Epoxy resin system, preparation method thereof and application of epoxy resin system in preparation of carbon fiber layer of high-pressure hydrogen storage cylinder

Abstract

The invention provides an epoxy resin system, a preparation method thereof and application of the epoxy resin system in preparation of a carbon fiber layer of a high-pressure hydrogen storage cylinder, and relates to the technical field of epoxy resin materials. The epoxy resin system contains epoxy resin, thermoplastic resin and a thixotropic agent. Due to the existence of the thixotropic agent, the viscosity of the epoxy resin system can be greatly reduced under the action of increased temperature and shear force; and in a normal temperature state, due to the existence of the thermoplastic resin, higher viscosity is presented. Therefore, the epoxy resin system has the characteristics of being in a high-viscosity state at normal temperature and being in a low-viscosity state under the action of increased temperature and shear force. The epoxy resin system can be widely applied to the preparation process of the carbon fiber layer of the high-pressure hydrogen storage cylinder.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resin materials, and in particular to an epoxy resin system, a preparation method thereof, and an application thereof in the preparation of a carbon fiber layer of a high-pressure hydrogen storage cylinder. Background Art

[0002] Hydrogen energy is a recognized clean energy with only water as a by-product, and it is the energy with the broadest development prospects in the future. The main current methods for storing and transporting hydrogen are high-pressure gaseous hydrogen storage. Especially in the context of new energy, high-pressure hydrogen storage cylinders have broad prospects in the field of hydrogen storage and great application prospects in the field of on-vehicle hydrogen storage.

[0003] At present, for the preparation process of the outer carbon fiber layer of high-pressure hydrogen storage cylinders, there are two mainstream forming methods: wet winding and dry winding. Among them:

[0004] The wet winding process refers to a method of directly winding the carbon fiber dry yarn impregnated with a low-viscosity liquid resin on a cylinder mandrel. Its advantages are simple process and low cost. The dry winding process refers to a process of first impregnating the carbon fiber dry yarn with a high-viscosity resin to obtain a prepreg tape, which can be stored for a long time and used as needed. Then, a process of using the prepreg tape to wind and form on a cylinder mandrel is adopted. Its advantages are stable winding process, stable resin content, and applicability to a wider range of winding processes.

[0005] However, both of the above two winding processes have certain disadvantages. The main problem is that the dry winding process has a complex process flow, high requirements for personnel and equipment, and high costs; while the wet winding process has a poor environmental condition, easy resin migration, uncontrollable resin content, resulting in unstable cylinder quality, and the wet winding process is prone to yarn slippage and cannot achieve a more excellent winding linearity.

[0006] In view of this, the present invention is specifically proposed. Summary of the Invention

[0007] The first object of the present invention is to provide an epoxy resin system, which can achieve the characteristic of being in a high-viscosity state at normal temperature and in a low-viscosity state under the action of elevated temperature and shear force.

[0008] The second object of the present invention is to provide a preparation method of an epoxy resin system.

[0009] The third object of the present invention is to provide an application of an epoxy resin system.

[0010] In order to achieve the above objects of the present invention, the following technical solutions are specifically adopted:

[0011] An epoxy resin system provided by the present invention includes: epoxy resin, thermoplastic resin, and thixotropic agent.

[0012] Further, the epoxy resin includes at least one of liquid bisphenol A diglycidyl ether, liquid bisphenol F diglycidyl ether, liquid glycidyl ester epoxy resin, and liquid aliphatic glycidyl ether epoxy resin;

[0013] The thermoplastic resin includes at least one of ultra-high molecular weight epoxy resin, polyether ketone, and polyether ether ketone;

[0014] The thixotropic agent includes at least one of fumed silica, organic bentonite, hydrogenated castor oil, and polyamide wax.

[0015] Further, the epoxy resin system further includes:

[0016] Toughening agent, curing agent, and accelerator.

[0017] Furthermore, the toughening agent includes at least one of liquid rubber and core-shell nanoparticles.

[0018] The curing agent includes at least one of liquid anhydride curing agents, amine curing agents, and polyetheramine curing agents;

[0019] Preferably, the curing agent includes one or a combination of several of methyltetrahydrophthalic anhydride (Me-THPA), methylhexahydrophthalic anhydride (Me-HHPA), methylnadic anhydride (MNA), and isophoronediamine (IPD);

[0020] The accelerator includes tertiary amines and their salts or imidazole accelerators;

[0021] Preferably, the accelerator includes one or a combination of several of 2,4-imidazole (2,4-EMI), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), and N,N-dimethylbenzylamine (BDMA).

[0022] Further, by mass, the epoxy resin system includes:

[0023] 30-50 parts of epoxy resin, 20-40 parts of thermoplastic resin, 10-30 parts of toughening agent, 3-15 parts of thixotropic agent, 40-80 parts of curing agent, and 1-6 parts of accelerator;

[0024] Preferably, by mass, the epoxy resin system includes:

[0025] 50 parts of epoxy resin, 25 parts of thermoplastic resin, 20 parts of toughening agent, 10 parts of thixotropic agent, 60 parts of curing agent, and 3 parts of accelerator.

[0026] A preparation method of the above epoxy resin system provided by the present invention, the method includes:

[0027] (A), Mix epoxy resin, thermoplastic resin, toughening agent, and thixotropic agent and shear-disperse them to obtain Resin A;

[0028] (B), Mix the curing agent and accelerator and shear-disperse them to obtain Resin B;

[0029] (C), Mix Resin A and Resin B and shear-disperse them to obtain an epoxy resin system.

[0030] Further, the conditions for shear dispersion in step (A) satisfy at least one of the following: the shear speed is 200 - 2000 rpm, the temperature is 90 - 110 °C, and the shear dispersion time is 2 h;

[0031] The conditions for shear dispersion in step (B) satisfy at least one of the following: the shear speed is 200 - 800 rpm, the temperature is 30 - 35 °C, and the shear dispersion time is 0.5 h;

[0032] The conditions for shear dispersion in step (C) satisfy at least one of the following: the shear speed is 200 - 1000 rpm, the temperature is 50 °C, and the shear dispersion time is 0.5 h.

[0033] Further, the mass ratio of Resin A to Resin B in step (C) is 100:65 - 85.

[0034] The present invention provides an application of the above epoxy resin system in preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder.

[0035] Further, the application includes:

[0036] Add the shear-dispersed epoxy resin system into an impregnation tank, pass the carbon fiber dry yarn through the impregnation tank, and wind it onto the inner liner of the gas cylinder by the wet winding method to form a carbon fiber layer;

[0037] During the winding process, the temperature of the epoxy resin system in the impregnation tank is 30 - 60 °C.

[0038] Compared with the prior art, the beneficial effects of the present invention are:

[0039] The epoxy resin system provided by the present invention contains epoxy resin, thermoplastic resin, and thixotropic agent. Due to the presence of the thixotropic agent, the viscosity of this epoxy resin system will be greatly reduced under the action of elevated temperature and shear force; while at room temperature, due to the presence of the thermoplastic resin, it shows a relatively high viscosity. Therefore, the above epoxy resin system can achieve the characteristics of being in a high-viscosity state at room temperature and a low-viscosity state under the action of elevated temperature and shear force.

[0040] The preparation method of the epoxy resin system provided by the present invention prepares the epoxy resin system by means of shear dispersion. Specifically: epoxy resin, thermoplastic resin, toughening agent, and thixotropic agent are mixed and then shear-dispersed to obtain resin A; at the same time, the curing agent and accelerator are mixed evenly and then shear-dispersed to obtain resin B; subsequently, resin A and resin B are mixed evenly and then shear-dispersed to obtain the epoxy resin system. The above preparation method has the advantages of simple preparation process and easy operation.

[0041] The above epoxy resin system provided by the present invention can be widely applied to the preparation process of the carbon fiber layer of high-pressure hydrogen storage cylinders. Specific embodiments

[0042] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0043] According to one aspect of the present invention, an epoxy resin system, the epoxy resin system includes: epoxy resin, thermoplastic resin, and thixotropic agent.

[0044] The epoxy resin system provided by the present invention contains epoxy resin, thermoplastic resin, and thixotropic agent. Due to the presence of the thixotropic agent, the viscosity of the epoxy resin system will be greatly reduced under the action of elevated temperature and shear force; while at room temperature, due to the presence of the thermoplastic resin, it exhibits a relatively high viscosity. Therefore, the above epoxy resin system can achieve the characteristics of being in a high-viscosity state at room temperature and in a low-viscosity state under the action of elevated temperature and shear force.

[0045] Note: The room temperature refers to 20-25°C; the elevated temperature refers to the temperature rising to 30-60°C.

[0046] It should be noted that the present invention introduces a thixotropic agent into the epoxy resin system, which improves the viscosity of the resin in a static state and ensures the stability of its resin content; while the viscosity of the epoxy resin system is greatly reduced under shear conditions, significantly improving the wettability.

[0047] In a preferred embodiment of the present invention, the epoxy resin includes at least one of liquid bisphenol A diglycidyl ether, liquid bisphenol F diglycidyl ether, liquid glycidyl ester epoxy resin, and liquid aliphatic glycidyl ether epoxy resin;

[0048] The thermoplastic resin includes at least one of ultra-high molecular weight epoxy resin (PKHH), polyether ketone (PEK), and polyether ether ketone (PEEK);

[0049] The thixotropic agent includes at least one of fumed silica, organic bentonite, hydrogenated castor oil, and polyamide wax.

[0050] In a preferred embodiment of the present invention, the epoxy resin system further includes: a toughening agent, a curing agent, and an accelerator.

[0051] As a preferred embodiment, the function of the above-mentioned toughening agent in the epoxy resin system is to toughen and modify the epoxy resin system of the present application.

[0052] As a preferred embodiment, the function of the above-mentioned curing agent in the epoxy resin system is to react with the epoxy groups in the epoxy resin system to form a crosslinked network by curing.

[0053] As a preferred embodiment, the function of the above-mentioned accelerator in the epoxy resin system is to promote the reaction between the curing agent and the epoxy groups.

[0054] In the above preferred embodiment, the toughening agent includes at least one of liquid rubber and core-shell nanoparticles.

[0055] In the above preferred embodiment, the curing agent includes at least one of liquid anhydride curing agents, amine curing agents, and polyetheramine curing agents;

[0056] Preferably, the curing agent includes one or a combination of several of Me-THPA, Me-HHPA, MNA, and IPD;

[0057] In the above preferred embodiment, the accelerator includes tertiary amines and their salts or imidazole accelerators;

[0058] Preferably, the accelerator includes one or a combination of several of 2,4-EMI, DMP-30, and BDMA.

[0059] In a preferred embodiment of the present invention, by mass, the epoxy resin system includes:

[0060] 30-50 parts of epoxy resin, 20-40 parts of thermoplastic resin, 10-30 parts of toughening agent, 3-15 parts of thixotropic agent, 40-80 parts of curing agent, and 1-6 parts of accelerator;

[0061] Preferably, by mass, the epoxy resin system includes:

[0062] 50 parts of epoxy resin, 25 parts of thermoplastic resin, 20 parts of toughening agent, 10 parts of thixotropic agent, 60 parts of curing agent, and 3 parts of accelerator.

[0063] In the present invention, by further adjusting and optimizing the dosage ratio of each component raw material, the technical effect of the epoxy resin system of the present invention is further optimized.

[0064] According to one aspect of the present invention, a method for preparing the above epoxy resin system, the method comprising:

[0065] (A) Mixing epoxy resin, thermoplastic resin, toughening agent, and thixotropic agent and then subjecting them to shear dispersion to obtain resin A;

[0066] (B) Mixing the curing agent and accelerator evenly and then subjecting them to shear dispersion to obtain resin B;

[0067] (C) Mixing resin A and resin B evenly and then subjecting them to shear dispersion to obtain the epoxy resin system.

[0068] The method for preparing the epoxy resin system provided by the present invention prepares the epoxy resin system by means of shear dispersion. Specifically: epoxy resin, thermoplastic resin, toughening agent, and thixotropic agent are mixed and then subjected to shear dispersion to obtain resin A; at the same time, the curing agent and accelerator are mixed evenly and then subjected to shear dispersion to obtain resin B; subsequently, resin A and resin B are mixed evenly and then subjected to shear dispersion to obtain the epoxy resin system. The above preparation method has the advantages of simple preparation process and easy operation.

[0069] In a preferred embodiment of the present invention, the conditions for shear dispersion in step (A) satisfy at least one of the following: the shear speed is 200 - 2000 rpm, the temperature is 90 - 110 °C, and the shear dispersion time is 2 h;

[0070] In a preferred embodiment of the present invention, the conditions for shear dispersion in step (B) satisfy at least one of the following: the shear speed is 200 - 800 rpm, the temperature is 30 - 35 °C, and the shear dispersion time is 0.5 h;

[0071] In a preferred embodiment of the present invention, the conditions for shear dispersion in step (C) satisfy at least one of the following: the shear speed is 200 - 1000 rpm, the temperature is 50 °C, and the shear dispersion time is 0.5 h.

[0072] In a preferred embodiment of the present invention, the mass ratio of resin A to resin B in step (C) is 100:65 - 85.

[0073] As a preferred embodiment, the mass ratio of resin A to resin B in step (C) is 100:65 - 85. The epoxy resin system obtained by mixing and shear dispersion in the above mass ratio has a better curing effect, while the epoxy resin system prepared outside the above mass ratio range has a poor curing effect and the various properties of the resin will decline.

[0074] According to one aspect of the present invention, an application of the above epoxy resin system in preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder.

[0075] The above epoxy resin system provided by the present invention can be widely applied to the preparation process of the carbon fiber layer of high-pressure hydrogen storage cylinders.

[0076] In a preferred embodiment of the present invention, the application includes: adding the shear-dispersed epoxy resin system into an impregnation tank, passing the dry carbon fiber yarn through the impregnation tank, and winding it onto the inner liner of the gas cylinder by the wet winding method to form a carbon fiber layer;

[0077] During the winding process, the temperature of the epoxy resin system in the impregnation tank is 30-60°C.

[0078] As a preferred embodiment, adding the shear-dispersed epoxy resin system into the impregnation tank and maintaining the temperature at 30-60°C can effectively maintain the low-viscosity state of the epoxy resin system.

[0079] It should be noted that during the preparation process of the carbon fiber layer of the high-pressure hydrogen storage cylinder in this application, due to the characteristic that the epoxy resin system can be in a high-viscosity state at normal temperature and in a low-viscosity state under the action of elevated temperature and shear force, the resin in the impregnation tank is under the action of both temperature and shear force, with a low viscosity and excellent impregnation effect; when the impregnation is completed and the carbon fiber impregnated with the resin solution leaves the impregnation tank, the temperature decreases and the shear force disappears, so the resin viscosity rises rapidly, the glue solution no longer migrates, and yarn slipping will not occur, and it can be applicable to various winding linearities. At the same time, existing wet winding equipment can be directly used, and there are no special requirements for personnel; and it is environmentally friendly. By stably controlling the resin content of the carbon fiber, the quality of the gas cylinder is stable, taking into account the advantages of the wet winding process and the dry winding process and avoiding the disadvantages of the two process methods.

[0080] Next, the technical solution of the present invention will be further described in combination with examples and comparative examples.

[0081] Example 1

[0082] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, including:

[0083] (1), adding 50 parts of bisphenol A diglycidyl ether, 20 parts of ultra-high molecular weight epoxy resin (PKHH), 10 parts of liquid rubber, and 5 parts of organic bentonite into a mixing kettle for high-speed shear dispersion, with a shear speed of 2000 rpm, a temperature of 100°C, and a mixing time of 2 h to obtain resin component A.

[0084] (2), adding 50 parts of Me-THPA, 1 part of 2,4-EMI, and 1 part of BDMA into a mixing kettle for high-speed shear dispersion, with a shear speed of 800 rpm, a temperature of 30°C, and a mixing time of 0.5 h to obtain resin component B.

[0085] (3) Resin components A and B can be stored separately. When in use, mix resin component A and resin component B according to a ratio of 100:70. Then perform high-speed shear dispersion at 1000 rpm for 0.5 h to obtain the final finished resin C.

[0086] (4) Add the finished resin C to an impregnation tank at 50°C, and pass the carbon fiber dry yarn through the impregnation tank and wind it around the inner liner of the gas cylinder.

[0087] It is found that there is no dry yarn in the carbon fiber, and it can be completely impregnated with the sizing agent; moreover, the carbon fiber impregnated with resin C will not have resin migration when wound around the inner liner. After testing, the resin content is relatively stable.

[0088] Example 2

[0089] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, comprising:

[0090] (1) Add 50 parts of bisphenol F diglycidyl ether, 30 parts of ultra-high molecular weight epoxy resin (PKHH), 10 parts of core-shell nanoparticles, and 5 parts of fumed silica to a mixing kettle for high-speed shear dispersion. The shear speed is 1000 rpm, the temperature is 90°C, and the mixing time is 1.5 h to obtain resin component A.

[0091] (2) Add 55 parts of Me-HHPA, 0.5 part of 2,4-EMI, and 1 part of DMP-30 to a mixing kettle for high-speed shear dispersion. The shear speed is 800 rpm, the temperature is 35°C, and the mixing time is 0.5 h to obtain resin component B.

[0092] (3) Resin components A and B can be stored separately. When in use, mix resin component A and resin component B according to a ratio of 100:67. Then perform high-speed shear dispersion at 1000 rpm to obtain the final finished resin C.

[0093] (4) Add the finished resin C to an impregnation tank at 50°C, and pass the carbon fiber dry yarn through the impregnation tank and wind it around the inner liner of the gas cylinder.

[0094] It is found that there is no dry yarn in the carbon fiber, and it can be completely impregnated with the sizing agent; moreover, the carbon fiber impregnated with resin C will not have resin migration when wound around the inner liner. After testing, the resin content is relatively stable.

[0095] Example 3

[0096] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, comprising:

[0097] (1) Add 25 parts of liquid bisphenol F diglycidyl ether, 25 parts of liquid bisphenol A diglycidyl ether, 30 parts of ultra-high molecular weight epoxy resin (PKHH), 5 parts of core-shell nanoparticles, 5 parts of liquid rubber, and 5 parts of fumed silica into a mixing kettle for high-speed shear dispersion. The shear speed is 1000 rpm, the temperature is 100 °C, and the mixing time is 2 h to obtain resin component A.

[0098] (2) Add 55 parts of Me-HHPA, 0.5 part of 2,4-EMI, and 1 part of DMP-30 into a mixing kettle for high-speed shear dispersion. The shear speed is 800 rpm, the temperature is 35 °C, and the mixing time is 0.5 h to obtain resin component B.

[0099] (3) Resin components A and B can be stored separately. When in use, mix resin component A and resin component B according to a ratio of 100:80. Then perform high-speed shear dispersion at 1000 rpm to obtain the final finished resin C.

[0100] (4) Add the finished resin C into an impregnation tank at 50 °C, and pass the carbon fiber dry yarn through the impregnation tank and wind it around the inner liner of the gas cylinder.

[0101] It is found that there is no dry yarn in the carbon fiber and it can be completely impregnated with the sizing agent; moreover, the carbon fiber impregnated with resin C will not cause resin migration when wound around the inner liner. After testing, the resin content is relatively stable.

[0102] Example 4

[0103] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, comprising:

[0104] (1) Add 25 parts of liquid bisphenol F diglycidyl ether, 25 parts of liquid bisphenol A diglycidyl ether, 25 parts of ultra-high molecular weight epoxy resin (PKHH), 10 parts of core-shell nanoparticles, 10 parts of liquid rubber, and 10 parts of fumed silica into a mixing kettle for high-speed shear dispersion. The shear speed is 1000 rpm, the temperature is 110 °C, and the mixing time is 2 h to obtain resin component A.

[0105] (2) Add 30 parts of Me-THPA, 30 parts of Me-HHPA, 2 parts of 2,4-EMI, and 1 part of DMP-30 into a mixing kettle for high-speed shear dispersion. The shear speed is 800 rpm, the temperature is 30 °C, and the mixing time is 0.5 h to obtain resin component B.

[0106] (3) Resin components A and B can be stored separately. When in use, mix resin component A and resin component B according to a ratio of 100:80. Then perform high-speed shear dispersion at 1000 rpm to obtain the final finished resin C.

[0107] (4) Add the finished resin C to the impregnation tank at 50°C, and pass the dry carbon fiber yarn through the impregnation tank and wind it around the inner liner of the gas cylinder.

[0108] It is found that there is no dry carbon fiber yarn, and the sizing agent can be completely soaked; moreover, when the carbon fiber impregnated with resin C is wound around the inner liner, resin migration does not occur. After testing, the resin content is relatively stable.

[0109] Comparative Example 1

[0110] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, comprising:

[0111] (1) Add 50 parts of liquid bisphenol A diglycidyl ether and 10 parts of liquid rubber to the mixing kettle for high-speed shear dispersion. The shear speed is 1000 rpm, the temperature is 80°C, and the mixing time is 2 h to obtain resin component A.

[0112] In this comparative example, component A does not contain thermoplastic resin and thixotropic agent.

[0113] (2) Add 50 parts of Me-THPA, 1 part of 2,4-EMI, and 1 part of DMP-30 to the mixing kettle for high-speed shear dispersion. The shear speed is 800 rpm, the temperature is 30°C, and the mixing time is 0.5 h to obtain resin component B.

[0114] (3) Resin components A and B can be stored separately. When in use, mix resin component A and resin component B according to a ratio of 100:85. Then carry out high-speed shear dispersion at 1000 rpm to obtain the final finished resin C.

[0115] (4) Add the finished resin C to the impregnation tank at 30°C, and pass the dry carbon fiber yarn through the impregnation tank and wind it around the inner liner of the gas cylinder.

[0116] It is found that there is no dry carbon fiber yarn, and the sizing agent can be completely soaked; however, when the carbon fiber impregnated with resin C is wound around the inner liner, obvious resin migration occurs, and a large amount of sizing agent drips during the process. After testing, the resin content fluctuates greatly.

[0117] Comparative Example 2

[0118] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, comprising:

[0119] (1) Add 45 parts of liquid bisphenol F diglycidyl ether, 30 parts of liquid bisphenol A diglycidyl ether, 10 parts of core-shell nanoparticles, 10 parts of liquid rubber, and 10 parts of fumed silica to the mixing kettle for high-speed shear dispersion. The shear speed is 1000 rpm, the temperature is 110°C, and the mixing time is 2 h to obtain resin component A.

[0120] (2)-(4) The same as Example 4.

[0121] This comparative example is different from Example 4 in that it does not contain a thermoplastic resin (ultra-high molecular weight epoxy resin).

[0122] It was found that the resin viscosity was relatively low. The carbon fiber dry yarn was impregnated with the resin and wound around the gas cylinder mandrel, and there was still glue overflow after the temperature dropped.

[0123] Comparative Example 3

[0124] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, comprising:

[0125] (1) Add 30 parts of liquid bisphenol F diglycidyl ether, 30 parts of liquid bisphenol A diglycidyl ether, 25 parts of ultra-high molecular weight epoxy resin (PKHH), 10 parts of core-shell nanoparticles, and 10 parts of liquid rubber to a mixing kettle for high-speed shear dispersion. The shear speed is 1000 rpm, the temperature is 110 °C, and the mixing time is 2 h to obtain resin component A.

[0126] (2)-(4) are the same as Example 4.

[0127] This comparative example is different from Example 4 in that it does not contain a thixotropic agent (fumed silica).

[0128] It was found that the resin did not thin rapidly under the action of shear dispersion and the 50 °C impregnation tank, resulting in incomplete fiber impregnation and the presence of dry yarns.

[0129] Example 5

[0130] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, comprising:

[0131] (1)-(3) are the same as Example 4;

[0132] (4) Add finished resin C to an impregnation tank at 65 °C, and pass the carbon fiber dry yarn through the impregnation tank and wind it around the inner cylinder of the gas cylinder.

[0133] It was found that due to the too high impregnation temperature, the resin reacted in the impregnation tank, shortening the pot life of the resin.

[0134] Example 6

[0135] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage cylinder, comprising:

[0136] (1)-(3) are the same as Example 4;

[0137] (4) Add finished resin C to an impregnation tank at 22 °C, and pass the carbon fiber dry yarn through the impregnation tank and wind it around the inner cylinder of the gas cylinder.

[0138] It was found that due to the low impregnation temperature and high resin viscosity, the fiber could not completely absorb the carbon fiber, resulting in the existence of dry yarn.

[0139] Example 7

[0140] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage bottle, comprising:

[0141] (1), (2), same as Example 4;

[0142] (3) Resin components A and B can be stored separately. When in use, resin component A and resin component B are mixed in a ratio of 100:60. Then, high-speed shearing and dispersion are performed at 1000 rpm to obtain the final finished product resin C.

[0143] (4) Same as Example 4.

[0144] It was found that due to the lack of component B in the resin, the resin could not be completely cured, the cross-linking density decreased, and the mechanical properties of the resin decreased.

[0145] Example 8

[0146] A method for preparing a carbon fiber layer of a high-pressure hydrogen storage bottle, comprising:

[0147] (1), (2), same as Example 4;

[0148] (3) Resin components A and B can be stored separately. When in use, resin component A and resin component B are mixed in a ratio of 100:90. Then, high-speed shearing and dispersion are performed at 1000 rpm to obtain the final finished product resin C.

[0149] (4) Same as Example 4.

[0150] It was found that due to the lack of component A in the resin, there were residual component B substances in the resin system, which also led to a decrease in cross-linking density and a decrease in the mechanical properties of the resin.

[0151] Test Example 1

[0152] In order to show that the resin system prepared by the present application has the advantages of good impregnation effect, stable glue content, no migration of glue, etc., it can be well applied to the preparation process of carbon fiber layer of high-pressure hydrogen storage bottle. The applicant tested Examples 1 to 4 and Comparative Examples 1 to 3. The viscosity of the resin was tested using a viscometer, and the glue content and its discrete value were counted. The specific data are shown in the table below:

[0153]

[0154]

[0155] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An epoxy resin system, characterized in that, the epoxy resin system includes: epoxy resin, thermoplastic resin and thixotropic agent.

2. The epoxy resin system according to claim 1, characterized in that, the epoxy resin includes at least one of liquid bisphenol A diglycidyl ether, liquid bisphenol F diglycidyl ether, liquid glycidyl ester epoxy resin, and liquid aliphatic glycidyl ether epoxy resin; the thermoplastic resin includes at least one of ultra-high molecular weight epoxy resin, polyether ketone, and polyether ether ketone; the thixotropic agent includes at least one of fumed silica, organic bentonite, hydrogenated castor oil, and polyamide wax.

3. The epoxy resin system according to claim 1, characterized in that, the epoxy resin system further includes: toughness agent, curing agent and accelerator.

4. The epoxy resin system according to claim 3, characterized in that, the toughness agent includes at least one of liquid rubber and core-shell nanoparticles; the curing agent includes at least one of liquid anhydride curing agents, amine curing agents, and polyetheramine curing agents; Preferably, the curing agent includes one or a combination of several of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and isophoronediamine; the accelerator includes tertiary amines and their salts or imidazole accelerators; Preferably, the accelerator includes one or a combination of several of 2,4-imidazole, 2,4,6-tris(dimethylaminomethyl)phenol, and N,N-dimethylbenzylamine.

5. The epoxy resin system according to any one of claims 1 to 4, characterized in that, by mass, the epoxy resin system includes: 30-50 parts of epoxy resin, 20-40 parts of thermoplastic resin, 10-30 parts of toughness agent, 3-15 parts of thixotropic agent, 40-80 parts of curing agent, and 1-6 parts of accelerator; Preferably, by mass, the epoxy resin system includes: 50 parts of epoxy resin, 25 parts of thermoplastic resin, 20 parts of toughness agent, 10 parts of thixotropic agent, 60 parts of curing agent, and 3 parts of accelerator.

6. A preparation method of the epoxy resin system according to any one of claims 1 to 5, characterized in that, the method includes: (A), mixing epoxy resin, thermoplastic resin, toughness agent, and thixotropic agent and then subjecting them to shear dispersion to obtain resin A; (B), mixing the curing agent and the accelerator and then subjecting them to shear dispersion to obtain resin B; (C), mixing resin A and resin B and then subjecting them to shear dispersion to obtain the epoxy resin system.

7. The preparation method of the epoxy resin system according to claim 6, characterized in that, the conditions of shear dispersion in step (A) satisfy at least one of the following: the shear speed is 200-2000 rpm, the temperature is 90-110 °C, and the shear dispersion time is 2 h; the conditions of shear dispersion in step (B) satisfy at least one of the following: the shear speed is 200-800 rpm, the temperature is 30-35 °C, and the shear dispersion time is 0.5 h; In step (C), the conditions for shear dispersion satisfy at least one of the following: the shear speed is 200 to 1000 rpm, the temperature is 50 °C, and the shear dispersion time is 0.5 h.

8. The method for preparing an epoxy resin system according to claim 6, wherein, in step (C), the mass ratio of resin A to resin B in the mixture is 100:65 to 85.

9. An application of the epoxy resin system according to any one of claims 1 to 5 in the preparation of a carbon fiber layer of a high-pressure hydrogen storage cylinder.

10. The application of the epoxy resin system according to claim 9 in the preparation of a carbon fiber layer of a high-pressure hydrogen storage cylinder, wherein, the application includes: adding the shear-dispersed epoxy resin system into an impregnation tank, passing carbon fiber dry yarn through the impregnation tank, and winding it onto the inner liner of the gas cylinder by the wet winding method to form a carbon fiber layer; during the winding process, the temperature of the epoxy resin system in the impregnation tank is 30 to 60 °C.

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