtained, but the polymerization rate is low. The heating temperature is generally preferably 60°C to 80°C, and more preferably 65°C to 75°C.

[0025] The present invention has no particular limitation on the holding time of heating, but it is considered that too short a holding time leads to incomplete polymerization reaction and low conversion rate of monomer D, and too long a holding time leads to a lengthy preparation cycle of the composite material. The holding time is generally 30 min to 180 min, more preferably 30 min to 150 min, and most preferably 60 min to 120 min.

[0026] The principle of the present invention is as follows:

[0027] The present invention adopts the strategy of "low initiator addition" to suppress the number of primary free radicals generated by the initiator molecules, so that the free radicals are not easily terminated by double radicals, and the thermoplastic resin in the obtained composite material has a high weight average molecular weight (M w >500kg / mol).

[0028] The in-situ polymerization of the present invention is carried out at room temperature (ultraviolet irradiation) or medium temperature (heating at 60°C to 80°C). The lower polymerization temperature slows down the movement rate of free radicals, and the free radical molecular chain can achieve "localized polymerization" in a specific area, rather than uniformly in the entire polymerization system. This form of "localized polymerization" is conducive to the formation and entanglement of long polymer chains, and the thermoplastic resin in the resulting composite material has a high weight average molecular weight (Mw >500kg / mol), the composite material has excellent performance.

[0029] The present invention adjusts the ratio of each compound in monomer D so that the refractive index of the thermoplastic resin obtained after in-situ polymerization of monomer D can be close to the refractive index of the continuous fiber material, so that the obtained composite material can have high transparency (the transmittance T in the spectral range of 500nm to 800nm ​​is greater than 80%).

[0030] Beneficial effects:

[0031] (1) The present invention adopts the dual strategies of "low initiator addition" and "localized polymerization" to make the thermoplastic resin have a high molecular weight or an ultra-high molecular weight, thereby producing a high-performance composite material;

[0032] (2) The composite material prepared by the present invention can have high transparency, and its light transmittance T in the spectral range of 500nm to 800nm ​​is greater than 80%;

[0033] (3) The preparation method of the present invention is simple and easy to implement, and is very suitable for large-scale production of low-cost continuous fiber reinforced thermoplastic resin-based composite materials. DETAILED DESCRIPTION

[0034] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0035] The monomer components, photoinitiators, thermal initiators and solvents involved in the examples were purchased from Bidex Pharmaceuticals, Sinopharm Group or Aladdin Reagents; the continuous fiber material is a commercially available product.

[0036] Weight average molecular weight M w Test: The prepared continuous fiber reinforced thermoplastic resin-based composite material was immersed in hexafluoroisopropanol to dissolve the thermoplastic resin, and a solution with a concentration of 1 mg / mL was prepared and injected into a gel chromatograph at a column temperature of 40°C (with PMMA with a narrow molecular weight distribution as the standard calibrant) for measurement.

[0037] Calculation of the content of thermoplastic resin in the composite material: First, weigh the prepared continuous fiber reinforced thermoplastic resin-based composite material, and record its mass as W1. Then, soak the composite material in chloroform for 24 hours to fully dissolve the thermoplastic resin in the composite material. Finally, take out the composite material soaked in chloroform, wipe the chloroform on its surface with a test paper, and evaporate the remaining chloroform at room temperature until its mass is constant, and record its mass as W2. The content of thermoplastic resin in the composite material (W R ) can be calculated using the following formula:

[0038]

[0039] Tensile strength test of composite materials: refer to ASTM D3039 / D3039M 08 standard test method for mechanical properties of continuous fiber reinforced resin matrix composite materials, and use a universal material testing machine to test the tensile strength of composite materials. Set the tensile speed to 1mm / min, and take the average value of the sample after 8-10 parallel tests as the final result.

[0040] Example 1

[0041] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0042] S1: Add photoinitiator G to monomer D, mix well to obtain polymerization system J; wherein monomer D is composed of methyl methacrylate and butyl acrylate, the mass ratio of the two is 7:3, and photoinitiator G is benzoin ethyl ether, the addition amount of which is 500ppm of the mass of monomer D;

[0043] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous carbon fiber;

[0044] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation to obtain a continuous fiber reinforced thermoplastic resin matrix composite material; wherein the ultraviolet irradiation wavelength is 270nm and the irradiation intensity is 1500mW / cm 2 The irradiation time is 180 minutes. The content of the thermoplastic resin in the composite material is 90wt%.

[0045] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 150 MPa.

[0046] Example 2

[0047] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0048] S1: Add photoinitiator G to monomer D, mix well to obtain polymerization system J; wherein monomer D is composed of styrene and methyl acrylate, the mass ratio of the two is 3:2, and photoinitiator G is α,α-dimethylbenzil ketal, and the addition amount thereof is 200ppm of the mass of monomer D;

[0049] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous glass fiber;

[0050] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation to obtain a continuous fiber reinforced thermoplastic resin matrix composite material; wherein the ultraviolet irradiation wavelength is 300nm and the irradiation intensity is 500mW / cm 2 The irradiation time is 120 minutes. The content of the thermoplastic resin in the composite material is 50wt%.

[0051] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 680 MPa.

[0052] Comparative Example 1

[0053] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material, the specific steps are basically the same as those in Example 2, except that the irradiation intensity is 50 mW / cm 2 The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 410 MPa. This is because the light intensity is too low, so the photoinitiator absorbs less light energy, so the time (induction period) for the photoinitiator to crack and generate primary free radicals is longer, and the conversion rate of the resin monomer per unit time is lower, so the molecular weight of the thermoplastic resin is lower, and the tensile strength of the composite material is also lower.

[0054] Example 3

[0055] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0056] S1: adding photoinitiator G to monomer D, and mixing them evenly to obtain polymerization system J; wherein monomer D is acrylonitrile, and photoinitiator G is 1-hydroxy-cyclohexyl benzophenone, and the addition amount thereof is 100 ppm based on the mass of monomer D;

[0057] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous polyester fiber;

[0058] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation to obtain a continuous fiber reinforced thermoplastic resin matrix composite material; wherein the ultraviolet irradiation wavelength is 365nm and the irradiation intensity is 400mW / cm 2 The irradiation time is 90 minutes. The content of the thermoplastic resin in the composite material is 20wt%.

[0059] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 900 MPa.

[0060] Example 4

[0061] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0062] S1: Add photoinitiator G to monomer D, mix well to obtain polymerization system J; wherein monomer D is vinyl acetate, and photoinitiator G is 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, and the addition amount thereof is 50 ppm based on the mass of monomer D;

[0063] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is continuous nylon fiber;

[0064] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation to obtain a continuous fiber reinforced thermoplastic resin matrix composite material; wherein the ultraviolet irradiation wavelength is 390nm and the irradiation intensity is 200mW / cm 2 The irradiation time is 60 minutes. The content of the thermoplastic resin in the composite material is 20wt%.

[0065] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 1020 MPa.

[0066] Example 5

[0067] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0068] S1: adding photoinitiator G to monomer D, and mixing them evenly to obtain polymerization system J; wherein monomer D is styrene, and photoinitiator G is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the addition amount thereof is 150ppm based on the mass of monomer D;

[0069] S2: impregnating the continuous fiber material into the polymerization system J to obtain the prepreg system Y; wherein the continuous fiber material is a continuous ultra-high molecular weight polyethylene fiber;

[0070] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation to obtain a continuous fiber reinforced thermoplastic resin matrix composite material; wherein the ultraviolet irradiation wavelength is 400nm and the irradiation intensity is 100mW / cm 2 The irradiation time is 5 minutes. The content of the thermoplastic resin in the composite material is 60wt%.

[0071] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 500 MPa.

[0072] Comparative Example 2

[0073] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material, the specific steps are basically the same as those in Example 5, except that the amount of photoinitiator G added is 800 ppm, and the weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin-based composite material is w The molecular weight of the synthesized thermoplastic resin is low, and the tensile strength of the composite material is also low.

[0074] Example 6

[0075] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0076] S1: Add photoinitiator G to monomer D, mix well to obtain polymerization system J; wherein monomer D is methyl methacrylate, photoinitiator G is composed of 1-hydroxy-cyclohexyl benzophenone and benzoin ethyl ether, the mass ratio of the two is 4:1, and the addition amount is 300ppm of the mass of monomer D;

[0077] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous aramid fiber;

[0078] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation to obtain a continuous fiber reinforced thermoplastic resin matrix composite material; wherein the ultraviolet irradiation wavelength is 395nm and the irradiation intensity is 1200mW / cm 2 The irradiation time is 80 minutes. The content of the thermoplastic resin in the composite material is 30wt%.

[0079] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 780 MPa.

[0080] Example 7

[0081] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0082] S1: Add photoinitiator G to monomer D, mix well to obtain polymerization system J; wherein monomer D is composed of methyl methacrylate, styrene and butyl acrylate, the mass ratio of the three is 1:1:1, and photoinitiator G is composed of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 1-hydroxy-cyclohexyl benzophenone, the mass ratio of the two is 1:1, and the addition amount is 100ppm of the mass of monomer D;

[0083] S2: impregnating a continuous fiber material into a polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous polyarylate fiber;

[0084] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation to obtain a continuous fiber reinforced thermoplastic resin matrix composite material; wherein the ultraviolet irradiation wavelength is 320nm and the irradiation intensity is 750mW / cm 2 The irradiation time is 100 minutes. The content of the thermoplastic resin in the composite material is 35wt%.

[0085] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 1200 MPa.

[0086] Example 8

[0087] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0088] S1: Add photoinitiator G to monomer D, mix well to obtain polymerization system J; wherein monomer D is composed of vinyl acetate and butyl acrylate, the mass ratio of the two is 1:1, and photoinitiator G is composed of α,α-dimethylbenzil ketal, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 1-hydroxy-cyclohexyl benzophenone, the mass ratio of the three is 2:1:1, and the addition amount is 75ppm of the mass of monomer D;

[0089] S2: impregnating the continuous fiber material into the polymerization system J to obtain the prepreg system Y; wherein the continuous fiber material is continuous basalt fiber;

[0090] S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation to obtain a continuous fiber reinforced thermoplastic resin matrix composite material; wherein the ultraviolet irradiation wavelength is 365nm and the irradiation intensity is 500mW / cm 2 The irradiation time is 150 minutes. The content of the thermoplastic resin in the composite material is 25wt%.

[0091] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 1360 MPa.

[0092] Comparative Example 3

[0093] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material, wherein the specific steps are basically the same as those of Example 8, except that the irradiation time is 3 min; the weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin-based composite material is w The molecular weight of the composite material is 400 kg / mol, and the tensile strength of the composite material is 625 MPa. This is because the short irradiation time leads to insufficient polymerization reaction, low conversion rate of the resin monomer, low molecular weight, and low tensile strength of the composite material.

[0094] Example 9

[0095] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0096] S1: Add thermal initiator R to monomer D, mix well and obtain polymerization system J; wherein monomer D is composed of acrylonitrile and tert-butyl acrylate, the mass ratio of the two is 4:1, and thermal initiator R is azobisisobutyronitrile, the addition amount of which is 500ppm of the mass of monomer D;

[0097] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous carbon fiber;

[0098] S3: Initiate in-situ polymerization of the prepreg system Y by heating to obtain a continuous fiber reinforced thermoplastic resin matrix composite material, wherein the heating temperature is 60° C. and the holding time is 180 min. The content of the thermoplastic resin in the composite material is 40 wt%.

[0099] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 810 MPa.

[0100] Comparative Example 4

[0101] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material, wherein the specific steps are basically the same as those of Example 9, except that the heating temperature is 90° C.; the weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin-based composite material is w The molecular weight of the thermoplastic resin is 360 kg / mol, and the tensile strength of the composite material is 600 MPa. This is because the higher reaction temperature makes the free radical movement faster, but the high-speed free radicals are prone to double radical termination, resulting in a lower molecular weight of the thermoplastic resin, and thus a lower tensile strength of the composite material.

[0102] Example 10

[0103] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0104] S1: Add thermal initiator R to monomer D, mix well to obtain polymerization system J; wherein monomer D is methyl methacrylate, thermal initiator R is benzoyl peroxide, and the addition amount thereof is 200 ppm based on the mass of monomer D;

[0105] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous glass fiber;

[0106] S3: Initiate in-situ polymerization of the prepreg system Y by heating to obtain a continuous fiber reinforced thermoplastic resin matrix composite material, wherein the heating temperature is 65° C. and the holding time is 150 min. The content of the thermoplastic resin in the composite material is 30 wt%.

[0107] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 880 MPa.

[0108] Comparative Example 5

[0109] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material, wherein the specific steps are basically the same as those of Example 10, except that the content of the thermoplastic resin in the composite material is 95wt%; the weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin-based composite material is w The tensile strength of the composite material is 120 MPa, which is because the excessively high resin content leads to a sharp weakening of the reinforcement effect of the continuous fibers.

[0110] Embodiment 11

[0111] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0112] S1: Add thermal initiator R to monomer D, mix well to obtain polymerization system J; wherein monomer D is styrene, and thermal initiator R is potassium persulfate, and the addition amount thereof is 100 ppm of the mass of monomer D;

[0113] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous polyester fiber;

[0114] S3: Initiate in-situ polymerization of the prepreg system Y by heating to obtain a continuous fiber reinforced thermoplastic resin matrix composite material, wherein the heating temperature is 70° C. and the holding time is 120 min. The content of the thermoplastic resin in the composite material is 50 wt%.

[0115] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 650 MPa.

[0116] Example 12

[0117] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0118] S1: Add thermal initiator R to monomer D, mix well to obtain polymerization system J; wherein monomer D is acrylonitrile, and thermal initiator R is tetramethylbutyl peroxyneodecanoate, and the addition amount thereof is 50 ppm based on the mass of monomer D;

[0119] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is continuous nylon fiber;

[0120] S3: Initiate in-situ polymerization of the prepreg system Y by heating to obtain a continuous fiber reinforced thermoplastic resin matrix composite material, wherein the heating temperature is 75° C. and the holding time is 100 min. The content of the thermoplastic resin in the composite material is 20 wt%.

[0121] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 950 MPa.

[0122] Embodiment 13

[0123] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0124] S1: Add thermal initiator R to monomer D, mix well to obtain polymerization system J; wherein monomer D is vinyl acetate, and thermal initiator R is diisopropyl peroxydicarbonate, and the addition amount thereof is 150ppm based on the mass of monomer D;

[0125] S2: impregnating the continuous fiber material into the polymerization system J to obtain the prepreg system Y; wherein the continuous fiber material is a continuous ultra-high molecular weight polyethylene fiber;

[0126] S3: Initiate in-situ polymerization of the prepreg system Y by heating to obtain a continuous fiber reinforced thermoplastic resin matrix composite material, wherein the heating temperature is 80° C. and the holding time is 60 min. The content of the thermoplastic resin in the composite material is 12 wt%.

[0127] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 1000 MPa.

[0128] Embodiment 14

[0129] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0130] S1: Add thermal initiator R to monomer D, mix well to obtain polymerization system J; wherein monomer D is composed of methyl methacrylate, styrene and butyl acrylate, the mass ratio of the three is 3:2:1, and thermal initiator R is composed of azobisisobutyronitrile and benzoyl peroxide, the mass ratio of the two is 1:1, and the addition amount is 300ppm of the mass of monomer D;

[0131] S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous aramid fiber;

[0132] S3: Initiate in-situ polymerization of the prepreg system Y by heating to obtain a continuous fiber reinforced thermoplastic resin matrix composite material, wherein the heating temperature is 70° C. and the holding time is 130 min. The content of the thermoplastic resin in the composite material is 40 wt%.

[0133] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 710 MPa.

[0134] Embodiment 15

[0135] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0136] S1: Add thermal initiator R to monomer D, mix well to obtain polymerization system J; wherein monomer D is composed of methyl methacrylate and methyl acrylate, the mass ratio of the two is 5:4, and thermal initiator R is composed of azobisisobutyronitrile and potassium persulfate, the mass ratio of the two is 1:1, and the addition amount is 100ppm of the mass of monomer D;

[0137] S2: impregnating a continuous fiber material into a polymerization system J to obtain a prepreg system Y; wherein the continuous fiber material is a continuous polyarylate fiber;

[0138] S3: Initiate in-situ polymerization of the prepreg system Y by heating to obtain a continuous fiber reinforced thermoplastic resin matrix composite material, wherein the heating temperature is 65° C. and the holding time is 150 min. The content of the thermoplastic resin in the composite material is 15 wt%.

[0139] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 1340 MPa.

[0140] Example 16

[0141] A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material comprises the following steps:

[0142] S1: Add thermal initiator R to monomer D, mix well to obtain polymerization system J; wherein monomer D is composed of styrene and methyl acrylate, the mass ratio of the two is 7:3, and thermal initiator R is azobisisobutyronitrile, the addition amount of which is 75ppm of the mass of monomer D;

[0143] S2: impregnating the continuous fiber material into the polymerization system J to obtain the prepreg system Y; wherein the continuous fiber material is continuous basalt fiber;

[0144] S3: Initiate in-situ polymerization of the prepreg system Y by heating to obtain a continuous fiber reinforced thermoplastic resin matrix composite material, wherein the heating temperature is 60° C. and the holding time is 180 min. The content of the thermoplastic resin in the composite material is 15 wt%.

[0145] The weight average molecular weight M of the thermoplastic resin in the obtained continuous fiber reinforced thermoplastic resin matrix composite material is w The tensile strength of the composite material is 1650 MPa.

Claims

1. A continuous fiber reinforced thermoplastic resin-based composite material, characterized in that: It comprises a thermoplastic resin and a continuous fiber material; wherein the weight average molecular weight M of the thermoplastic resin is w ≥500kg / mol, and its content in the composite material is 5wt% to 90wt%.

2. The continuous fiber reinforced thermoplastic resin-based composite material according to claim 1, characterized in that: The weight average molecular weight M of the thermoplastic resin w ≥1000kg / mol, and its content in the composite material is 5wt% to 50wt%; the continuous fiber material is one or more of continuous carbon fiber, glass fiber, polyester fiber, nylon fiber, ultra-high molecular weight polyethylene fiber, aramid fiber, polyarylate fiber or basalt fiber.

3. The continuous fiber reinforced thermoplastic resin-based composite material according to claim 1, characterized in that: The raw material monomer D of the thermoplastic resin is one or more of methacrylate, acrylate, styrene, acrylonitrile or vinyl acetate.

4. The continuous fiber reinforced thermoplastic resin-based composite material according to claim 1, characterized in that: The composite material has a light transmittance T>80% in the spectral range of 500nm to 800nm.

5. A method for preparing a continuous fiber reinforced thermoplastic resin-based composite material according to any one of claims 1 to 4, characterized in that The following steps are involved: S1: Add photoinitiator G or thermal initiator R to monomer D, mix well and obtain polymerization system J; S2: impregnating the continuous fiber material into the polymerization system J to obtain a prepreg system Y; S3: Initiate in-situ polymerization of the prepreg system Y by ultraviolet irradiation or heating to obtain a thermoplastic resin-based composite material.

6. The method for preparing a continuous fiber reinforced thermoplastic resin-based composite material according to claim 5, characterized in that: The monomer D is one or more of methacrylate, acrylate, styrene, acrylonitrile or vinyl acetate.

7. The method for preparing a continuous fiber reinforced thermoplastic resin-based composite material according to claim 5, characterized in that: The photoinitiator G is one or more of benzoin ethyl ether, α,α-dimethylbenzil ketal, 1-hydroxy-cyclohexyl benzophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and its added amount is 50ppm to 500ppm of the mass of the monomer D; the thermal initiator R is one or more of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, tetramethylbutyl peroxyneodecanoate, or diisopropyl peroxydicarbonate, and its added amount is 50ppm to 500ppm of the mass of the monomer D.

8. The method for preparing a continuous fiber reinforced thermoplastic resin-based composite material according to claim 5, characterized in that: The continuous fiber material is one or more of continuous carbon fiber, glass fiber, polyester fiber, nylon fiber, ultra-high molecular weight polyethylene fiber, aramid fiber, polyarylate fiber or basalt fiber.

9. The method for preparing a continuous fiber reinforced thermoplastic resin-based composite material according to claim 5, characterized in that The wavelength of the ultraviolet radiation in step S3 is 270nm-400nm and the intensity is 100mW / cm 2 ~1500mW / cm 2 , time is 5min~180min.

10. The method for preparing a continuous fiber reinforced thermoplastic resin-based composite material according to claim 5, characterized in that The heating temperature in step S3 is 60° C. to 80° C., and the holding time is 30 min to 180 min.

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