Thermoplastic resin-based bulletproof plate and preparation method thereof

Abstract

The invention relates to a thermoplastic resin-based bulletproof plate and a preparation method thereof. The bulletproof plate comprises a thermoplastic resin TP and a continuous fiber material. Wherein the weight-average molecular weight Mw of the thermoplastic resin TP is larger than or equal to 1000 kg / mol, the Barcol hardness of the thermoplastic resin TP is larger than or equal to 60 HBa, and the content of the thermoplastic resin TP in the bulletproof plate ranges from 5 wt% to 25 wt%. The preparation method comprises the following steps: (1) adding or not adding rubber R into a monomer M, adding a photoinitiator PI, and uniformly mixing to obtain a polymerization system P; the monomer M is methacrylate, isobornyl acrylate or a mixture of the methacrylate and the isobornyl acrylate; the addition amount of the photoinitiator PI is 50 ppm to 150 ppm of the mass of the monomer M; (2) fully impregnating a continuous fiber material in the polymerization system P, and then laminating and extruding to obtain a pre-impregnated system Y; (3) initiating in-situ polymerization of the pre-impregnation system Y through temperature-controlled pulse ultraviolet radiation to obtain the thermoplastic resin-based bulletproof plate, the temperature-controlled pulse ultraviolet radiation comprises the following steps: after ultraviolet radiation is started, stopping radiation when the temperature of the pre-impregnation system Y is raised to T, and then starting radiation again when the temperature is reduced to T-5 until the temperature is raised to T; repeating until the M conversion rate alpha is greater than or equal to 80%; wherein 45 DEG C < = T < = 75 DEG C. The novel bulletproof plate of the continuous fiber reinforced ultra-high molecular weight resin is prepared, the preparation conditions are mild, the remarkable lightweight effect can be achieved under the condition that the same protection grade is achieved, and the bulletproof plate has important economic value.

Description

Technical Field

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

[0002] Fiber bulletproof panels are lightweight ballistic protective equipment made of high-performance synthetic fibers as the main material. The fibers are impregnated with resin and then several prepregs are laminated and pressed together. They are widely used in military, police and civilian protection fields. Compared with traditional metal or ceramic bulletproof panels, fiber bulletproof panels have the advantages of light weight, high specific strength, and good flexibility. They have become one of the core materials of modern bulletproof equipment. Currently, fiber bulletproof panels mainly use soft adhesives (such as thermoplastic polyurethane elastomers) for interlayer bonding. Although soft adhesives can dissipate the kinetic energy of the bullet through viscoelastic deformation, their low modulus delays the transmission of the bullet impact stress to the fiber. This results in a decrease in the proportion of energy dissipation dominated by fiber tensile fracture, while an increase in the proportion of energy dissipation in the adhesive layer. This imbalance in the energy dissipation mechanism limits the improvement of the protective performance of the bulletproof panel. To improve the protective performance of the bulletproof panel, the conventional solution is to increase its thickness, but this will lead to an increase in its surface density, which conflicts with the demand for lightweight development.

[0003] In order to overcome the inherent defects of soft adhesives, the use of high-modulus hard thermoplastic resins with a rigid molecular structure as a substitute adhesive is a potential effective solution. With its high strength and rigidity, hard thermoplastic resins can quickly transfer the impact stress of bullets to the fiber reinforcement phase, prompting high-performance fibers to undergo rapid tensile fracture, thereby significantly improving the fiber-dominated energy absorption efficiency and giving full play to the protective capabilities of the main body (fiber) of the bulletproof plate. However, conventional hard thermoplastic resins usually do not have ultra-high molecular weight, and their brittleness is relatively high. They are prone to cracking under the impact of projectiles, resulting in interruption of the stress transfer path, thereby weakening the protective performance of the fiber bulletproof plate. To solve this problem, ultra-high molecular weight hard thermoplastic resins can be used as bulletproof plate adhesives. Its ultra-long molecular chain structure not only gives the resin the characteristics of high strength and high modulus, but also reduces its brittleness, ultimately optimizing the bulletproof performance of the fiber bulletproof plate.

[0004] However, the extremely high melt viscosity of ultra-high molecular weight thermoplastic resins with rigid main chains makes them difficult to form into ballistic armor panels using traditional hot melt compression molding methods. To address this issue, in-situ polymerization technology offers a potential innovative solution. This technology involves fully impregnating fibers with low-viscosity thermoplastic resin monomers or prepolymers, followed by in-situ polymer synthesis around the fibers under relatively mild conditions. This approach promises to allow the ultra-high molecular weight thermoplastic resin to be composited with the fibers, enabling the successful production of fiber-based ballistic armor panels with superior protective properties. To date, several patents have reported on this technology. For example, patent CN111875729B describes the formation of carbon fiber composites by in-situ polymerization of methacrylic resin on the reinforcement surface; patent CN116589639A reports on an in-situ injection pultrusion method for fiber-reinforced composites; patent CN117069974B utilizes room temperature in-situ infusion transfer molding to produce fiber-reinforced composites; and patent CN117447802A demonstrates an in-situ polymerization method for thermoplastic methyl acrylate resin-based composite reinforcements. However, the existing technology suffers from improper preparation of the polymerization system and a lack of precise control of the in-situ polymerization process. Currently, the thermoplastic resins obtained by in-situ polymerization usually do not have an ultra-high molecular weight (≥1000kg / mol), and bulletproof panels reinforced with continuous fiber-reinforced ultra-high molecular weight resins are rarely reported. Summary of the Invention

[0005] The purpose of the present invention is to solve the problem that the protective performance of existing fiber bulletproof plates is limited due to the inherent defects of soft adhesives, and to provide a new thermoplastic resin-based bulletproof plate and a preparation method thereof.

[0006] The present invention first provides a thermoplastic resin-based bulletproof plate, which comprises a thermoplastic resin TP and a continuous fiber material; wherein the weight average molecular weight M of the thermoplastic resin TP is w ≥1000kg / mol. The ultra-high molecular weight of the resin corresponds to its ultra-long and highly entangled molecular chains. This specific microstructure gives it the characteristics of high strength and high modulus, so that its Barcol hardness is relatively high (≥60HBa). This high-hardness ultra-high molecular weight resin can quickly transfer the kinetic energy of the bullet to the fiber reinforcement phase when used as a component of the bulletproof plate matrix, prompting the high-performance fibers to undergo rapid tensile fracture, thereby significantly improving the fiber-dominated energy absorption efficiency and giving full play to the protective ability of the bulletproof plate body (fiber). The present invention does not particularly limit the content of TP in the bulletproof plate, but considering that too high a resin content causes the reinforcing effect of the continuous fibers to be sharply weakened, too low a resin content causes insufficient bonding between the continuous fibers. Both of these situations will reduce the protective performance of the bulletproof plate. Its content in the bulletproof plate is generally 5wt% to 25wt%, preferably 10wt% to 20wt%.

[0007] The present invention requires that the continuous fiber has the three major characteristics of light weight, high strength and high modulus. The continuous fiber is one or more of continuous ultra-high molecular weight polyethylene fiber, aramid fiber, and polyarylate fiber; the continuous fiber material needs to effectively dissipate the kinetic energy of the bullet. The continuous fiber material is one or more of non-woven fabric, three-dimensional braided fabric, and woven fabric.

[0008] The present invention requires that the monomer M of the thermoplastic resin has a rigid molecular chain and the monomer molecule contains a relatively large side group structure. Therefore, the monomer M of the thermoplastic resin TP is methacrylate, isobornyl acrylate, or a mixture of the two.

[0009] The present invention takes into account that ultra-high molecular weight thermoplastic resins can still be brittle due to their rigid backbones. When meeting higher protection requirements, they require toughening modifications to effectively prevent the resin from experiencing extensive cracking and failure under projectile impact loads. Therefore, the ballistic plate also contains a rubber R selected from isoprene-based rubber, butadiene-based rubber, and ethylene-propylene rubber. A low content of rubber R results in insufficient toughening of the resin, while a high content of rubber R significantly reduces the resin's strength and modulus, losing its high-strength and high-modulus properties. The content of R in the R / TP composition is generally 5% to 30% by weight, preferably 10% to 20% by weight.

[0010] The present invention also provides a method for preparing a thermoplastic resin-based bulletproof plate, comprising the following steps:

[0011] Step S1: Add or not add rubber R and photoinitiator PI to monomer M, and mix well to obtain polymerization system P. The monomer M is methacrylate, isobornyl acrylate, or a mixture thereof; the amount of photoinitiator PI added is 50 ppm to 150 ppm of the mass of monomer M.

[0012] Step S2: fully impregnating the continuous fiber material into the polymer system P, and then laminating and extruding to obtain a prepreg system Y;

[0013] Step S3: Initiating in-situ polymerization of the prepreg system Y through temperature-controlled pulsed ultraviolet irradiation to obtain a thermoplastic resin-based bulletproof plate; the temperature-controlled pulsed ultraviolet irradiation is as follows: after the ultraviolet irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to T, and then the irradiation is restarted when the temperature drops to T-5 until the temperature rises to T; this cycle is repeated until the M conversion rate α is ≥80%; wherein 45°C ≤ T ≤ 75°C.

[0014] The monomer M mentioned above needs to be a liquid with low viscosity and good fluidity at room temperature so as to better wet the continuous fiber material. Therefore, the monomer M in the present invention is methacrylate, isobornyl acrylate or a mixture of the two.

[0015] The present invention does not particularly limit the type of photoinitiator PI, but considering that the polymerization rate of cleavage-type free radical photoinitiators is faster than that of hydrogen abstraction-type initiators, the present invention selects a cleavage-type photoinitiator to initiate polymerization. Preferably, the photoinitiator PI 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.

[0016] The present invention has no strict limitation on the amount of photoinitiator PI added, but considering the weight average molecular weight M of the thermoplastic resin TP, w ≥1000kg / mol. The amount of PI added should not be too high, otherwise a large number of free radicals will be generated, which will easily terminate with double radicals, making it difficult to synthesize ultra-high molecular weight TP. Therefore, the amount of photoinitiator PI added is generally 50ppm to 150ppm of the weight of monomer M, preferably 50ppm to 100ppm of the weight of monomer M.

[0017] Whether to add rubber R in step S1 depends on the protection level and requirements. The addition of an appropriate amount of rubber R allows the thermoplastic resin TP to have both high rigidity and a certain degree of toughness, and its bulletproof plate can meet higher protection requirements. When adding rubber R, it is necessary to ensure that rubber R forms an island-type phase separation structure with monomer M, wherein monomer M is a continuous phase (sea phase) and rubber R is a dispersed phase (island phase). Given that monomer M has a polar molecular structure, non-polar rubber R is preferred to achieve good phase separation. Based on this, the rubber R is one or more of isoprene-based rubber, butadiene-based rubber, and ethylene-propylene rubber.

[0018] The present invention does not impose strict restrictions on the amount of rubber R added, but the following technical impacts must be considered: the interfacial interaction between the rubber R and the monomer M will cause the initial viscosity of the polymerization system P to increase, thereby affecting the polymerization behavior of the monomer M. When the rubber R is added in an appropriate amount, the system viscosity is within an optimal range. At this time, the diffusion movement of the monomer M is less affected, and the free radical diradical termination reaction is hindered, which can significantly improve the polymerization rate, product molecular weight, and monomer conversion rate. However, when the rubber R is added in an excessive amount, the excessive system viscosity will severely restrict the diffusion movement of the monomer M, thereby hindering the free radical chain growth reaction and hindering the synthesis of the ultra-high molecular weight thermoplastic resin TP. Based on this, the content of the rubber in the R / M composition is generally 5wt% to 30wt%, preferably 10wt% to 20wt%.

[0019] In step S2, the continuous fibers and their materials must be easily wetted by the polymer system P. Therefore, the continuous fibers are one or more of continuous ultra-high molecular weight polyethylene fibers, aramid fibers, and polyarylate fibers; and the continuous fiber materials are one or more of weft-free fabrics, three-dimensional braids, and woven fabrics. The purpose of post-lamination extrusion is to squeeze out excess polymer system P, thereby ensuring a high fiber content in the armor plate and fully utilizing the continuous fibers' reinforcement and primary protective properties.

[0020] In step S3, the present invention abandons traditional continuous ultraviolet irradiation and adopts temperature-controlled pulse ultraviolet irradiation. This is because continuous ultraviolet irradiation causes the prepolymerization system to heat up rapidly. Excessively high polymerization temperature makes the free radical movement too intense, significantly increases the probability of double radical termination, and even causes "violent polymerization", which is not conducive to obtaining ultra-high molecular weight resin. The reason why the temperature-controlled pulse irradiation process sets a lower limit (≥80%) for the M conversion rate α is that if the conversion rate is too low, the unreacted monomer will cause a large number of structural defects to form inside the product, thereby significantly deteriorating the various properties of the product. In addition, the setting basis of temperature T is as follows: the lower limit temperature (45°C) is higher than room temperature because the monomers in the present invention usually contain larger side group structures, and the steric hindrance effect generated by them will significantly hinder the efficient in-situ polymerization at room temperature; the upper limit temperature (75°C) is set because it is considered that too high a temperature will accelerate the volatilization of the monomer, resulting in a low polymerization yield. At the same time, high temperature will greatly increase the probability of free radical double radical termination, causing the molecular weight of the product to drop significantly.

[0021] In the present invention, the wavelength of ultraviolet irradiation only needs to meet the wavelength range of the ultraviolet light source. Therefore, the wavelength of ultraviolet irradiation is 365nm to 395nm. In addition, the present invention has no special restrictions on the intensity of ultraviolet irradiation, but considering that too low light intensity makes the photoinitiator absorb less light energy, so that the time (induction period) for the photoinitiator to decompose and produce primary free radicals is longer, and the in-situ polymerization efficiency is low; too high light intensity will cause the temperature of the prepreg system Y to be difficult to control, the main chain of the polymer to break and other side reactions, and the resulting thermoplastic resin TP is difficult to have an ultra-high molecular weight. The intensity of ultraviolet irradiation is generally 100mW / cm 2 ~500mW / cm 2 is better, preferably 200mW / cm 2 ~400mW / cm 2 .

[0022] Because the upper limit of the temperature T set in step S3 is relatively low and the content of photoinitiator PI in the polymerization system P is extremely low, the monomer M conversion rate α is typically no higher than 90%. Therefore, the present invention includes a step S4 after step S3, the purpose of which is to remove residual monomers from the thermoplastic resin-based bulletproof plate. Specifically, step S4 involves heat-treating the UV-irradiated thermoplastic resin-based bulletproof plate at 60°C to 100°C for 1 to 5 hours until the M conversion rate α reaches ≥ 99%. This temperature range is determined based on the following considerations: on the one hand, the temperature must be high enough to promote the self-polymerization of residual monomers; on the other hand, excessively high temperatures will lead to excessive monomer volatilization, resulting in a large number of structural defects within the resin. The heat treatment time is inversely proportional to the temperature: higher temperatures can shorten the treatment time, while lower temperatures require a longer treatment time to ensure optimal treatment results.

[0023] The principles of the present invention are as follows:

[0024] The present invention uses temperature-controlled pulsed UV irradiation to initiate in-situ polymerization of a specific polymerization system around a continuous fiber material, thereby producing a thermoplastic resin-based bulletproof plate. The polymerization system primarily consists of a "hard monomer" with a rigid molecular structure and a trace amount of photoinitiator. The rigid "hard monomer" ensures that the molecular chain of the resin after polymerization is also rigid, while the trace amount of photoinitiator generates low-concentration free radicals under UV irradiation, effectively suppressing the rapid termination of diradicals and thus promoting the synthesis of ultrahigh molecular weight resin. Furthermore, temperature-controlled pulsed UV irradiation prevents local overheating of the prepolymerization system, and the set temperature range allows the free radicals to maintain moderate mobility but be less susceptible to termination reactions, which also facilitates the efficient synthesis of ultrahigh molecular weight resin. Following temperature-controlled pulsed UV irradiation, the thermoplastic resin-based bulletproof plate is then heat-treated to remove any residual monomers.

[0025] The resulting resin combines a rigid molecular chain structure with an ultra-high molecular weight, typically imparting the mechanical properties of "hard but not brittle." If the resin remains brittle, an appropriate amount of rubber can be added for toughening. This high-strength, high-modulus resin rapidly transfers the impact stress of a bullet to the reinforcing fibers, promoting synergistic tensile fracture in the fibers and rapidly dissipating the bullet's kinetic energy. These advantages contribute to the excellent ballistic performance of the ballistic-resistant panels produced by this invention.

[0026] Beneficial effects:

[0027] (1) The present invention combines a high-strength, high-modulus, ultra-high molecular weight resin with a continuous fiber material to prepare a thermoplastic resin-based bulletproof plate that can achieve a significant lightweight effect while achieving the same level of protection;

[0028] (2) The present invention adopts in-situ polymerization technology to prepare thermoplastic resin-based bulletproof plates. Compared with the traditional hot melt method, the preparation conditions are milder, the cost is lower, and it has important economic value. DETAILED DESCRIPTION

[0029] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, 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 equally within the scope limited by the appended claims of the application.

[0030] The monomer M, photoinitiator PI, rubber R and solvent involved in the examples were purchased from Bidex Pharmaceuticals, Sinopharm Group or Aladdin Reagent; the continuous fiber material is a commercially available product.

[0031] Resin weight average molecular weight M w Testing: First, the armor plate was soaked in chloroform for 24 hours to dissolve the thermoplastic resin TP. The chloroform solution was then evaporated, and the remaining TP was dissolved in hexafluoroisopropanol to a concentration of 1 mg / mL. This solution was then injected into a gel permeation chromatography instrument at a column temperature of 40°C (using PMMA with a narrow molecular weight distribution as the standard calibrant).

[0032] Resin Barcol hardness determination: First, the armor plate was immersed in chloroform for 24 hours to dissolve the thermoplastic resin TP. The chloroform solution was then evaporated, the TP extracted, pulverized, and hot-pressed into a resin sheet ≥3 mm thick. Hardness testing was performed using a 934-1 Barcol hardness tester. Barcol hardness was measured at the center, interior, and edge of the resin sheet. The experiment was repeated three times, and the data were averaged.

[0033] Calculation of the content of thermoplastic resin TP in the bulletproof plate: First, weigh the prepared thermoplastic resin-based bulletproof plate and record its mass as W1. Then, soak the bulletproof plate in chloroform for 24 hours to fully dissolve the thermoplastic resin in the composite material. Finally, take out the bulletproof plate soaked in chloroform, wipe the chloroform on its surface with a test paper, and evaporate the remaining chloroform at room temperature until its mass reaches a constant weight, and record its mass as W2. The content of thermoplastic resin in the bulletproof plate (W R ) can be calculated using the following formula:

[0034]

[0035] Test of monomer M conversion rate: The prepared thermoplastic resin-based bulletproof plate was crushed, and the crushed sample was subjected to differential scanning calorimetry (DSC) testing. The standard polymerization exothermic enthalpy of monomer M was recorded as ΔH0 (unit: J / g, calculated based on the standard polymerization heat of monomer M in the polymer manual), the enthalpy of the exothermic peak in the first round of the DSC heating curve was recorded as ΔH1, and the content of thermoplastic resin TP in the bulletproof plate was recorded as W. R, monomer M, the monomer M conversion rate α can be calculated using the following formula:

[0036]

[0037] The test conditions for the ballistic performance of thermoplastic resin-based bullet-proof plates are as follows:

[0038] Firearms: Type 79 submachine gun;

[0039] Projectile: 7.62×25mm Type 79 submachine gun cartridge (lead core bullet, velocity 500-515 m / s);

[0040] Shooting distance and angle: 5m, 0°;

[0041] Standard: According to GA141-2001 test standard;

[0042] Target plate backing material: clay;

[0043] The target plate of 250mm×300mm was placed on a target stand with a backing of clay for testing. The surface density of each target plate was 3.5kg / m 2 ~10.0kg / m 2 Through its limiting surface density (AD min ) to evaluate its ballistic performance. min It refers to the minimum surface density value of the bulletproof material that can meet the protection requirements under the premise of meeting the specific protection level requirements. min The smaller it is, the better the protection.

[0044] Example 1

[0045] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0046] Step S1: adding a photoinitiator 1-hydroxy-cyclohexyl benzophenone to the monomer methyl methacrylate, and mixing them uniformly to obtain a polymerization system P. The amount of 1-hydroxy-cyclohexyl benzophenone added is 100 ppm of methyl methacrylate;

[0047] Step S2: fully impregnating the ultra-high molecular weight polyethylene fiber non-woven fabric into the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0048] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 60°C, and then the irradiation is restarted when the temperature drops to 55°C and raised to 60°C; this cycle is repeated until the conversion rate of methyl methacrylate α = 85%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 200mW / cm2 .

[0049] Step S4: heat-treating the UV-irradiated bulletproof plate at 80° C. for 4 hours until the conversion rate α of methyl methacrylate reaches ≥99%.

[0050] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1000kg / mol, Barcol hardness is 80HBa, and the content of resin in the bulletproof plate is 18wt%. AD of the bulletproof plate min =4.8kg / m 2 .

[0051] Comparative Example 1

[0052] A method for preparing a thermoplastic resin-based bulletproof plate, wherein the specific implementation steps are basically the same as those in Example 1, except that the amount of the photoinitiator 1-hydroxy-cyclohexyl benzophenone added is 1000 ppm of the monomer methyl methacrylate, and the weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is 1000 ppm. w =500kg / mol, Barcol hardness is 50HBa, AD of bulletproof plate min =8.0kg / m 2 This is because excessive initiator addition results in a high number of free radicals, which are prone to double-radical termination, resulting in a low molecular weight thermoplastic resin. The resin's low molecular weight results in a low Barcol hardness, and the resulting ballistic performance of the armor plate is poor.

[0053] Example 2

[0054] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0055] Step S1: adding a photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide to the monomer isobornyl acrylate, and mixing them uniformly to obtain a polymerization system P. The amount of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide added is 80 ppm of isobornyl acrylate;

[0056] Step S2: fully impregnating the aramid fiber three-dimensional braid into the polymer system P, and then laminating and extruding to obtain a prepreg system Y;

[0057] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: After the UV irradiation begins, the temperature of the prepreg system Y rises to 50°C, and then the irradiation is stopped. When the temperature drops to 45°C, the irradiation is resumed and continued until the temperature rises to 50°C. This cycle is repeated until the conversion rate of isobornyl acrylate α = 82%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 300mW / cm 2.

[0058] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1100kg / mol, Barcol hardness is 70HBa, and the content of resin in the bulletproof plate is 25wt%. AD of the bulletproof plate min =5.8kg / m 2 .

[0059] Example 3

[0060] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0061] Step S1: Adding a photoinitiator, benzoin ethyl ether, and isoprene-based rubber to the monomer hydroxyethyl methacrylate, and mixing them uniformly to obtain a polymerization system P. The amount of benzoin ethyl ether added is 150 ppm of the hydroxyethyl methacrylate; and the amount of isoprene-based rubber is 10 wt% of the mass of the hydroxyethyl methacrylate.

[0062] Step S2: fully impregnating the polyarylate fiber non-woven fabric into the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0063] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 55°C, and then the irradiation is restarted when the temperature drops to 50°C and raised to 55°C; this cycle is repeated until the conversion rate of hydroxyethyl methacrylate α = 83%. The UV irradiation wavelength is 395nm, and the irradiation intensity is 400mW / cm 2 .

[0064] Step S4: heat-treating the bulletproof plate after UV irradiation at 100° C. for 2 h until the conversion rate α of hydroxyethyl methacrylate reaches ≥99%.

[0065] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1050kg / mol, Barcol hardness is 75HBa, and the content of resin in the bulletproof plate is 20wt%. AD min =5.0kg / m 2 .

[0066] Comparative Example 2

[0067] A method for preparing a thermoplastic resin-based bulletproof plate, wherein the specific implementation steps are basically the same as those in Example 3, except that the temperature-controlled pulsed ultraviolet irradiation is as follows: after the ultraviolet irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 90°C, and then the irradiation is restarted when the temperature drops to 85°C until the temperature rises to 90°C; this cycle is repeated until the conversion rate of hydroxyethyl methacrylate α = 92%; the weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =700kg / mol, Barcol hardness is 55HBa, AD of bulletproof plate min =7.5kg / m 2 This is because the excessively high temperature of prepreg system Y causes violent free radical motion, significantly increasing the probability of double radical termination and resulting in a lower molecular weight resin. This lower molecular weight results in a lower Barcol hardness, and the resulting ballistic performance of the armor plate is poor.

[0068] Example 4

[0069] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0070] Step S1: Adding a photoinitiator α,α-dimethylbenzil ketal and butadiene-based rubber to the monomer methyl methacrylate, and mixing them evenly to obtain a polymerization system P. The amount of α,α-dimethylbenzil ketal added is 100 ppm of the methyl methacrylate; the amount of isoprene-based rubber added is 20 wt% of the mass of the methyl methacrylate;

[0071] Step S2: fully impregnating the ultra-high molecular weight polyethylene fiber non-woven fabric into the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0072] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 65°C, and then the irradiation is restarted when the temperature drops to 60°C and the temperature is raised to 65°C. This cycle is repeated until the conversion rate of methyl methacrylate α = 88%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 500mW / cm 2 .

[0073] Step S4: heat-treating the bullet-proof plate after UV irradiation at 90° C. for 3 h until the conversion rate α of methyl methacrylate reaches ≥99%.

[0074] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1200kg / mol, Barcol hardness is 78HBa, and the content of resin in the bulletproof plate is 10wt%. AD of the bulletproof plate min =3.5kg / m 2 .

[0075] Example 5

[0076] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0077] Step S1: Adding a photoinitiator 1-hydroxy-cyclohexyl benzophenone and ethylene-propylene rubber to the monomer propyl methacrylate, and mixing them evenly to obtain a polymerization system P. The amount of 1-hydroxy-cyclohexyl benzophenone added is 100 ppm of the propyl methacrylate; the amount of ethylene-propylene rubber added is 5 wt% of the mass of the propyl methacrylate;

[0078] Step S2: fully impregnating the aramid fiber woven fabric with the polymer system P, and then laminating and extruding to obtain the prepreg system Y;

[0079] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 60°C, and then the irradiation is restarted when the temperature drops to 55°C and raised to 60°C. This cycle is repeated until the conversion rate of propyl methacrylate α = 87%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 100mW / cm 2 .

[0080] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1050kg / mol, Barcol hardness is 79HBa, and the content of resin in the bulletproof plate is 25wt%. AD min =5.5kg / m 2 .

[0081] Example 6

[0082] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0083] Step S1: Adding a photoinitiator 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone and ethylene propylene rubber to the monomer isobornyl acrylate, and mixing them uniformly to obtain a polymerization system P. The amount of 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone added is 75 ppm of isobornyl acrylate; the amount of ethylene propylene rubber added is 30 wt% of the mass of isobornyl acrylate;

[0084] Step S2: fully impregnating the polyarylate fiber three-dimensional braid into the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0085] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation begins, the irradiation is stopped when the temperature of the prepreg system Y reaches 70°C; then, when the temperature drops to 65°C, the irradiation is resumed and continued until the temperature rises to 70°C; this cycle is repeated until the conversion rate of isobornyl acrylate reaches α = 90%. The UV irradiation wavelength is 395 nm, and the irradiation intensity is 200 mW / cm 2 .

[0086] Step S4: heat-treating the bulletproof plate after UV irradiation at 65° C. for 5 hours until the conversion rate α of isobornyl acrylate reaches ≥99%.

[0087] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1150kg / mol, Barcol hardness is 72HBa, and the content of resin in the bulletproof plate is 25wt%. AD min =5.3kg / m 2 .

[0088] Example 7

[0089] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0090] Step S1: adding a photoinitiator 1-hydroxy-cyclohexyl benzophenone to the monomer methyl methacrylate, and mixing them uniformly to obtain a polymerization system P. The amount of 1-hydroxy-cyclohexyl benzophenone added is 75 ppm of methyl methacrylate;

[0091] Step S2: fully impregnating the ultra-high molecular weight polyethylene fiber non-woven fabric into the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0092] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 65°C, and then the irradiation is restarted when the temperature drops to 60°C and the temperature is raised to 65°C. This cycle is repeated until the conversion rate of methyl methacrylate α = 84%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 300mW / cm 2 .

[0093] Step S4: heat-treating the bullet-proof plate after UV irradiation at 80° C. for 4.5 hours until the conversion rate of methyl methacrylate α is ≥99%.

[0094] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w=1080kg / mol, Barcol hardness is 82HBa, and the content of resin in the bulletproof plate is 5wt%. AD min =6.0kg / m 2 .

[0095] Example 8

[0096] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0097] Step S1: adding a photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide to the monomer hydroxyethyl methacrylate, and mixing them uniformly to obtain a polymerization system P. The amount of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide added is 50 ppm of the hydroxyethyl methacrylate;

[0098] Step S2: fully impregnating the ultra-high molecular weight polyethylene fiber / aramid fiber three-dimensional mixed fabric into the polymerization system P, followed by lamination and extrusion to obtain a prepreg system Y;

[0099] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 70°C, and then the irradiation is restarted when the temperature drops to 65°C and raised to 70°C; this cycle is repeated until the conversion rate of hydroxyethyl methacrylate α reaches 80%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 200mW / cm 2 .

[0100] Step S4: heat-treating the bullet-proof plate after UV irradiation at 90° C. for 3.5 hours until the conversion rate of methyl methacrylate α is ≥99%.

[0101] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1120kg / mol, Barcol hardness is 82HBa, and the content of resin in the bulletproof plate is 13wt%. min =4.5kg / m 2 .

[0102] Example 9

[0103] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0104] Step S1: Adding a photoinitiator PI (a mixture of 1-hydroxy-cyclohexyl benzophenone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide in an equal weight ratio) and an isoprene-based rubber to a monomer M (a mixture of methyl methacrylate and hydroxyethyl methacrylate in an equal weight ratio) and mixing them uniformly to obtain a polymerization system P. The amount of the photoinitiator PI added is 100 ppm based on the weight of the monomer M; the amount of the isoprene-based rubber is 15 wt% based on the weight of the monomer M.

[0105] Step S2: fully impregnating the aramid fiber / polyarylate fiber three-dimensional mixed fabric into the polymerization system P, and then laminating and extruding to obtain the prepreg system Y;

[0106] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 60°C, and then the irradiation is restarted when the temperature drops to 55°C and the temperature rises to 60°C. This cycle is repeated until the conversion rate α of the monomer M reaches 85%. The UV irradiation wavelength is 395nm, and the irradiation intensity is 350mW / cm 2 .

[0107] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1000kg / mol, Barcol hardness is 62HBa, and the content of resin in the bulletproof plate is 20wt%. AD of the bulletproof plate min =6.2kg / m 2 .

[0108] Example 10

[0109] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0110] Step S1: Adding a photoinitiator PI (a mixture of 1-hydroxy-cyclohexyl benzophenone and benzoin ethyl ether in an equal weight ratio) and a butadiene-based rubber to a monomer M (a mixture of methyl methacrylate and isobornyl acrylate in an equal weight ratio) and mixing them uniformly to obtain a polymerization system P. The amount of the photoinitiator PI added is 100 ppm based on the weight of the monomer M; the amount of the butadiene-based rubber added is 10 wt% based on the weight of the monomer M.

[0111] Step S2: fully impregnating the polyarylate fiber woven fabric with the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0112] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 75°C, and then the irradiation is restarted when the temperature drops to 70°C and the temperature rises to 75°C. This cycle is repeated until the conversion rate α of the monomer M reaches 93%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 200mW / cm 2 .

[0113] Step S4: heat-treating the bullet-proof plate after UV irradiation at 70° C. for 5 h until the conversion rate α of the monomer M reaches ≥99%.

[0114] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1025kg / mol, Barcol hardness is 72HBa, and the content of resin in the bulletproof plate is 19wt%. AD min =6.7kg / m 2 .

[0115] Comparative Example 3

[0116] A method for preparing a thermoplastic resin-based bulletproof plate, wherein the specific implementation steps are basically the same as those of Example 10, except that in step S2, only the polyarylate fiber woven fabric fully impregnated with the polymerization system P is laminated without extrusion, so that the resin content in the bulletproof plate is 70 wt % and the bulletproof plate has an area density (AD) of 10 kg / m 2 This is because the high resin content means that the main structure that bears the bullet's impact is the resin rather than the fiber, which greatly reduces the fiber's reinforcing effect. As a result, the bulletproof performance of the bulletproof plate is extremely poor.

[0117] Example 11

[0118] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0119] Step S1: Adding a photoinitiator PI (a mixture of α,α-dimethylbenzil ketal and benzoin ethyl ether in an equal weight ratio) and a butadiene-based rubber to a monomer M (a mixture of methyl methacrylate and propyl methacrylate in an equal weight ratio) and mixing them uniformly to obtain a polymerization system P. The amount of the photoinitiator PI added is 100 ppm based on the weight of the monomer M; the amount of the butadiene-based rubber is 20 wt% based on the weight of the monomer M.

[0120] Step S2: fully impregnating the ultra-high molecular weight polyethylene fiber non-woven fabric into the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0121] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the temperature of the prepreg system Y rises to 45°C, and then the irradiation is stopped. When the temperature drops to 40°C, the irradiation is restarted and continued until the temperature rises to 45°C. This cycle is repeated until the conversion rate α of the monomer M reaches 80%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 500mW / cm 2 .

[0122] Step S4: heat-treating the bullet-proof plate after UV irradiation at 80° C. for 4 hours until the conversion rate α of the monomer M reaches ≥99%.

[0123] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1250kg / mol, Barcol hardness is 80HBa, and the content of resin in the bulletproof plate is 16wt%. AD min =4.0kg / m 2 .

[0124] Example 12

[0125] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0126] Step S1: adding a photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide to the monomer methyl methacrylate, and mixing them uniformly to obtain a polymerization system P. The amount of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide added is 75 ppm of methyl methacrylate;

[0127] Step S2: fully impregnating the ultra-high molecular weight polyethylene fiber three-dimensional braid into the polymerization system P, and then laminating and extruding to obtain the prepreg system Y;

[0128] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation is started, the irradiation is stopped when the temperature of the prepreg system Y rises to 55°C, and then the irradiation is restarted when the temperature drops to 50°C and the temperature is raised to 55°C. This cycle is repeated until the conversion rate of methyl methacrylate α = 83%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 200mW / cm 2 .

[0129] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1175kg / mol, Barcol hardness is 81HBa, and the content of resin in the bulletproof plate is 12wt%. min =5.0kg / m 2 .

[0130] Comparative Example 4

[0131] A method for preparing a thermoplastic resin-based bulletproof plate, wherein the specific implementation steps are basically the same as those of Example 10, except that the temperature-controlled pulsed ultraviolet irradiation is as follows: after the ultraviolet irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 35°C, and then the irradiation is restarted when the temperature drops to 30°C until the temperature rises to 35°C; this cycle is repeated until the conversion rate of methyl methacrylate α = 70%; the weight average molecular weight M of the thermoplastic resin in the bulletproof plate is w =600kg / mol, Barcol hardness is 45HBa. AD of bulletproof plate min =7.5kg / m 2 This is because the excessively low temperature of prepreg system Y slows the reaction between monomer molecules and free radicals, hindering chain growth and resulting in low monomer conversion and resin molecular weight. The resin's low molecular weight results in a low Barcol hardness and increased brittleness, resulting in poor ballistic performance.

[0132] Example 13

[0133] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0134] Step S1: adding a photoinitiator 1-hydroxy-cyclohexyl benzophenone to the monomer hydroxyethyl methacrylate, and mixing them uniformly to obtain a polymerization system P. The amount of 1-hydroxy-cyclohexyl benzophenone added is 100 ppm of the hydroxyethyl methacrylate;

[0135] Step S2: fully impregnating the ultra-high molecular weight polyethylene fiber non-woven fabric into the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0136] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 60°C, and then the irradiation is restarted when the temperature drops to 55°C and the temperature is raised to 60°C. This cycle is repeated until the conversion rate of hydroxyethyl methacrylate α reaches 85%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 200mW / cm 2 .

[0137] Step S4: heat-treating the bulletproof plate after UV irradiation at 80° C. for 5 h until the conversion rate α of hydroxyethyl methacrylate reaches ≥99%.

[0138] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1000kg / mol, Barcol hardness is 80HBa, and the content of resin in the bulletproof plate is 18wt%. AD of the bulletproof plate min=4.5kg / m 2 .

[0139] Example 14

[0140] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0141] Step S1: Adding a photoinitiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide to a monomer M (a mixture of methyl methacrylate and hydroxyethyl methacrylate in an equal weight ratio), and mixing them uniformly to obtain a polymerization system P. The amount of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide added is 80 ppm of the monomer M;

[0142] Step S2: fully impregnating the aramid fiber three-dimensional braid into the polymer system P, and then laminating and extruding to obtain a prepreg system Y;

[0143] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation begins, the irradiation is stopped when the temperature of the prepreg system Y reaches 50°C, and then the irradiation is restarted when the temperature drops to 45°C and continued until the temperature reaches 50°C. This cycle is repeated until the conversion rate of hydroxyethyl methacrylate α reaches 82%. The UV irradiation wavelength is 365nm, and the irradiation intensity is 300mW / cm 2 .

[0144] Step S4: heat-treating the UV-irradiated bulletproof plate at 100° C. for 2.5 h until the conversion rate α of hydroxyethyl methacrylate reaches ≥99%.

[0145] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1100kg / mol, Barcol hardness is 70HBa, and the content of resin in the bulletproof plate is 25wt%. AD of the bulletproof plate min =5.3kg / m 2 .

[0146] Example 15

[0147] A thermoplastic resin-based bulletproof plate and a preparation method thereof, the preparation method comprising the following steps:

[0148] Step S1: Adding a photoinitiator, benzoin ethyl ether, and a butadiene-based rubber to a monomer M (a mixture of methyl methacrylate and isobornyl acrylate in an equal weight ratio) and mixing them uniformly to obtain a polymerization system P. The amount of the photoinitiator PI added is 150 ppm based on the weight of the monomer M; the butadiene-based rubber is 25 wt% based on the weight of the monomer M.

[0149] Step S2: fully impregnating the polyarylate fiber non-woven fabric into the polymerization system P, and then laminating and extruding to obtain a prepreg system Y;

[0150] Step S3: Initiate in-situ polymerization of the prepreg system Y by temperature-controlled pulsed UV irradiation to obtain a thermoplastic resin-based bulletproof plate. The temperature-controlled pulsed UV irradiation is as follows: after the UV irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to 55°C, and then the irradiation is restarted when the temperature drops to 50°C and raised to 55°C. This cycle is repeated until the conversion rate α of the monomer M reaches 83%. The UV irradiation wavelength is 395nm, and the irradiation intensity is 400mW / cm 2 .

[0151] Step S4: heat-treating the bullet-proof plate after UV irradiation at 90° C. for 3 hours until the conversion rate α of the monomer M reaches ≥99%.

[0152] The weight average molecular weight M of the thermoplastic resin in the obtained thermoplastic resin-based bulletproof plate is w =1050kg / mol, Barcol hardness is 75HBa, and the content of resin in the bulletproof plate is 20wt%. AD min =4.8kg / m 2 .

Claims

1. A thermoplastic resin-based bulletproof plate, characterized in that: It comprises a thermoplastic resin TP and a continuous fiber material; wherein the weight average molecular weight M of the thermoplastic resin TP is w ≥1000kg / mol, Barcol hardness ≥60HBa, and its content in the bulletproof plate is 5wt% to 25wt%.

2. The thermoplastic resin-based bulletproof plate according to claim 1, characterized in that: The continuous fiber is one or more of continuous ultra-high molecular weight polyethylene fiber, aramid fiber, and polyarylate fiber; the continuous fiber material is one or more of non-woven fabric, three-dimensional braided fabric, and woven fabric.

3. The thermoplastic resin-based bulletproof plate according to claim 1, characterized in that: The monomer M of the thermoplastic resin TP is methacrylate, isobornyl acrylate or a mixture thereof.

4. The thermoplastic resin-based bulletproof plate according to claim 1, characterized in that: The bulletproof plate further contains rubber R selected from isoprene-based rubber, butadiene-based rubber and ethylene-propylene rubber; the content of R in the R / TP composition is 5 wt% to 30 wt%.

5. The method for preparing a thermoplastic resin-based bulletproof plate according to any one of claims 1 to 4, characterized in that The following steps are involved: Step S1: adding or not adding rubber R and photoinitiator PI to monomer M, and mixing evenly to obtain polymerization system P; the monomer M is methacrylate, isobornyl acrylate or a mixture thereof; the amount of photoinitiator PI added is 50ppm to 150ppm of the mass of monomer M. Step S2: fully impregnating the continuous fiber material into the polymer system P, and then laminating and extruding to obtain a prepreg system Y; Step S3: Initiating in-situ polymerization of the prepreg system Y through temperature-controlled pulsed ultraviolet irradiation to obtain a thermoplastic resin-based bulletproof plate; the temperature-controlled pulsed ultraviolet irradiation is as follows: after the ultraviolet irradiation starts, the irradiation is stopped when the temperature of the prepreg system Y rises to T, and then the irradiation is restarted when the temperature drops to T-5 until the temperature rises to T; this cycle is repeated until the M conversion rate α is ≥80%; wherein 45°C ≤ T ≤ 75°C.

6. The method for preparing a thermoplastic resin-based bulletproof plate according to claim 5, wherein: The rubber R is one or more of isoprene-based rubber, butadiene-based rubber and ethylene-propylene rubber; the content of R in the R / M composition is 5wt% to 30wt%.

7. The method for preparing a thermoplastic resin-based bulletproof plate according to claim 5, wherein: The photoinitiator PI 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.

8. The method for preparing a thermoplastic resin-based bulletproof plate according to claim 5, wherein: The continuous fiber is one or more of continuous ultra-high molecular weight polyethylene fiber, aramid fiber, and polyarylate fiber; the continuous fiber material is one or more of non-woven fabric, three-dimensional braided fabric, and woven fabric.

9. The method for preparing a thermoplastic resin-based bulletproof plate according to claim 5, wherein: The wavelength of ultraviolet radiation in step S3 is 365nm-395nm, and the intensity of ultraviolet radiation is 100-500mW / cm 2 .

10. The method for preparing a thermoplastic resin-based bulletproof plate according to claim 5, wherein: After step S3, there is step S4, wherein the ultraviolet irradiated thermoplastic resin-based bulletproof plate is heat-treated at 60° C. to 100° C. for 1 hour to 5 hours until the M conversion rate α is ≥99%.

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