Carbon fiber reinforced resin-based composite material and preparation method thereof

Abstract

The invention discloses a carbon fiber reinforced resin-based composite material and a preparation method thereof, and the method comprises the following steps: (1) mixing vinyl ester resin, a reactive diluent, an ultraviolet light initiator and a thermal initiator to obtain a mixed glue solution; and (2) immersing carbon fibers into the mixed glue solution for light curing to obtain the composite material. The winding forming technology and the photocuring technology are combined to be used for preparing the composite material, the rapid forming method of the carbon fiber reinforced resin matrix composite material is provided, multiple defects of a traditional thermocuring forming technology are overcome, and the rapid forming method has the advantages of being short in production period, small in energy consumption, small in environmental pollution, good in device surface quality and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite material preparation. Specifically, the present invention relates to a carbon fiber reinforced resin matrix composite material and a preparation method thereof. Background Art

[0002] Fiber reinforced resin matrix composite materials (FRP) are high-performance materials composed of fiber reinforcements and mixed sizing. Due to their characteristics such as light weight, high strength, and corrosion resistance, they are widely used in aerospace, transportation, military, etc. The current conventional forming processes for such materials are thermal curing and thermoplastic methods. While these traditional methods have been widely used, they have significant defects such as high energy consumption, long production cycles, and large environmental pollution. Therefore, developing a new generation of curing and forming processes for fiber reinforced resin matrix composite materials has great social and economic value. Summary of the Invention

[0003] Aiming at the defects of the traditional thermoforming process, the present invention provides a carbon fiber reinforced resin matrix composite material and a preparation method thereof. Through this method, not only can the production efficiency of the carbon fiber reinforced resin matrix composite material be significantly improved, and the energy consumption during the curing and forming process be reduced, but also the high-precision and stable process effectively guarantees the high performance of the product.

[0004] The first aspect of the present invention provides a method for preparing a carbon fiber reinforced resin matrix composite material, comprising:

[0005] (1) Mix vinyl ester resin, reactive diluent, ultraviolet light initiator, and thermal initiator to obtain a mixed sizing;

[0006] (2) Immerse carbon fiber into the mixed sizing for photocuring to obtain a composite material. Further, the mass ratio of the vinyl ester resin, the reactive diluent, the ultraviolet light initiator, and the thermal initiator is (10 - 20):(20 - 30):(0.1 - 0.5):(0.3 - 0.6).

[0007] Further, in step (1), mixing the vinyl ester resin, reactive diluent, ultraviolet light initiator, and thermal initiator to prepare a mixed sizing includes: while heating, mixing the vinyl ester resin, reactive diluent, and ultraviolet light initiator for ultrasonic treatment, adding the thermal initiator after cooling, and then performing defoaming in a vacuum drying oven to obtain the mixed sizing.

[0008] Further, the heating temperature is 40 - 60°C.

[0009] Further, the ultrasonic treatment time is 20 min - 30 min.

[0010] Further, the vacuum degree in the defoaming process is -0.1 to -0.3 MPa, and the treatment time is 20 min - 30 min.

[0011] Further, in step (1), during the mixing of the vinyl ester resin, the reactive diluent, the ultraviolet light initiator, and the thermal initiator, an auxiliary agent is further added. The auxiliary agent includes at least one of a toughening agent, an antifoaming agent, and an antioxidant.

[0012] Further, in step (1), the vinyl ester resin includes at least one of bisphenol A epoxy acrylate, phenolic epoxy acrylate, epoxidized oil acrylate, and modified epoxy acrylate.

[0013] Further, in step (1), the reactive diluent includes at least one of a monofunctional acrylate derivative, a bifunctional acrylate derivative, and a polyfunctional acrylate derivative.

[0014] Further, in step (1), the ultraviolet light initiator includes at least one of acylphosphine oxides, benzophenone compounds, and benzoin compounds.

[0015] Further, in step (1), the thermal initiator includes at least one of acyl peroxides, ester peroxides, and ketone peroxides.

[0016] Further, in step (2), the tow size of the carbon fiber is 3K - 12K.

[0017] Further, in step (2), dipping the carbon fiber into the mixed adhesive solution includes: using a winding device, and dipping the carbon fiber into the mixed adhesive solution by wet winding and then winding it on the surface of a mandrel.

[0018] Further, the parameters of the winding device include at least one of the following:

[0019] The winding method of the winding device is circumferential winding;

[0020] The winding layer number of the carbon fiber tow is 2 - 4 layers;

[0021] The advancing distance of the carbon fiber tow is 40 - 200 mm;

[0022] The step of the carbon fiber tow is 0.5 - 0.8 times the width of a single tow yarn sheet;

[0023] The winding tension of the carbon fiber tow is 0 - 50 N;

[0024] The winding rate of the carbon fiber tow is 10 - 40° / min.

[0025] Further, in step (2), the photocuring includes: after removing the sample wound on the surface of the core mold from the mold, transferring it to under an ultraviolet lamp device for illumination first, and then transferring it to under an infrared lamp device for illumination.

[0026] Further, the wavelength range of the ultraviolet light of the ultraviolet lamp device is 320 - 400 nm; and / or the irradiation power of the ultraviolet lamp device is 100 - 200 W; and / or the irradiation distance of the ultraviolet device is 5 - 30 cm; and / or the irradiation time of the ultraviolet lamp device is 1 - 2 min; the ambient temperature during the photocuring process is 20 - 50 °C.

[0027] Further, the wavelength range of the infrared light of the infrared lamp device is 750 - 1500 nm; and / or the irradiation power of the infrared lamp device is 1000 - 2000 W; and / or the irradiation distance of the infrared device is 5 - 20 cm; and / or the irradiation time of the infrared lamp device is 5 - 10 min.

[0028] The second aspect of the present invention provides a carbon fiber reinforced resin matrix composite material, which is prepared by using the method described in the first aspect.

[0029] The present invention has at least the following beneficial effects compared with the prior art:

[0030] (1) The present invention uses vinyl ester resin, reactive diluent, ultraviolet light initiator, thermal initiator and carbon fiber as raw materials to prepare a carbon fiber reinforced resin matrix composite material, and can prepare a mixed adhesive with a dense three-dimensional cross-linked network structure, so as to improve its mechanical properties, heat resistance, dimensional stability and other properties, thereby endowing the composite material with more excellent comprehensive properties.

[0031] (2) The present invention provides a method for preparing a carbon fiber reinforced resin matrix composite material by winding molding and light source curing. By this method, not only can the production efficiency of the carbon fiber reinforced resin matrix composite material be significantly improved and the energy consumption during the curing and molding process be reduced, but also the molding process is stable and the surface accuracy of the product is easy to control.

[0032] (3) The present invention combines the winding molding technology with the photocuring technology, expands the rapid molding method of fiber reinforced resin matrix composite materials, and this method is expected to be applied to the production process of pressure vessels and pipelines in the fields of construction, transportation, military and so on. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The above and / or additional aspects and advantages of the present invention will become obvious and easy to understand from the description of the embodiments in conjunction with the following drawings, wherein:

[0034] Figure 1 is the photocuring temperature curve of the sample in Example 1 of the present invention. Specific implementation method

[0036] To make the objectives, technical solutions and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions of the present invention in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. The following examples are only descriptive and not restrictive, and the protection scope of the present invention cannot be limited thereby. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0037] The technical solution of this application is completed based on the following principle: The photocuring reaction is a chemical reaction initiated by a light source with a certain energy. The reaction system consists of monomers or oligomers, reactive diluents and initiators. The ground-state molecules of the initiator absorb light energy and undergo electronic transitions to become excited-state molecules. Since the excited-state molecules have high energy and cannot exist stably, some of them are deactivated, and the other part undergoes electron and energy transfer to become active species. Free radical photoinitiators can generate free radical active species, induce the addition reaction of vinyl ester resin on the carbon-carbon double bond (C=C), and then crosslink to form a three-dimensional network molecular structure. The key to the photocuring technology is the radical polymerization induced by light source irradiation. However, carbon fiber itself is an opaque material and is not suitable for simply using the photocuring method to prepare deeply cured samples. However, the dark graphite sheet structure of carbon fiber has a high absorbance, so it has a certain photothermal effect and can be applied to the resin system of photothermal dual-curing to prepare photocured composites.

[0038] The first aspect of the present invention provides a method for preparing a carbon fiber reinforced resin matrix composite material. According to an embodiment of the present invention, the method includes:

[0039] S1: Mix vinyl ester resin, reactive diluent, ultraviolet photoinitiator and thermal initiator to prepare a mixed adhesive solution

[0040] Specifically, vinyl ester resin (VE) has the characteristics of both unsaturated resin and epoxy resin at the same time. The double bonds at both ends of the molecular chain are extremely active, enabling the vinyl resin to cure quickly and form a highly crosslinked rigid network structure, making it have good mechanical properties and corrosion resistance; on the one hand, the reactive diluent can adjust the system viscosity to improve its photocuring performance, and on the other hand, it can adjust the network structure after resin curing to change its mechanical properties; since carbon fiber shows poor penetrability to light sources in the ultraviolet to infrared wavelength bands, neither the photoinitiator nor the thermal initiator alone can cure the adhesive solution deep in the fiber. However, through the synergistic effect of the two initiators, the surface adhesive solution of the prepreg is cured by ultraviolet light, and the deep adhesive solution is cured by the thermal effect during the curing process and the photothermal effect of carbon fiber on near-infrared light, thereby obtaining high-performance, photocured products.

[0041] According to an embodiment of the present invention, the method for preparing a mixed colloid by mixing the vinyl ester resin, the reactive diluent, the ultraviolet initiator, and the thermal initiator includes:

[0042] With stirring, the vinyl ester resin, the reactive diluent, and the ultraviolet initiator are mixed and subjected to ultrasonic treatment, and after cooling, the thermal initiator is added, and then defoaming is carried out in a vacuum drying oven to obtain a mixed glue solution, wherein the heating temperature is 40-60 °C; the ultrasonic treatment time is 20 min-30 min; the vacuum degree during the defoaming process is -0.1 to -0.3 MPa, and the treatment time is 20 min-30 min.

[0043] According to an embodiment of the present invention, the mass ratio of the vinyl ester resin, the reactive diluent, the ultraviolet initiator, and the thermal initiator is (10-20):(20-30):(0.1-0.5):(0.3-0.6). The inventors found that if the content of the reactive diluent is too high, the viscosity of the resin system will be significantly reduced, and the comprehensive performance of the cured product will be significantly deteriorated, which is not conducive to the high performance of the composite material. If the content of the reactive diluent is too low, there will be a phenomenon of concentrated heat release during the curing process, which will cause the resin to turn yellow, and the high-viscosity resin system is not conducive to the wet winding production method; if the content of the photoinitiator is too high, the absorption of ultraviolet light by the initiator during the photocuring process will reduce its penetration depth, which is not conducive to the deep curing of the product. If the content of the photoinitiator is too low, the photocuring efficiency will decrease, and the curing effect of the product will be poor; if the content of the thermal initiator is too high, the generation of excessive free radicals will cause the termination reaction to advance, resulting in insufficient curing degree. If the content is too low, the mixed glue solution cannot react sufficiently. Thus, a carbon fiber reinforced resin matrix composite material with excellent curing performance, mechanical performance, heat resistance performance, etc. can be prepared by using the mixed glue solution composed of the present application.

[0044] According to an embodiment of the present invention, the vinyl ester resin includes at least one of bisphenol A type epoxy acrylate, phenolic epoxy acrylate, epoxidized oil acrylate, and modified epoxy acrylate. The vinyl ester resin in the present invention has the following characteristics: ① It contains two or more carbon-carbon double bond groups with relatively high activity and can participate in free radical or cationic reactions during the curing process; ② It has one or more benzene ring rigid structures to improve the mechanical properties of the mixed glue solution. ③ It is liquid at room temperature and has an appropriate viscosity, so a composite material with excellent curing performance and processing performance can be prepared.

[0045] According to an embodiment of the present invention, the reactive diluent includes at least one of monofunctional acrylate derivatives such as 2-hydroxy-3-phenoxypropyl acrylate, difunctional acrylate derivatives such as 2-hydroxy-1,3-propanediyl diacrylate, polyfunctional acrylate derivatives such as trimethylolpropane triacrylate, and acrylic acid modified compounds. The reactive diluent in the present invention has the following characteristics: ① It has one or more carbon-carbon double bond groups with relatively high activity and can participate in free radical or cationic reactions during the curing process; ② It is liquid at room temperature, has a boiling point higher than 150 °C, and has a lower viscosity than the selected resin, and can be used to adjust the viscosity of the system. Thus, a composite material with excellent curing performance and processing performance can be obtained by using the reactive diluent with this composition.

[0046] According to an embodiment of the present invention, the ultraviolet light initiator includes at least one of acylphosphine oxides such as trimethylbenzoyl-diphenylphosphine oxide, benzophenones such as 2,4-dihydroxybenzophenone, and benzoins such as α,α-dimethoxy-α-phenylacetophenone. The ultraviolet light initiator in the present invention has the following characteristics: ① The near-ultraviolet light with an absorption wavelength range of 320-400 nm is the best. The larger the wavelength, the higher the penetration depth of the light source; ② Its state at room temperature is solid or liquid, has good thermal stability, and has a certain solubility in vinyl ester resin; ③ It can form free radical or cationic active species by absorbing ultraviolet light, and then initiate the addition crosslinking of carbon-carbon double bonds. Thus, the curing performance of the composite material can be improved by using the ultraviolet light initiator with this composition.

[0047] According to an embodiment of the present invention, the thermal initiator includes at least one of acyl peroxides, ester peroxides, and ketone peroxides. The thermal initiator in the present invention has the following characteristics: ① The cracking temperature range is within 30-150 °C; ② Its state at room temperature is solid or liquid, and has a certain solubility in vinyl ester resin; ③ It can generate free radical or cationic active species, and then initiate the addition crosslinking of carbon-carbon double bonds. Thus, the curing performance of the composite material can be improved by using the thermal initiator with this composition.

[0048] Furthermore, additives can be added during the mixing process of the vinyl ester resin, reactive diluent, ultraviolet light initiator, and thermal initiator. The additives include at least one of toughening agents, defoaming agents, and antioxidants. For example, toughening agents include, but are not limited to, styrene-based, polyolefin-based, polyester-based products, and nanoparticles, etc.; defoaming agents include, but are not limited to, silicone-based and polyether-modified silicone defoaming agents; antioxidants include, but are not limited to, hindered phenols and aromatic amine antioxidants.

[0049] S2: Immerse the carbon fiber into the mixed adhesive solution for photocuring

[0050] In some embodiments, immersing the carbon fiber into the mixed glue includes: using a winding device, immersing the carbon fiber into the mixed glue by a wet winding method and then winding it on the surface of the core mold. Specifically, the program parameters that need to be modified are input into the operating software of the winding device (CNCFW-1-600 model), the trolley, arm, and spindle of the winding device are returned to the starting position, the device is on standby, the one-way plate winding mold is installed, the carbon fiber spool is loaded and fixed, 300g to 500g of the mixed glue is added to the resin tank, the carbon fiber tow is pulled and fixed to the mold, the winding program is started, and the carbon fiber tow is soaked in the mixed glue and then wound on the mold.

[0051] Furthermore, the winding program parameters include: the winding method is hoop winding, the number of winding layers is 2 to 4 layers, the forward distance of the tow is 40 to 200 mm, the step is 0.5 to 0.8 times the width of a single bundle of yarn, the winding tension is 0 to 50 N, and the winding rate is 10 to 40° / min. Therefore, through the controllable molding process parameters of the winding equipment, it is easier to achieve continuous, uniform, and precise production of long fiber products; at the same time, this molding method is easy to combine with light curing technology to prepare high-performance light-curing composite materials.

[0052] According to an embodiment of the present invention, the carbon fiber includes continuous fibers with a tow specification of 3K to 12K, and different types can be selected according to product requirements, such as high-strength carbon fiber, high-modulus carbon fiber, high-strength medium-modulus carbon fiber, etc. The inventor found that the specifications of carbon fiber tows have a great influence on the design of winding molding process. If the number of carbon fiber tows is less than 3K, on ​​the one hand, the yarn sheet width of the tow itself is small, and it is easy to form gaps between the tows during the winding molding process. On the other hand, the fiber cannot withstand a certain degree of tension level, resulting in poor surface accuracy of the product, which will cause the comprehensive performance of the composite material to be significantly reduced; if the number of carbon fiber tows is greater than 12K, on ​​the one hand, the yarn sheet width of the tow is too large, and the fiber is prone to yarn folding and hair winding after passing through multiple rollers of the equipment. On the other hand, the resin is not easy to fully infiltrate the large tow fibers, resulting in uneven resin content between various parts of the product, large differences in curing degree after curing, and even defects caused by resin shrinkage, which is also not conducive to the high performance of composite products. Therefore, the use of the carbon fiber specifications of the present application is conducive to the production process of the winding molding process, and can effectively improve the production efficiency and comprehensive performance of the product.

[0053] In some embodiments, the photocuring includes: after removing the sample wound on the surface of the core mold from the mold, transferring it to under an ultraviolet lamp device for light irradiation first, and then transferring it to under an infrared lamp device for light irradiation. Specifically, through the irradiation of ultraviolet light, the surface layer adhesive of the prepreg undergoes photocuring and releases a thermal effect, and the temperature of the product rises initially; then through the irradiation of infrared light, the photothermal effect of the carbon fiber further increases the temperature of the product, enabling the deep layer adhesive to fully undergo photothermal curing, and finally obtaining a thoroughly cured carbon fiber composite material.

[0054] Furthermore, the wavelength range of the ultraviolet light of the ultraviolet lamp device is 320 - 400 nm; and / or the irradiation power of the ultraviolet lamp device is 100 - 200 W; and / or the irradiation distance of the ultraviolet device is 5 - 30 cm; and / or the irradiation time of the ultraviolet lamp device is 1 - 2 min; the ambient temperature during the photocuring process is 20 - 50 °C.

[0055] Furthermore, the wavelength range of the infrared light of the infrared lamp device is 750 - 1500 nm; and / or the irradiation power of the infrared lamp device is 1000 - 2000 W; and / or the irradiation distance of the infrared device is 5 - 20 cm; and / or the irradiation time of the infrared lamp device is 5 - 10 min.

[0056] Furthermore, before curing the obtained wound sample, a permeable paper or a transparent glass plate is pre-fixed on the surface of the sample to improve the surface quality of the product through surface processing.

[0057] The present invention provides a method for preparing a carbon fiber reinforced resin matrix composite material through winding molding and photocuring. According to the method of the embodiments of the present invention, not only can the production efficiency of the carbon fiber reinforced resin matrix composite material be significantly improved and the energy consumption during the curing and molding process be reduced, but also the high-precision and stable process molding process effectively guarantees the high performance of the product. Specifically, the tensile strength of the photocuring mixed adhesive in the composite material obtained by the present invention can reach 77.8 MPa, and the tensile modulus can reach 1.92 GPa, indicating that the mixed adhesive has good mechanical properties and meets the requirements of composite material applications; the curing time of the carbon fiber reinforced resin matrix composite material obtained by the present invention is within 11 min, the tensile strength can reach 1686 MPa, and the tensile modulus can reach 89.1 GPa, indicating that the unidirectional plate of the composite material has excellent mechanical properties.

[0058] The second aspect of the present invention provides a carbon fiber reinforced resin matrix composite material, which is prepared by using the method described in the first aspect. It should be noted that the above-mentioned characteristics and advantages for preparing the carbon fiber reinforced resin matrix composite material also apply to this carbon fiber reinforced resin matrix composite material, and will not be elaborated here.

[0059] The present invention will be further described by way of examples below, but the protection scope of the present invention is not limited to these embodiments. The present invention can also have various other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes and deformations should all fall within the protection scope of the appended claims of the present invention.

[0060] Example 1

[0061] (1) Weigh 75 g of vinyl ester resin bisphenol A dimethacrylate, 210 g of reactive diluent 2-hydroxy-3-phenoxypropyl acrylate, and 2.85 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, heat to 40 °C through an ultrasonic oscillator and disperse for 30 min to promote uniform mixing. After cooling, add 2.85 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Then, evacuate to -0.2 MPa through a vacuum drying oven for 30 min to remove bubbles and obtain a mixed adhesive solution.

[0062] (2) Design a winding molding program and set the following winding program parameters: the winding method is circumferential winding, the number of winding layers is 4 layers, the forward distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 0 N, and the winding rate is 40° / min. After returning the trolley, boom, and spindle of the winding equipment to the starting position, the equipment stands by. Install a unidirectional plate winding mold with specifications of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, infiltrate the 12K carbon fiber tow using an epoxy sizing agent (the epoxy sizing agent includes 100 parts by weight of water, 3 parts by weight of epoxy resin (E51), and 0.7 parts by weight of polyoxyethylene ether emulsifier (OP-10), and the solid content of the epoxy sizing agent is 2.5%) into the mixed adhesive solution, tow and fix it to the mold, and start the winding program.

[0063] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it under an ultraviolet lamp and cure with 160 W ultraviolet light at room temperature for 10 s, then transfer it under an infrared lamp and cure with 1200 W infrared light for 10 min, and cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate. Figure 1 It is the corresponding photocuring temperature curve. As can be seen from the figure, when irradiated with ultraviolet light for 10 s, the temperature of the sample rises initially. When irradiated with infrared light for 10 min, the temperature of the sample further increases, and the curing exothermic reaction occurs completely.

[0064] Example 2

[0065] (1) Weigh 75 g of vinyl ester resin bisphenol A dimethacrylate, 210 g of reactive diluent 2-hydroxy-3-phenoxypropyl acrylate, and 2.85 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, and heat them to 40 °C through an ultrasonic oscillator and disperse for 30 min to promote uniform mixing. After cooling, add 2.85 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Then, evacuate to -0.2 MPa through a vacuum drying oven for 30 min to remove bubbles, and the required mixed adhesive solution is obtained.

[0066] (2) Design a winding molding program and set the following winding program parameters: the winding method is circumferential winding, the number of winding layers is 4 layers, the forward distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 15 N, and the winding speed is 40° / min. After returning the trolley, boom, and main shaft of the winding equipment to the starting position, the equipment is on standby. Install a unidirectional plate winding mold with specifications of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, immerse the 12K carbon fiber tow treated with epoxy sizing agent (the epoxy sizing agent includes 100 parts by weight of water, 3 parts by weight of epoxy resin (E51), and 0.7 parts by weight of polyoxyethylene ether emulsifier (OP-10), and the solid content of the epoxy sizing agent is 2.5%) into the mixed adhesive solution, and the mass ratio is approximately carbon fiber:mixed adhesive solution = 1:1. Then, tow and fix it to the mold and start the winding program.

[0067] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it under an ultraviolet lamp and cure it with 160 W ultraviolet light at room temperature for 10 s, and then transfer it to an infrared lamp device and cure it with 1200 W infrared light for 10 min. Cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate.

[0068] Example 3

[0069] (1) Weigh 75 g of vinyl ester resin bisphenol A dimethacrylate, 210 g of reactive diluent 2-hydroxy-3-phenoxypropyl acrylate, and 2.85 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, and heat them to 40 °C through an ultrasonic oscillator and disperse for 30 min to promote uniform mixing. After cooling, add 2.85 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Then, evacuate to -0.2 MPa through a vacuum drying oven for 30 min to remove bubbles, and the required mixed adhesive solution is obtained.

[0070] (2) Design the winding forming process and set the following winding process parameters: the winding method is circumferential winding, the number of winding layers is 4 layers, the advancing distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 30 N, the winding speed is 40° / min. After returning the trolley, boom, and main shaft of the winding equipment to the starting position, the equipment stands by. Install a unidirectional plate winding mold with specifications of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, immerse the 12K carbon fiber tow treated with epoxy sizing agent (the epoxy sizing agent includes 100 parts by weight of water, 3 parts by weight of epoxy resin (E51), and 0.7 parts by weight of polyoxyethylene ether emulsifier (OP-10), and the solid content of the epoxy sizing agent is 2.5%) in the mixed adhesive solution, traction and fix it to the mold, and start the winding process.

[0071] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it under the ultraviolet lamp equipment and cure it with 160 W ultraviolet light for 10 s at room temperature, then transfer it to the infrared lamp equipment and cure it with 1200 W infrared light for 10 min, and cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate.

[0072] Example 4

[0073] (1) Weigh 75 g of vinyl ester resin bisphenol A dimethacrylate, 210 g of reactive diluent 2-hydroxy-3-phenoxypropyl acrylate, and 2.85 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, heat it to 40 °C with an ultrasonic oscillator and disperse it for 30 min to promote uniform mixing. After cooling, add 2.85 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Evacuate it to -0.2 MPa with a vacuum drying oven for 30 min to remove bubbles and obtain the required mixed adhesive solution.

[0074] (2) Design the winding forming process and set the following winding process parameters: the winding method is circumferential winding, the number of winding layers is 4 layers, the forward distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 30 N, the winding speed is 40° / min. After returning the trolley, boom, and spindle of the winding equipment to the starting position, the equipment stands by. Install a unidirectional plate winding mold with a specification of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, soak the 12K carbon fiber tow using vinyl sizing agent (the vinyl resin sizing agent includes 100 parts by weight of water, 3 parts by weight of acrylic acid modified bisphenol A type epoxy resin, and 0.7 parts by weight of polyoxyethylene ether emulsifier (OP-10), and the solid content of the vinyl resin sizing agent is 2.5%), the mass ratio is approximately carbon fiber:mixed adhesive solution = 1:1, tow and fix it to the mold, and start the winding process.

[0075] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it to an ultraviolet lamp device and cure it with 160 W ultraviolet light at room temperature for 10 s, then transfer it to an infrared lamp device and cure it with 1200 W infrared light for 10 min, and cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate.

[0076] Example 5

[0077] (1) Weigh 75 g of vinyl ester resin bisphenol A dimethacrylate, 210 g of reactive diluent 2-hydroxy-3-phenoxypropyl acrylate, and 2.85 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, heat it to 40°C with an ultrasonic oscillator and disperse for 30 min to promote uniform mixing. After cooling, add 2.85 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Vacuumize to -0.2 MPa with a vacuum drying oven for 30 min to obtain the required mixed adhesive solution.

[0078] (2) Design the winding forming process and set the following winding process parameters: The winding method is circumferential winding, the number of winding layers is 4 layers, the advancing distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 30 N, and the winding speed is 40° / min. After returning the trolley, boom, and spindle of the winding equipment to the starting position, the equipment stands by. Install a unidirectional plate winding mold with specifications of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, soak the 12K carbon fiber tow treated with polyurethane sizing agent (the raw materials of the polyurethane sizing agent include isophorone diisocyanate and polyether polyol (PEG2000) with a mass ratio of 1:10 reactants, polyoxyethylene ether emulsifier (OP-10), and water. Among them, the mass ratio of water to the reactants of isophorone diisocyanate and polyether polyol and polyoxyethylene ether emulsifier is 100:3:0.7, and the solid content of the polyurethane sizing agent is 2.5%) in the mixed adhesive solution, and the mass ratio is approximately carbon fiber: mixed adhesive solution = 1:1. Then tow and fix it to the mold and start the winding process.

[0079] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it to an ultraviolet lamp device and cure it with 160 W ultraviolet light at room temperature for 10 s, then transfer it to an infrared lamp device and cure it with 1200 W infrared light for 10 min, and cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate.

[0080] Example 6

[0081] (1) Weigh 75 g of bisphenol A ethoxylate diacrylate, 210 g of reactive diluent diallyl terephthalate, and 2.85 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, heat it to 40 °C with an ultrasonic oscillator and disperse for 30 min to promote uniform mixing. After cooling, add 2.85 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Vacuumize to -0.2 MPa with a vacuum drying oven for 30 min to remove bubbles and obtain the required mixed adhesive solution.

[0082] (2) Design the winding forming process and set the following winding process parameters: the winding method is circumferential winding, the number of winding layers is 4 layers, the advancing distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 30 N, and the winding speed is 40° / min. After returning the trolley, boom, and main shaft of the winding equipment to the starting position, the equipment stands by. Install a unidirectional plate winding mold with specifications of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, immerse the 12K carbon fiber tow using an epoxy sizing agent (the epoxy sizing agent includes 100 parts by weight of water, 3 parts by weight of epoxy resin (E51), and 0.7 parts by weight of polyoxyethylene ether emulsifier (OP-10), and the solid content of the epoxy sizing agent is 2.5%) in the mixed adhesive solution, tow and fix it to the mold, and start the winding program.

[0083] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it to an ultraviolet lamp device and cure it with 160 W ultraviolet light at room temperature for 10 s, then transfer it to an infrared lamp device and cure it with 1200 W infrared light for 10 min, and cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate.

[0084] Example 7

[0085] (1) Weigh 75 g of bisphenol A ethoxylate diacrylate, 210 g of reactive diluent diallyl terephthalate, and 2.85 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, heat it to 40 °C with an ultrasonic oscillator and disperse it for 30 min to promote uniform mixing. After cooling, add 2.85 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Evacuate to -0.2 MPa with a vacuum drying oven for 30 min to remove bubbles and obtain the required mixed adhesive solution.

[0086] (2) Design the winding forming process and set the following winding process parameters: the winding method is circumferential winding, the number of winding layers is 4 layers, the advancing distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 30 N, and the winding speed is 40° / min. After returning the trolley, boom, and main shaft of the winding equipment to the starting position, the equipment stands by. Install a unidirectional plate winding mold with specifications of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, immerse the 12K carbon fiber tow using a vinyl sizing agent (the epoxy sizing agent includes 100 parts by weight of water, 3 parts by weight of epoxy resin (E51), and 0.7 parts by weight of polyoxyethylene ether emulsifier (OP-10), and the solid content of the epoxy sizing agent is 2.5%) in the mixed adhesive solution, tow and fix it to the mold, and start the winding program.

[0087] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it under an ultraviolet lamp and cure it with 160 W ultraviolet light at room temperature for 10 s, then transfer it to an infrared lamp and cure it with 1200 W infrared light for 10 min, and cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate.

[0088] Example 8

[0089] (1) Weigh 60 g of vinyl ester resin bisphenol A dimethacrylate, 180 g of reactive diluent 2-hydroxy-3-phenoxypropyl acrylate, and 1.20 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, heat it to 40 °C with an ultrasonic oscillator and disperse it for 30 min to promote uniform mixing. After cooling, add 3.60 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Evacuate to -0.2 MPa with a vacuum drying oven for 30 min to obtain the required mixed adhesive solution.

[0090] (2) Design the winding forming program and set the following winding program parameters: the winding method is circumferential winding, the number of winding layers is 4 layers, the forward distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 30 N, and the winding speed is 40 ° / min. After returning the trolley, boom, and main shaft of the winding equipment to the starting position, the equipment stands by. Install a unidirectional plate winding mold with specifications of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, immerse the 12K carbon fiber tow using vinyl sizing agent (the epoxy sizing agent includes 100 parts by weight of water, 3 parts by weight of epoxy resin (E51), and 0.7 parts by weight of polyoxyethylene ether emulsifier (OP-10), and the solid content of the epoxy sizing agent is 2.5%), and the mass ratio is approximately carbon fiber:mixed adhesive solution = 1:1. Pull and fix it to the mold and start the winding program.

[0091] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it under an ultraviolet lamp and cure it with 160 W ultraviolet light at room temperature for 10 s, then transfer it to an infrared lamp and cure it with 1200 W infrared light for 10 min, and cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate.

[0092] Example 9

[0093] (1) Weigh 90 g of vinyl ester resin bisphenol A dimethacrylate, 180 g of reactive diluent 2-hydroxy-3-phenoxypropyl acrylate, and 1.35 g of ultraviolet light initiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. Mix the vinyl ester resin, reactive diluent, and ultraviolet light initiator, and heat them to 40 °C using an ultrasonic oscillator for 30 min to promote uniform mixing. After cooling, add 4.05 g of thermal initiator tert-butyl peroxy(2-ethylhexanoate) and mix evenly. Then, evacuate to -0.2 MPa using a vacuum drying oven for 30 min to remove bubbles, and the required mixed adhesive solution is obtained.

[0094] (2) Design a winding molding program and set the following winding program parameters: the winding method is circumferential winding, the number of winding layers is 4 layers, the forward distance of the tow is 60 mm, the step is 1.6 mm, the winding tension is 30 N, and the winding rate is 40° / min. After returning the trolley, boom, and spindle of the winding equipment to the starting position, the equipment is on standby. Install a unidirectional plate winding mold with specifications of 300 mm * 300 mm * 4 mm, load and fix the carbon fiber spool, add the mixed adhesive solution prepared in step (1) to the resin tank, immerse the 12K carbon fiber tow treated with vinyl sizing agent (the epoxy sizing agent includes 100 parts by weight of water, 3 parts by weight of epoxy resin (E51), and 0.7 parts by weight of polyoxyethylene ether emulsifier (OP-10), and the solid content of the epoxy sizing agent is 2.5%) in the mixed adhesive solution, with a mass ratio of carbon fiber:mixed adhesive solution approximately 1:1, tow and fix it to the mold, and start the winding program.

[0095] (3) Remove the unidirectional plate winding mold, fix a layer of permeable paper on the surface of the obtained sample, first transfer it under an ultraviolet lamp and cure it with 160 W ultraviolet light at room temperature for 10 s, then transfer it to an infrared lamp device and cure it with 1200 W infrared light for 10 min, and cut and process the plate to obtain a carbon fiber reinforced resin matrix composite unidirectional plate.

[0096] Performance Test

[0097] 1. Curing process characterization: Use an infrared thermal imager to characterize the macroscopic curing process of the sample under different conditions, so as to monitor the curing process of the composite material. During the photothermal curing process, fix the infrared imager in a suitable position for filming, and use the supporting IR discovery software to process the infrared imaging video results to obtain the average temperature-time curve of the rectangular area on the surface of the sample.

[0098] 2. Composite material structure characterization: Use the method of measuring mass and volume to measure the mass and volume of the resin, carbon fiber, and composite material, and calculate the corresponding density.

[0099] m 复材 = m 树脂 + m纤维

[0100] V 复材 = V 树脂 + V 纤维 V 孔隙

[0101] Fiber% = 100% * V 纤维 / V 复材 , Pore% = 100 * V 孔隙 / V 复材 For the mixed adhesive solution and the composite spline, weigh the mass with a balance respectively, immerse the sample in deionized water filled in a graduated cylinder to measure the volume, and calculate the density; for carbon fiber, measure its bulk density with a density gradient instrument, calcine a certain mass of the composite material in a muffle furnace at 400 °C for 60 min, weigh the fiber mass after cooling, and calculate its volume. The mass of the pores is neglected, and the volume ratio is obtained through calculation.

[0102] 3. Mechanical property characterization: According to GB / T 3354-2014, cut the unidirectional plates of the carbon fiber reinforced resin matrix composites prepared in Examples 1-9 into tensile specimens of 250 mm * 12.5 mm * 1 mm, and paste non-woven fabric reinforced composite material reinforcement sheets of 50 mm * 12.5 mm * 1 mm at both ends. Each group of specimens has no less than 5. Use an Instron 6800 universal material testing machine to continuously load the samples at a speed of 2 mm / min at room temperature, record the load-displacement results of the specimens, and calculate the tensile strength and tensile modulus as the mechanical property results of the products.

[0103]

[0104] Among them, σ —— the tensile strength of the specimen, unit: MPa; P max —— the maximum load borne by the specimen before failure, unit: N; w —— the width of the specimen, unit: mm; h —— the thickness of the specimen, unit: mm.

[0105]

[0106] Among them, E —— the tensile modulus of the specimen, unit: GPa; Δσ —— the increment of the tensile strength of the specimen within the longitudinal strain range of 0.001 - 0.003, unit: MPa; Δε —— the strain increment of the specimen within the longitudinal strain range of 0.001 - 0.003, unit: mm / mm.

[0107] The above test results are shown in Table 1.

[0108] Table 1 Structural properties of the unidirectional plates of the carbon fiber reinforced resin matrix composites prepared in each example of the present invention

[0109]

[0110]

[0111] As can be seen from the results in Table 1, the curing times of the composite materials in Examples 1-9 are all within 11 min, and the tensile strength is not lower than 1116 MPa, and the tensile modulus is not lower than 70.9 GPa, indicating that the method for preparing the carbon fiber reinforced resin matrix composite material of the present invention using vinyl ester resin, reactive diluent, ultraviolet light initiator, thermal initiator and carbon fiber as raw materials not only has a short curing time, but also the obtained composite material has excellent mechanical properties. At the same time, in Examples 1-3 of the present invention, as the winding tension gradually increases, more resin is scraped out after the fiber passes through the roller, making the fiber volume content of the composite product higher, and the fibers are arranged more closely to each other, thereby endowing the composite material with a more perfect structure and better performance.

[0112] As described above, the above are only specific embodiments of the invention covered by the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should all be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A method for preparing a carbon fiber reinforced resin-based composite material, characterized in that: include: (1) mixing a vinyl ester resin, a reactive diluent, an ultraviolet light initiator and a thermal initiator to obtain a mixed glue solution; (2) Immersing the carbon fiber into the mixed adhesive solution for photocuring to obtain a composite material.

2. The method according to claim 1, characterized in that The mass ratio of the vinyl ester resin, the reactive diluent, the ultraviolet light initiator and the thermal initiator is (10-20):(20-30):(0.1-0.5):(0.3-0.6).

3. The method according to claim 1 or 2, characterized in that: In step (1), the vinyl ester resin, the reactive diluent, the ultraviolet light initiator and the thermal initiator are mixed to prepare the mixed glue solution, which comprises: The vinyl ester resin, the active diluent and the ultraviolet light initiator are mixed and ultrasonically treated with heating, and a thermal initiator is added after cooling, and then degassing is performed in a vacuum drying oven to obtain a mixed glue solution; Optionally, the heating temperature is 40-60°C; Optionally, the ultrasonic treatment time is 20min-30min; Optionally, the vacuum degree of the degassing process is -0.1 to -0.3 MPa, and the processing time is 20 min to 30 min.

4. The method according to claim 1 or 2, characterized in that: In step (1), an auxiliary agent is added during the mixing of the vinyl ester resin, the reactive diluent, the ultraviolet light initiator and the thermal initiator. The auxiliary agent includes at least one of a toughening agent, a defoaming agent and an antioxidant.

5. The composite material according to claim 1 or 2, characterized in that: In step (1), the vinyl ester resin includes at least one of bisphenol A epoxy acrylate, novolac epoxy acrylate, epoxidized oil acrylate and modified epoxy acrylate.

6. The composite material according to claim 1 or 2, characterized in that: In step (1), the reactive diluent includes at least one of a monofunctional acrylate derivative, a difunctional acrylate derivative, and a multifunctional acrylate derivative; Optionally, in step (1), the ultraviolet light initiator comprises at least one of acylphosphine oxides, benzophenone compounds and benzil compounds. Optionally, in step (1), the thermal initiator comprises at least one of acyl peroxide, ester peroxide and keto peroxide.

7. The composite material according to claim 1 or 2, characterized in that: In step (2), the tow specification of the carbon fiber is 3K to 12K.

8. The method according to claim 1 or 2, characterized in that: In step (2), immersing the carbon fiber into the mixed glue solution comprises: using a winding device to immerse the carbon fiber into the mixed glue solution by a wet winding method and then winding the carbon fiber on the surface of the core mold; Optionally, the parameters of the winding device include at least one of the following: The winding method of the winding device is hoop winding; The number of carbon fiber winding layers is 2 to 4; The carbon fiber tow advances a distance of 40 to 200 mm; The stepping of the carbon fiber bundle is 0.5 to 0.8 times the width of a single bundle yarn sheet; The winding tension of the carbon fiber tow is 0 to 50N; The winding rate of the carbon fiber tow is 10-40° / min.

9. The method according to claim 8, characterized in that In step (2), the photocuring comprises: After removing the sample wrapped around the surface of the core mold from the mold, transfer it to a UV lamp device for illumination, and then transfer it to an infrared lamp device for illumination; Optionally, the ultraviolet light wavelength range of the ultraviolet lamp device is 320-400nm; Optionally, the irradiation power of the ultraviolet lamp device is 100-200W; Optionally, the irradiation distance of the ultraviolet device is 5 to 30 cm; Optionally, the irradiation time of the ultraviolet lamp device is 1 to 2 minutes; Optionally, the ambient temperature of the photocuring process is 20 to 50°C; Optionally, the infrared light wavelength range of the infrared lamp device is 750-1500nm; Optionally, the irradiation power of the infrared lamp device is 1000-2000W; Optionally, the irradiation distance of the infrared device is 5 to 20 cm; Optionally, the irradiation time of the infrared lamp device is 5 to 10 minutes.

10. A carbon fiber reinforced resin-based composite material, characterized in that: The method according to any one of claims 1 to 9 is used to prepare the present invention.

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