Wet winding epoxy resin system as well as preparation method and application thereof

Abstract

The invention provides a wet winding epoxy resin system as well as a preparation method and application thereof. The epoxy resin system is prepared from the following components in parts by weight: 25 to 75 parts of polyfunctional epoxy resin, 10 to 30 parts of polyepoxy reactive diluent, 0.5 to 5 parts of inorganic solid filler, 20 to 100 parts of curing agent, 0.5 to 5 parts of accelerant, 0.1 to 2 parts of defoaming agent, 0.1 to 2 parts of flatting agent and 0.1 to 1 part of coupling agent. Therefore, the epoxy resin system disclosed by the invention has relatively high elastic modulus, proper toughness and relatively high strength, so that the stability of the epoxy resin system is greatly improved, the safety of the epoxy resin system for wet winding is improved, the condition that a gas storage cylinder subjected to wet winding of the epoxy resin system is easy to crack is avoided, and meanwhile, the service life of the gas storage cylinder is prolonged. The curing temperature of the epoxy resin system is low, and wet winding can be better achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrogen storage, and in particular relates to a wet-winding epoxy resin system and a preparation method and application thereof. Background Art

[0002] Carbon fiber winding hydrogen storage type IV bottle is the inevitable trend of current vehicle-mounted hydrogen storage. The application of its composite material layer and plastic liner greatly improves the hydrogen storage density of vehicle-mounted hydrogen storage bottle. Wet winding is the most mature winding process for carbon fiber winding hydrogen storage type IV bottle composite material layer. Epoxy resin is a thermosetting resin with excellent performance, which is widely used in the field of composite materials and is also the most mature and stable system in the field of wet winding.

[0003] The hydrogen storage bottle will have huge pressure changes during the process of filling hydrogen and charging and discharging gas, and the outer surface of the composite material layer will produce cracks of various states, which poses a huge threat to the overall safety. Therefore, the composite material layer and its resin system must have very excellent mechanical properties to withstand the huge changes in internal pressure, ensure its appearance is intact, and avoid damage to the hydrogen storage bottle. At the same time, in order to ensure the integrity of the plastic liner during the curing process, the curing temperature of the resin is usually required to be less than or equal to 120°C. In order to solve the above problems, the traditional solution is to toughen the epoxy resin system, greatly improve the toughness of the epoxy resin, so that the composite material layer can absorb the energy inside the hydrogen storage bottle, thereby eliminating the trend of crack generation and expansion. Although the high-toughness epoxy resin system can effectively eliminate the cracks on the outside of the hydrogen storage bottle, blindly toughening will lead to poor stability of the epoxy resin system, a significant decrease in mechanical strength, and irreversible changes in the size of the gas cylinder after multiple charging and discharging cycles, which also brings huge safety hazards.

[0004] Therefore, there is an urgent need for an epoxy resin system with high elastic modulus, high mechanical strength, suitable toughness and low curing temperature so as to be suitable for wet winding of hydrogen storage bottles. Summary of the invention

[0005] The present invention aims to solve one of the technical problems in the related art at least to a certain extent. To this end, the purpose of the present invention is to provide an epoxy resin system for wet winding and a preparation method and application thereof. As a result, the epoxy resin system of the present application has a high elastic modulus, suitable toughness and high strength, so that the stability of the epoxy resin system is greatly improved, the safety of the epoxy resin system for wet winding is improved, and the gas cylinders wet-wound by the epoxy resin system are prevented from being prone to cracks. At the same time, the curing temperature of the epoxy resin system of the present application is low, which can better achieve wet winding.

[0006] In one aspect of the present invention, the present invention provides an epoxy resin system for wet winding. According to an embodiment of the present invention, the above epoxy resin system includes the following components in parts by weight:

[0007] 25-75 parts of multifunctional epoxy resin, 10-30 parts of multi-epoxy reactive diluent, 0.5-5 parts of inorganic solid filler, 20-100 parts of curing agent, 0.5-5 parts of accelerator, 0.1-2 parts of defoaming agent, 0.1-2 parts of leveling agent and 0.1-1 parts of coupling agent.

[0008] According to the wet-winding epoxy resin system of the embodiment of the present invention, a multifunctional epoxy resin is used as the resin matrix. The cross-linked multifunctional epoxy resin has a high cross-linking density. In combination with inorganic solid fillers, the elastic modulus of the epoxy resin system can be greatly improved, and the rigidity of the cured product of the epoxy resin system can be greatly improved. It can ensure that the gas cylinder wet-wound by the epoxy resin system has good dimensional stability during pressure changes, thereby greatly improving the safety of the epoxy resin system for wet winding. Since the viscosity of the multifunctional epoxy resin is relatively large, adding a multi-epoxy reactive diluent to the epoxy resin system can reduce the viscosity of the entire epoxy resin system and improve the convenience of the epoxy resin system for wet winding without reducing the cross-linking density of the resin system, so that the epoxy resin has a higher elastic modulus and a higher cured product rigidity, and ensures that the epoxy resin system has a certain toughness. Therefore, the epoxy resin system of the present application has a high elastic modulus, suitable toughness and high strength, which greatly improves the stability of the epoxy resin system, improves the safety of the epoxy resin system for wet winding, and avoids the situation where gas cylinders wet-wound by the epoxy resin system are prone to cracks. At the same time, the curing temperature of the epoxy resin system of the present application is low, which can better achieve wet winding.

[0009] In addition, the epoxy resin system according to the above embodiment of the present invention may also have the following additional technical features:

[0010] In some embodiments of the present invention, the epoxy resin system includes the following components in parts by weight: 40-75 parts of the multifunctional epoxy resin, 10-20 parts of the multi-epoxy reactive diluent, 1-3 parts of the inorganic solid filler, 20-100 parts of the curing agent, 0.5-5 parts of the accelerator, 0.1-2 parts of the defoaming agent, 0.1-2 parts of the leveling agent and 0.1-1 parts of the coupling agent.

[0011] In some embodiments of the present invention, the multifunctional epoxy resin includes at least one of linear phenolic epoxy resin, o-cresol formaldehyde epoxy resin, resorcinol formaldehyde epoxy resin, tetraphenol ethane epoxy resin, TDE-85 epoxy resin, 4,4'-diaminodiphenylmethane epoxy resin and aminophenol trifunctional epoxy resin.

[0012] In some embodiments of the present invention, the polyepoxy reactive diluent includes at least one of an alicyclic epoxy reactive diluent, an aliphatic epoxy reactive diluent, and an aromatic reactive diluent.

[0013] In some embodiments of the present invention, the inorganic solid filler includes at least one of SiO2 solid filler and TiO2 solid filler.

[0014] In some embodiments of the present invention, the inorganic solid filler is a nano inorganic solid filler.

[0015] In some embodiments of the present invention, the alicyclic epoxy reactive diluent includes at least one of 1,4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether.

[0016] In some embodiments of the present invention, the aliphatic epoxy reactive diluent includes at least one of cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycerol triglycidyl ether, and trimethylolpropane triglycidyl ether.

[0017] In some embodiments of the present invention, the aromatic reactive diluent includes at least one of phenol glycidyl ether, resorcinol diglycidyl ether and p-tert-butylphenol glycidyl ether.

[0018] In another aspect of the present invention, the present invention provides a method for preparing a wet-wound epoxy resin system. According to an embodiment of the present invention, the method comprises:

[0019] (1) mixing 25-75 parts of a multifunctional epoxy resin, 10-30 parts of a multi-epoxy reactive diluent, 0.5-5 parts of an inorganic solid filler, 0.1-2 parts of a defoamer, 0.1-2 parts of a leveling agent, and 0.1-1 parts of a coupling agent to obtain a first mixture;

[0020] (2) mixing 0.5-5 parts of an accelerator and 20-100 parts of a curing agent to obtain a second mixture;

[0021] (3) Mixing the first mixture and the second mixture to obtain a wet-wound epoxy resin system.

[0022] According to the method for preparing a wet-wound epoxy resin system according to an embodiment of the present invention, a multifunctional epoxy resin, a multi-epoxy reactive diluent, an inorganic solid filler and other materials are mixed to obtain a first mixture, and a multifunctional epoxy resin is used as a resin matrix. The cross-linked multifunctional epoxy resin has a high cross-linking density. In combination with the inorganic solid filler, the elastic modulus of the epoxy resin system can be greatly improved, and the rigidity of the cured product of the epoxy resin system can be greatly improved, so that the gas cylinder wet-wound by the epoxy resin system can have good dimensional stability during the pressure change process, thereby greatly improving the safety of the epoxy resin system for wet winding; adding the multi-epoxy reactive diluent to the epoxy resin system can reduce the viscosity of the entire epoxy resin system, improve the convenience of the epoxy resin system for wet winding, and will not reduce the cross-linking density of the resin system, so that the epoxy resin has a high elastic modulus and a high cured product rigidity, and ensures that the epoxy resin system has a certain toughness. Therefore, the epoxy resin system prepared by the above method has a high elastic modulus, suitable toughness and high strength, which greatly improves the stability of the epoxy resin system, improves the safety of the epoxy resin system for wet winding, and avoids the situation that the gas cylinder wet-wound by the epoxy resin system is prone to cracks. At the same time, the curing temperature of the epoxy resin system prepared by the above method is low, which can better realize wet winding.

[0023] In addition, the method for preparing the wet-wound epoxy resin system according to the above embodiment of the present invention may also have the following additional technical features:

[0024] In some embodiments of the present invention, in step (1), the mixing method includes shear dispersion and ultrasonic dispersion.

[0025] In some embodiments of the present invention, the shear dispersion temperature is 10-50°C, and the shear dispersion time is 0.5-2h; the ultrasonic dispersion temperature is -10-10°C, and the ultrasonic dispersion time is 0.5-2h.

[0026] In some embodiments of the present invention, in step (2), the mixing temperature is 10-50° C., and the mixing time is 0.5-3 h.

[0027] In some embodiments of the present invention, in step (3), the mixing temperature is 10-40°C.

[0028] In the third aspect of the present invention, the present invention proposes a hydrogen storage device. According to an embodiment of the present invention, the above hydrogen storage device comprises the wet-wound epoxy resin system described in the above embodiment or the wet-wound epoxy resin system prepared by the method described in the above embodiment. Thus, during the cycle of charging and discharging or the process of filling gas, the hydrogen storage device is ensured to have good dimensional stability, thereby improving the safety of transportation and storage of the hydrogen storage device, and significantly reducing the probability of cracks in the composite material layer of the hydrogen storage device.

[0029] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0031] Figure 1 The present invention is a flowchart of a method for preparing a wet-wound epoxy resin system according to an embodiment of the present invention. DETAILED DESCRIPTION

[0032] Embodiments of the present invention are described in detail below, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, and should not be construed as limiting the present invention.

[0033] In one aspect of the present invention, the present invention proposes an epoxy resin system for wet winding. According to an embodiment of the present invention, the above-mentioned epoxy resin system includes the following components in parts by weight: 25-75 parts of multifunctional epoxy resin, 10-30 parts of multi-epoxy reactive diluent, 0.5-5 parts of inorganic solid filler, 20-100 parts of curing agent, 0.5-5 parts of accelerator, 0.1-2 parts of defoaming agent, 0.1-2 parts of leveling agent and 0.1-1 parts of coupling agent. As a result, the epoxy resin system of the present application has a high elastic modulus, suitable toughness and high strength, which greatly improves the stability of the epoxy resin system, improves the safety of the epoxy resin system for wet winding, and avoids the situation that the gas cylinder of the epoxy resin system wet winding is prone to cracks. At the same time, the curing temperature of the epoxy resin system of the present application is low, which can better achieve wet winding.

[0034] The following is a detailed description of how the above-mentioned wet winding epoxy resin system can achieve the above-mentioned effects:

[0035] The present application adopts a multifunctional epoxy resin as the resin matrix. The cross-linked multifunctional epoxy resin has a high cross-linking density. Combined with inorganic solid fillers, the elastic modulus of the epoxy resin system can be greatly improved, and the rigidity of the cured product of the epoxy resin system can be greatly improved. When the gas cylinder wet-wound by the epoxy resin system is in the process of filling and degassing or filling with gas, the gas cylinder will produce huge pressure changes. Since the epoxy resin system has a high elastic modulus and a high rigidity of the cured product, it can be ensured that the gas cylinder has good dimensional stability during the above-mentioned pressure change process, thereby greatly improving the safety of the epoxy resin system used for wet winding.

[0036] Since the viscosity of multifunctional epoxy resin is relatively high, it is necessary to reduce the viscosity of multifunctional epoxy resin in order to better use the epoxy resin system for wet winding. The traditional method mainly adds CTBN (carboxyl-terminated nitrile rubber) to the epoxy resin system, which can both reduce the viscosity of the multifunctional epoxy resin and increase the toughness of the epoxy resin system after curing. However, the addition of CTBN will cause the rigidity and tensile modulus of the cured epoxy resin to be greatly reduced. The present application adds a polyepoxy reactive diluent to the epoxy resin system, which has the following advantages: (1) reducing the viscosity of the entire epoxy resin system and improving the convenience of the epoxy resin system for wet winding; (2) the polyepoxy reactive diluent has at least two reactive functional groups, so the polyepoxy reactive diluent can participate in the cross-linking reaction of the epoxy resin, thereby not reducing the cross-linking density of the resin system, so that the epoxy resin has a higher elastic modulus and higher rigidity of the cured product; (3) because the main chain segment of the polyepoxy reactive diluent does not contain large sterically hindered groups such as benzene rings, the polyepoxy reactive diluent chain segments move more freely and have better flexibility, thereby enhancing the toughness of the epoxy resin system cured product.

[0037] Furthermore, the type of the above-mentioned curing agent is not particularly limited. As a preferred embodiment, the above-mentioned curing agent includes at least one of a liquid anhydride curing agent and an alicyclic amine curing agent, specifically, including but not limited to at least one of Me-THPA, Me-HHPA, MNA and IPD.

[0038] Furthermore, the type of the above-mentioned accelerator is not particularly limited. As a preferred embodiment, the above-mentioned accelerator includes tertiary ammonium, tertiary ammonium salt and imidazole substances, specifically, including but not limited to at least one of 2,4-EMI, DMP-30 and BDMA.

[0039] Furthermore, the type of the above-mentioned defoaming agent is not particularly limited. As a preferred embodiment, the above-mentioned defoaming agent includes substances such as polysiloxane and polyether-modified silicone oil, specifically, including but not limited to at least one of BYK-525, BYK-500 and BYK-1710.

[0040] Furthermore, the type of the leveling agent is not particularly limited. As a preferred embodiment, the leveling agent includes substances such as epoxy silane and amino silane, specifically including but not limited to at least one of BYK-9920 and BYK-333.

[0041] Furthermore, the type of the coupling agent is not particularly limited. As a preferred embodiment, the coupling agent includes substances such as silane coupling agents and phthalates, specifically, including but not limited to at least one of A-187 and YC-1027.

[0042] Furthermore, in the epoxy resin system, the weight portion of the multifunctional epoxy resin is 25-75 parts, the weight portion of the multi-epoxy reactive diluent is 10-30 parts, the weight portion of the inorganic solid filler is 0.5-5 parts, the weight portion of the curing agent is 20-100 parts, the weight portion of the accelerator is 0.5-5 parts, the weight portion of the defoaming agent is 0.1-2 parts, the weight portion of the leveling agent is 0.1-2 parts and the weight portion of the coupling agent is 0.1-1 parts. Thus, controlling the above components within the corresponding range is conducive to ensuring that the epoxy resin system prepared in the present application has a high elastic modulus, suitable toughness and high strength, so that the stability of the epoxy resin system is greatly improved, the safety of the epoxy resin system for wet winding is improved, and the gas cylinder wet-wound by the epoxy resin system is avoided. The situation that cracks are easy to appear. At the same time, it is conducive to ensuring that the curing temperature of the epoxy resin system of the present application is low, and wet winding can be better achieved.

[0043] According to some specific embodiments of the present invention, the epoxy resin system includes the following components in parts by weight: 40-75 parts of the multifunctional epoxy resin, 10-20 parts of the multi-epoxy reactive diluent, 1-3 parts of the inorganic solid filler, 20-100 parts of the curing agent, 0.5-5 parts of the accelerator, 0.1-2 parts of the defoaming agent, 0.1-2 parts of the leveling agent and 0.1-1 parts of the coupling agent. Thus, controlling the above components within the corresponding ranges is further beneficial to ensure that the epoxy resin system prepared in the present application has a higher elastic modulus, suitable toughness and higher strength, so that the stability of the epoxy resin system is greatly improved, the safety of the epoxy resin system for wet winding is improved, and the gas cylinders wet-wound by the epoxy resin system are avoided from being prone to cracks. At the same time, it is further beneficial to ensure that the curing temperature of the epoxy resin system of the present application is low, and wet winding can be better achieved.

[0044] In an embodiment of the present invention, the above-mentioned multifunctional epoxy resin includes but is not limited to at least one of linear phenolic epoxy resin, o-cresol formaldehyde epoxy resin, resorcinol formaldehyde epoxy resin, tetraphenol ethane epoxy resin (tert-PGEE), TDE-85 epoxy resin, 4,4'-diaminodiphenylmethane epoxy resin (AG-80) and aminophenol trifunctional epoxy resin (AFG-90). Thus, it can be ensured that the multifunctional epoxy resin after cross-linking has a higher cross-linking density and the epoxy resin system has a higher cured product rigidity.

[0045] In an embodiment of the present invention, the polyepoxy reactive diluent includes at least one of alicyclic epoxy reactive diluent, aliphatic epoxy reactive diluent and aromatic reactive diluent. Specifically, the alicyclic epoxy reactive diluent includes at least one of 1,4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether; the aliphatic epoxy reactive diluent includes at least one of cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycerol triglycidyl ether and trimethylolpropane triglycidyl ether; the aromatic reactive diluent includes at least one of phenol glycidyl ether, resorcinol diglycidyl ether and p-tert-butylphenol glycidyl ether. As a result, the viscosity of the entire epoxy resin system is further reduced, the convenience of the epoxy resin system for wet winding is improved, the epoxy resin system is further ensured to have a higher elastic modulus and higher cured product rigidity, the flexibility of the cured network of the epoxy resin system cured product is further enhanced, and the toughness of the epoxy resin system cured product is improved.

[0046] In an embodiment of the present invention, the inorganic solid filler includes but is not limited to at least one of SiO2 solid filler and TiO2 solid filler.

[0047] According to a specific embodiment of the present invention, the inorganic solid filler is a nano inorganic solid filler, and thus the inorganic solid filler can be dispersed more evenly in the epoxy resin system, thereby further improving the elastic modulus of the resin system and further improving the rigidity of the cured product of the epoxy resin system.

[0048] In another aspect of the present invention, the present invention provides a method for preparing a wet-wound epoxy resin system. According to an embodiment of the present invention, the method comprises:

[0049] S100: 25-75 parts of a multifunctional epoxy resin, 10-30 parts of a multi-epoxy reactive diluent, 0.5-5 parts of an inorganic solid filler, 0.1-2 parts of a defoamer, 0.1-2 parts of a leveling agent, and 0.1-1 parts of a coupling agent are mixed to obtain a first mixture.

[0050] In this step, 25-75 parts of a multifunctional epoxy resin, 10-30 parts of a multi-epoxy reactive diluent, 0.5-5 parts of an inorganic solid filler, 0.1-2 parts of a defoamer, 0.1-2 parts of a leveling agent and 0.1-1 parts of a coupling agent are mixed to obtain a first mixture. A multifunctional epoxy resin is used as the resin matrix. The cross-linked multifunctional epoxy resin has a high cross-linking density. In combination with inorganic solid fillers, the elastic modulus of the epoxy resin system can be greatly improved, and the rigidity of the cured product of the epoxy resin system can be greatly improved. The gas cylinder wet-wound by the epoxy resin system can have good dimensional stability during pressure changes, thereby greatly improving the safety of the epoxy resin system for wet winding. Adding a multi-epoxy active diluent to the epoxy resin system can reduce the viscosity of the entire epoxy resin system and improve the convenience of the epoxy resin system for wet winding without reducing the cross-linking density of the resin system, so that the epoxy resin has a higher elastic modulus and a higher cured product rigidity, and ensures that the epoxy resin system has a certain toughness.

[0051] According to a specific embodiment of the present invention, the above-mentioned mixing method includes shear dispersion and ultrasonic dispersion, whereby the multifunctional epoxy resin can be divided into smaller multifunctional epoxy resins by shearing, and then each component material is ultrasonically dispersed, so as to achieve the uniform distribution of each component in the first mixture to the greatest extent.

[0052] According to another specific embodiment of the present invention, the temperature of the shear dispersion is 10-50°C, and the time of the shear dispersion is 0.5-2h; the temperature of the ultrasonic dispersion is -10-10°C, and the time of the ultrasonic dispersion is 0.5-2h, thereby further achieving uniform distribution of each component in the first mixture.

[0053] In an embodiment of the present invention, the shear dispersion device includes but is not limited to a mixing kettle, and the ultrasonic dispersion device includes but is not limited to an ultrasonic disperser.

[0054] In an embodiment of the present invention, the above-mentioned multifunctional epoxy resin includes but is not limited to at least one of linear phenolic epoxy resin, o-cresol formaldehyde epoxy resin, resorcinol formaldehyde epoxy resin, tetraphenol ethane epoxy resin (tert-PGEE), TDE-85 epoxy resin, 4,4'-diaminodiphenylmethane epoxy resin (AG-80) and aminophenol trifunctional epoxy resin (AFG-90). Thus, it can be ensured that the multifunctional epoxy resin after cross-linking has a higher cross-linking density and the epoxy resin system has a higher cured product rigidity.

[0055] In an embodiment of the present invention, the polyepoxy reactive diluent includes at least one of alicyclic epoxy reactive diluent, aliphatic epoxy reactive diluent and aromatic reactive diluent. Specifically, the alicyclic epoxy reactive diluent includes at least one of 1,4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether; the aliphatic epoxy reactive diluent includes at least one of cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycerol triglycidyl ether and trimethylolpropane triglycidyl ether; the aromatic reactive diluent includes at least one of phenol glycidyl ether, resorcinol diglycidyl ether and p-tert-butylphenol glycidyl ether. As a result, the viscosity of the entire epoxy resin system is further reduced, the convenience of the epoxy resin system for wet winding is improved, the epoxy resin system has a higher elastic modulus and a higher rigidity of the cured product, and the main chain segment of the polyepoxy reactive diluent does not contain large steric hindrance groups such as benzene rings, so that the movement of the polyepoxy reactive diluent chain segment is freer and the chain segment has better flexibility, thereby further enhancing the toughness of the epoxy resin system cured product.

[0056] In an embodiment of the present invention, the inorganic solid filler includes but is not limited to at least one of SiO2 solid filler and TiO2 solid filler.

[0057] According to another specific embodiment of the present invention, the inorganic solid filler is a nano inorganic solid filler, and thus the inorganic solid filler can be dispersed more evenly in the epoxy resin system, thereby further improving the elastic modulus of the resin system and further improving the rigidity of the cured product of the epoxy resin system.

[0058] S200: 0.5-5 parts of accelerator and 20-100 parts of curing agent are mixed to obtain a second mixture.

[0059] In this step, 0.5-5 parts of an accelerator and 20-100 parts of a curing agent are mixed to obtain a second mixture.

[0060] According to another specific embodiment of the present invention, the mixing temperature of the accelerator and the curing agent is 10-50°C, and the mixing time is 0.5-3h. Therefore, limiting the mixing temperature within the above range can ensure that the accelerator and the curing agent have good stability, thereby avoiding heat absorption and initiation of curing reaction during the mixing process; limiting the mixing time within the above range can avoid long-term mixing treatment causing mechanical friction between the accelerator and the curing agent to generate heat, which leads to the initiation of curing reaction during the mixing process.

[0061] In an embodiment of the present invention, the type of the above-mentioned curing agent is not particularly limited. As a preferred embodiment, the above-mentioned curing agent includes at least one of a liquid anhydride curing agent and an alicyclic amine curing agent, specifically, including but not limited to at least one of Me-THPA, Me-HHPA, MNA and IPD.

[0062] In the embodiment of the present invention, the type of the above-mentioned promoter is not particularly limited. As a preferred embodiment, the above-mentioned promoter includes tertiary ammonium, tertiary ammonium salt and imidazole substances, specifically, including but not limited to at least one of 2,4-EMI, DMP-30 and BDMA.

[0063] S300: Mixing the first mixture and the second mixture to obtain a wet winding epoxy resin system

[0064] In this step, the first mixture and the second mixture are mixed, and after cooling, the wet-wound epoxy resin system is obtained. Thus, the epoxy resin system prepared by the above method has a high elastic modulus, suitable toughness and high strength, so that the stability of the epoxy resin system is greatly improved, the safety of the epoxy resin system for wet winding is improved, and the gas cylinders wet-wound by the epoxy resin system are prevented from being prone to cracks. At the same time, the curing temperature of the epoxy resin system prepared by the above method is low, and wet winding can be better achieved.

[0065] According to another specific embodiment of the present invention, the temperature for mixing the first mixture and the second mixture is 10-40° C., so that the first mixture and the second mixture can be mixed at room temperature, thereby saving preparation costs.

[0066] In the third aspect of the present invention, the present invention proposes a hydrogen storage device. According to an embodiment of the present invention, the above hydrogen storage device comprises the wet-wound epoxy resin system described in the above embodiment or the wet-wound epoxy resin system prepared by the method described in the above embodiment. Thus, during the cycle of charging and discharging or the process of filling gas, the hydrogen storage device is ensured to have good dimensional stability, thereby improving the safety of transportation and storage of the hydrogen storage device, and significantly reducing the probability of cracks in the composite material layer of the hydrogen storage device.

[0067] According to a specific embodiment of the present invention, the hydrogen storage device includes a plastic liner and a winding layer arranged on the periphery of the plastic liner, and the winding layer is obtained by winding fibers impregnated with the epoxy resin system on the periphery of the plastic liner and curing them.

[0068] The embodiments of the present invention are described in detail below. It should be noted that the embodiments described below are exemplary and are only used to explain the present invention, and cannot be interpreted as limiting the present invention. In addition, if not explicitly stated, all reagents used in the following embodiments are commercially available, or can be synthesized according to this article or known methods, and the reaction conditions not listed are also easily available to those skilled in the art.

[0069] Example 1

[0070] This embodiment provides a method for preparing a wet-winding epoxy resin system, the steps of which are as follows:

[0071] (1) adding 45 parts of multifunctional epoxy resin AG-80, 10 parts of multi-epoxy reactive diluent DGE, 1 part of SiO2 solid nanofiller, 0.5 parts of defoamer BYK-525, 0.5 parts of leveling agent BYK-9920, and 0.5 parts of coupling agent YC-1027 into a mixing kettle for high-speed shear dispersion, the shear speed is 1500 rpm, the shear temperature is 30° C., the shear dispersion mixing time is 2 h, and a mixed solution is obtained, and then the mixed solution is transferred to an ultrasonic disperser for ultrasonic dispersion, the ultrasonic dispersion temperature is 0° C., and the ultrasonic time is 1 h, thereby obtaining a first mixture;

[0072] (2) adding 80 parts of curing agent Me-HHPA and 2 parts of accelerator 2,4-EMI into a mixing kettle and stirring and mixing them at a stirring speed of 500 rpm, a stirring temperature of 30° C., and a stirring and mixing time of 1 hour to obtain a second mixture;

[0073] (3) The first mixture and the second mixture are mixed at a mixing temperature of 10° C. and cooled to obtain an epoxy resin system.

[0074] Example 2

[0075] This embodiment provides a method for preparing a wet-winding epoxy resin system, the steps of which are as follows:

[0076] (1) adding 60 parts of multifunctional epoxy resin AG-80, 15 parts of multi-epoxy reactive diluent DGE, 2 parts of SiO2 solid nanofiller, 0.5 parts of defoamer BYK-525, 0.5 parts of leveling agent BYK-9920, and 0.5 parts of coupling agent YC-1027 into a mixing kettle for high-speed shear dispersion, the shear speed is 1500 rpm, the shear temperature is 30° C., the shear dispersion mixing time is 1.5 h, and a mixed solution is obtained, and then the mixed solution is transferred to an ultrasonic disperser for ultrasonic dispersion, the ultrasonic dispersion temperature is 5° C., and the ultrasonic time is 0.5 h, thereby obtaining a first mixture;

[0077] (2) adding 80 parts of curing agent Me-HHPA and 2 parts of accelerator 2,4-EMI into a mixing kettle and stirring and mixing them at a stirring speed of 500 rpm, a stirring temperature of 30° C., and a stirring and mixing time of 1 hour to obtain a second mixture;

[0078] (3) The first mixture and the second mixture are mixed at a mixing temperature of 10° C. and cooled to obtain an epoxy resin system.

[0079] Example 3

[0080] This embodiment provides a method for preparing a wet-winding epoxy resin system, the steps of which are as follows:

[0081] (1) adding 75 parts of multifunctional epoxy resin AG-80, 20 parts of multi-epoxy reactive diluent DGE, 3 parts of SiO2 solid nanofiller, 0.5 parts of defoamer BYK-525, 0.5 parts of leveling agent BYK-9920, and 0.5 parts of coupling agent YC-1027 into a mixing kettle for high-speed shear dispersion, the shear speed is 1500 rpm, the shear temperature is 30° C., the shear dispersion mixing time is 2 h, and a mixed solution is obtained, and then the mixed solution is transferred to an ultrasonic disperser for ultrasonic dispersion, the ultrasonic dispersion temperature is 0° C., and the ultrasonic time is 1 h, thereby obtaining a first mixture;

[0082] (2) adding 80 parts of curing agent Me-HHPA and 2 parts of accelerator 2,4-EMI into a mixing kettle and stirring and mixing them at a stirring speed of 500 rpm, a stirring temperature of 30° C., and a stirring and mixing time of 1 hour to obtain a second mixture;

[0083] (3) The first mixture and the second mixture are mixed at a mixing temperature of 10° C. and cooled to obtain an epoxy resin system.

[0084] Example 4

[0085] This embodiment provides a method for preparing a wet-winding epoxy resin system, the steps of which are as follows:

[0086] (1) adding 35 parts of multifunctional epoxy resin AG-80, 30 parts of multi-epoxy reactive diluent DGE, 0.5 parts of SiO2 solid nanofiller, 0.5 parts of defoamer BYK-525, 0.5 parts of leveling agent BYK-9920, and 0.5 parts of coupling agent YC-1027 into a mixing kettle for high-speed shear dispersion, the shear speed is 1500 rpm, the shear temperature is 30° C., the shear dispersion mixing time is 2 h, and a mixed solution is obtained, and then the mixed solution is transferred to an ultrasonic disperser for ultrasonic dispersion, the ultrasonic dispersion temperature is 0° C., and the ultrasonic time is 1 h, thereby obtaining a first mixture;

[0087] (2) adding 80 parts of curing agent Me-HHPA and 2 parts of accelerator 2,4-EMI into a mixing kettle and stirring and mixing them at a stirring speed of 500 rpm, a stirring temperature of 30° C., and a stirring and mixing time of 1 hour to obtain a second mixture;

[0088] (3) The first mixture and the second mixture are mixed at a mixing temperature of 10° C. and cooled to obtain an epoxy resin system.

[0089] Example 5

[0090] This embodiment provides a method for preparing a wet-winding epoxy resin system, the steps of which are as follows:

[0091] (1) adding 25 parts of multifunctional epoxy resin AG-80, 30 parts of multi-epoxy reactive diluent DGE, 5 parts of SiO2 solid nanofiller, 0.5 parts of defoamer BYK-525, 0.5 parts of leveling agent BYK-9920, and 0.5 parts of coupling agent YC-1027 into a mixing kettle for high-speed shear dispersion, the shear speed is 1500 rpm, the shear temperature is 30° C., the shear dispersion mixing time is 2 h, and a mixed solution is obtained, and then the mixed solution is transferred to an ultrasonic disperser for ultrasonic dispersion, the ultrasonic dispersion temperature is 0° C., and the ultrasonic time is 1 h, thereby obtaining a first mixture;

[0092] (2) adding 80 parts of curing agent Me-HHPA and 2 parts of accelerator 2,4-EMI into a mixing kettle and stirring and mixing them at a stirring speed of 500 rpm, a stirring temperature of 30° C., and a stirring and mixing time of 1 hour to obtain a second mixture;

[0093] (3) The first mixture and the second mixture are mixed at a mixing temperature of 10° C. and cooled to obtain an epoxy resin system.

[0094] Comparative Example 1

[0095] This comparative example provides a method for preparing a wet-wound epoxy resin system, the steps of which are as follows:

[0096] (1) adding 20 parts of multifunctional epoxy resin AG-80, 5 parts of multi-epoxy reactive diluent DGE, 0.1 parts of SiO2 solid nanofiller, 0.5 parts of defoamer BYK-525, 0.5 parts of leveling agent BYK-9920, and 0.5 parts of coupling agent YC-1027 into a mixing kettle for high-speed shear dispersion, the shear speed is 1500 rpm, the shear temperature is 30° C., the shear dispersion mixing time is 2 h, and a mixed solution is obtained, and then the mixed solution is transferred to an ultrasonic disperser for ultrasonic dispersion, the ultrasonic dispersion temperature is 0° C., and the ultrasonic time is 1 h, thereby obtaining a first mixture;

[0097] (2) adding 80 parts of curing agent Me-HHPA and 2 parts of accelerator 2,4-EMI into a mixing kettle and stirring and mixing them at a stirring speed of 500 rpm, a stirring temperature of 30° C., and a stirring and mixing time of 1 hour to obtain a second mixture;

[0098] (3) The first mixture and the second mixture are mixed at a mixing temperature of 10° C. and cooled to obtain an epoxy resin system.

[0099] Comparative Example 2

[0100] This comparative example provides a method for preparing a wet-wound epoxy resin system, the steps of which are as follows:

[0101] (1) adding 80 parts of multifunctional epoxy resin AG-80, 35 parts of multi-epoxy reactive diluent DGE, 5 parts of SiO2 solid nanofiller, 0.5 parts of defoamer BYK-525, 0.5 parts of leveling agent BYK-9920, and 0.5 parts of coupling agent YC-1027 into a mixing kettle for high-speed shear dispersion, the shear speed is 1500 rpm, the shear temperature is 30° C., the shear dispersion mixing time is 2 h, and a mixed solution is obtained, and then the mixed solution is transferred to an ultrasonic disperser for ultrasonic dispersion, the ultrasonic dispersion temperature is 0° C., and the ultrasonic time is 1 h, thereby obtaining a first mixture;

[0102] (2) adding 80 parts of curing agent Me-HHPA and 2 parts of accelerator 2,4-EMI into a mixing kettle and stirring and mixing them at a stirring speed of 500 rpm, a stirring temperature of 30° C., and a stirring and mixing time of 1 hour to obtain a second mixture;

[0103] (3) The first mixture and the second mixture are mixed at a mixing temperature of 10° C. and cooled to obtain an epoxy resin system.

[0104] The epoxy resin systems obtained in Examples 1-6 and Comparative Examples 1-2 were tested, and the test results are shown in Table 1.

[0105] Table 1

[0106]

[0107] As can be seen from Table 1, compared with Comparative Examples 1 and 2, Examples 1-5 of the present application control the weight of the multifunctional epoxy resin to be 25-75 parts, the weight of the multi-epoxy reactive diluent to be 10-30 parts, the weight of the inorganic solid filler to be 0.5-5 parts, the weight of the defoamer to be 0.1-2 parts, the weight of the leveling agent to be 0.1-2 parts, and the weight of the coupling agent to be 0.1-1 parts, so that the prepared epoxy resin system has the advantages of high elastic modulus, high mechanical strength, suitable toughness and low curing temperature, which can fully meet the wet winding of the hydrogen storage bottle. Specifically, the epoxy resin system prepared in the present application has a viscosity of 450-650mPa·s at 23°C, a trial period of not less than 9h, an elastic modulus of not less than 3.3Gpa, a tensile strength of not less than 80MPa, an elongation at break of greater than 3.3%, and a Tg of greater than 122°C.

[0108] In the description of the present invention, it is to be understood that the terms “center”, “longitudinal”, “lateral”, “length”, “width”, “thickness”, “up”, “down”, “front”, “back”, “left”, “right”, “vertical”, “horizontal”, “top”, “bottom”, “inside”, “outside”, “clockwise”, “counterclockwise”, “axial”, “radial”, “circumferential”, etc., indicating orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0109] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0110] In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

Claims

1. A wet winding epoxy resin system, characterized in that: The composition comprises the following components in parts by weight: 25-75 parts of multifunctional epoxy resin, 10-30 parts of multi-epoxy reactive diluent, 0.5-5 parts of inorganic solid filler, 20-100 parts of curing agent, 0.5-5 parts of accelerator, 0.1-2 parts of defoaming agent, 0.1-2 parts of leveling agent and 0.1-1 parts of coupling agent.

2. The epoxy resin system according to claim 1, characterized in that The composition comprises the following components in parts by weight: 40-75 parts of the multifunctional epoxy resin, 10-20 parts of the multi-epoxy reactive diluent, 1-3 parts of the inorganic solid filler, 20-100 parts of the curing agent, 0.5-5 parts of the accelerator, 0.1-2 parts of the defoaming agent, 0.1-2 parts of the leveling agent and 0.1-1 parts of the coupling agent.

3. The epoxy resin system according to claim 1 or 2, characterized in that: The multifunctional epoxy resin includes at least one of linear phenolic epoxy resin, o-cresol formaldehyde epoxy resin, resorcinol formaldehyde epoxy resin, tetraphenol ethane epoxy resin, TDE-85 epoxy resin, 4,4'-diaminodiphenylmethane epoxy resin and aminophenol trifunctional epoxy resin; and / or, the polyepoxy reactive diluent comprises at least one of a cycloaliphatic epoxy reactive diluent, an aliphatic epoxy reactive diluent and an aromatic reactive diluent; And / or, the inorganic solid filler includes at least one of SiO2 solid filler and TiO2 solid filler; And / or, the inorganic solid filler is a nano inorganic solid filler.

4. The epoxy resin system according to claim 3, characterized in that The alicyclic epoxy reactive diluent comprises at least one of 1,4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether; and / or, the aliphatic epoxy reactive diluent comprises at least one of cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, polyglycerol triglycidyl ether and trimethylolpropane triglycidyl ether; And / or, the aromatic reactive diluent includes at least one of phenol glycidyl ether, resorcinol diglycidyl ether and p-tert-butylphenol glycidyl ether.

5. A method for preparing a wet-wound epoxy resin system, characterized in that: include: (1) mixing 25-75 parts of a multifunctional epoxy resin, 10-30 parts of a multi-epoxy reactive diluent, 0.5-5 parts of an inorganic solid filler, 0.1-2 parts of a defoamer, 0.1-2 parts of a leveling agent, and 0.1-1 parts of a coupling agent to obtain a first mixture; (2) mixing 0.5-5 parts of an accelerator and 20-100 parts of a curing agent to obtain a second mixture; (3) Mixing the first mixture and the second mixture to obtain a wet-wound epoxy resin system.

6. The method according to claim 5, characterized in that In step (1), the mixing method includes shear dispersion and ultrasonic dispersion.

7. The method according to claim 6, characterized in that The temperature of the shear dispersion is 10-50°C, and the time of the shear dispersion is 0.5-2h; the temperature of the ultrasonic dispersion is -10-10°C, and the time of the ultrasonic dispersion is 0.5-2h.

8. The method according to claim 5, characterized in that In step (2), the mixing temperature is 10-50° C., and the mixing time is 0.5-3 h.

9. The method according to claim 5, characterized in that In step (3), the mixing temperature is 10-40°C.

10. A hydrogen storage device, characterized in that: The invention comprises the wet-wound epoxy resin system according to any one of claims 1 to 4 or the wet-wound epoxy resin system prepared by the method according to any one of claims 5 to 9.

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