Fiber composite winding bottle and preparation method thereof

Abstract

The invention provides a fiber composite material winding bottle and a preparation method thereof, the fiber composite material winding bottle comprises an inner layer, a middle layer and an outer layer from inside to outside, the inner layer is composed of a nylon fiber composite material layer, the middle layer is composed of a carbon fiber composite material layer, and the outer layer is composed of a carbon fiber composite material layer. The outer layer is composed of a glass fiber composite material layer or a carbon fiber composite material layer. The inner layer, the middle layer and the outer layer of the winding bottle are made of different fiber materials according to the actual requirements of different layers of the winding bottle, and the thermoplastic liner-free hydrogen storage bottle which is high in strength, high in interlayer binding force, high in preparation efficiency and capable of being effectively recycled is prepared.

Description

Technical Field

[0001] The invention belongs to the technical field of fiber-wound gas cylinders and relates to a fiber composite material wound bottle and a preparation method thereof. Background Art

[0002] High-pressure gas cylinders are key equipment in the field of gas storage. Existing high-pressure gas cylinders mainly include four types: pure steel metal cylinders, steel liner fiber-wound bottles, aluminum liner fiber-wound bottles, and plastic liner fiber-wound bottles. In mobile scenarios such as hydrogen fuel vehicles, the weight / capacity of steel or aluminum metal liner is relatively large, resulting in high energy consumption. Therefore, fiber-wound bottles with plastic liner have received increasing attention. However, existing fiber-wound bottles with plastic liner have the following disadvantages: (1) The plastic liner itself has low strength and is prone to deformation during the winding process; (2) The plastic liner and the winding layer may separate under extreme working conditions; (3) The plastic liner itself has limited pressure bearing capacity, and the weight / capacity ratio still needs to be reduced; (4) In order to improve the strength of the wrapped bottle, the existing wrapped bottle uses a large amount of thermosetting epoxy resin. The product cannot be effectively recycled after reaching the service life, forming a large amount of plastic pollutants. Therefore, thermoplastic liner-free fiber-wound bottles have become one of the development directions of high-pressure gas cylinders. Summary of the invention

[0003] In view of the problems existing in the prior art, the present invention provides a fiber composite material wrapped bottle and a preparation method thereof. The present invention uses the in-situ polymerization technology of polyamide materials, combines the actual needs of different layers of the wrapped bottle, uses different fiber materials to form the inner layer, middle layer and outer layer of the wrapped bottle, and prepares a thermoplastic linerless hydrogen storage bottle with high strength, high inter-layer bonding strength, high preparation efficiency and effective recycling.

[0004] Specifically, the present invention provides a fiber composite material wrapped bottle, which comprises an inner layer, an intermediate layer and an outer layer from the inside to the outside, the inner layer is composed of one or more nylon fiber composite layers from the inside to the outside, the intermediate layer is composed of one or more carbon fiber composite layers from the inside to the outside, and the outer layer is composed of one or more glass fiber composite layers or carbon fiber composite layers from the inside to the outside; wherein, a nylon fiber composite layer is composed of a layer of wound nylon fiber and a resin matrix, a carbon fiber composite layer is composed of a layer of wound carbon fiber and a resin matrix, and a glass fiber composite layer is composed of a layer of wound glass fiber and a resin matrix, the resin in the resin matrix of the nylon fiber composite layer and the carbon fiber composite layer in the intermediate layer is polyamide, and the resin in the resin matrix of the carbon fiber composite layer and the glass fiber composite layer in the outer layer is polyamide or epoxy resin, the polyamide is formed by polymerization of lactam, and the epoxy resin is formed by cross-linking and curing of an epoxy resin matrix through an epoxy resin curing agent.

[0005] In one or more embodiments, the inner layer is composed of 4 to 10 layers of nylon fiber composite material from inside to outside.

[0006] In one or more embodiments, the middle layer consists of 7 to 11 carbon fiber composite material layers from the inside to the outside.

[0007] In one or more embodiments, the outer layer consists of 4 to 10 glass fiber composite material layers or carbon fiber composite material layers from the inside to the outside.

[0008] In one or more embodiments, in the inner layer, the nylon fibers in the innermost nylon fiber composite material layer are arranged in the form of a hoop winding, and the nylon fibers in the two adjacent nylon fiber composite material layers are arranged in the form of a hoop winding and a spiral winding, respectively, the winding angle of the hoop winding is 90°, and the winding angle of the spiral winding is 15-45°, and the winding angle of the nylon fibers in each nylon fiber composite material layer where the nylon fibers are arranged in the form of a spiral winding increases layer by layer from the inside to the outside.

[0009] In one or more embodiments, in the middle layer, the carbon fibers in the innermost carbon fiber composite material layer are arranged in a hoop-winding form, and the carbon fibers in two adjacent carbon fiber composite material layers are arranged in a hoop-winding form and a spiral-winding form, respectively, the winding angle of the hoop-winding is 90°, and the winding angle of the spiral winding is 15-45°, and the winding angle of the carbon fiber in each carbon fiber composite material layer where the carbon fiber is arranged in a spiral-winding form increases layer by layer from the inside to the outside.

[0010] In one or more embodiments, in the outer layer, the glass fibers in the innermost glass fiber composite layer or the carbon fibers in the innermost carbon fiber composite layer are arranged in a hoop-winding form, and the glass fibers in two adjacent glass fiber composite layers or the carbon fibers in two adjacent carbon fiber composite layers are arranged in a hoop-winding form and a spiral-winding form, respectively, the winding angle of the hoop-winding is 90°, and the winding angle of the spiral winding is 15-45°, and the winding angle of the glass fibers in each glass fiber composite layer where the glass fibers are arranged in a spiral-winding form or the winding angle of the carbon fibers in each carbon fiber composite layer where the carbon fibers are arranged in a spiral-winding form increases layer by layer from the inside to the outside.

[0011] In one or more embodiments, the lactam is selected from one or more of butyrolactam, valerolactam, caprolactam, enantholactam, capryllactam, nonanolactam, decanolactam, undecanolactam, and laurolactam.

[0012] In one or more embodiments, the epoxy resin matrix is ​​selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate and aliphatic epoxy resin.

[0013] In one or more embodiments, the epoxy resin curing agent is selected from one or more of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, acetic anhydride, hexanoic anhydride, succinic anhydride, cyclohexanecarboxylic anhydride, aniline and metaphenylenediamine.

[0014] In one or more embodiments, the resin matrix of the nylon fiber composite layer, the carbon fiber composite layer and the glass fiber composite layer contains a stabilizer, and the stabilizer includes a hindered phenol antioxidant, a phosphite antioxidant and a thioester antioxidant. The mass of the stabilizer is 0.3-1.5wt% of the mass of the resin matrix, and the mass of the hindered phenol antioxidant, the phosphite antioxidant and the thioester antioxidant is 0.1-0.5wt% of the mass of the resin matrix, respectively.

[0015] In one or more embodiments, the nylon fiber is nylon 6 fiber or nylon 66 fiber, and the fineness of the nylon fiber is 420-3000D and the number of pores is 24-96F.

[0016] In one or more embodiments, the carbon fiber surface is coated with a vinyl ester or polyamide sizing agent.

[0017] In one or more embodiments, the nylon fiber content of the inner layer is 60-70 wt %, the carbon fiber content of the middle layer is 60-70 wt %, and the glass fiber or carbon fiber content of the outer layer is 60-70 wt %.

[0018] In one or more embodiments, the total number of nylon fiber composite layers in the inner layer, carbon fiber composite layers in the middle layer, and glass fiber composite layers or carbon fiber composite layers in the outer layer is 22-28 layers.

[0019] The present invention also provides a method for preparing the fiber composite material wrapped bottle described in any embodiment of the present invention, comprising the following steps:

[0020] (1) providing a water-soluble preform;

[0021] (2) providing a first monomer solution and a second monomer solution, wherein the first monomer solution comprises a first monomer and a catalyst, and the second monomer solution comprises a second monomer and an activator, and the first monomer and the second monomer are lactams, and the first monomer solution and the second monomer solution are uniformly mixed to obtain a first raw material solution;

[0022] (3) uniformly attaching the first raw material liquid to the surface of the nylon fiber;

[0023] (4) winding the nylon fiber to which the first raw material liquid is attached onto the water-soluble preform, winding one or more layers of the nylon fiber from the inside out, and heating the nylon fiber wound on the water-soluble preform so that the first monomer and the second monomer on the surface of the nylon fiber react to form polyamide, thereby obtaining a composite of the inner layer and the water-soluble preform;

[0024] (5) providing a third monomer solution and a fourth monomer solution, wherein the third monomer solution comprises a third monomer and a catalyst, and the fourth monomer solution comprises a fourth monomer and an activator, and the third monomer and the fourth monomer are lactams, and uniformly mixing the third monomer solution and the fourth monomer solution to obtain a second raw material solution;

[0025] (6) uniformly attaching the second raw material liquid to the surface of the carbon fiber;

[0026] (7) Winding the carbon fiber attached with the second raw material liquid onto the composite of the inner layer and the water-soluble preform, winding one or more layers of carbon fiber from the inside to the outside, and heating the carbon fiber wound on the water-soluble preform so that the third monomer and the fourth monomer on the surface of the carbon fiber react to form polyamide, thereby obtaining a composite of the fiber composite material wound around the bottle inner layer, the middle layer and the water-soluble preform;

[0027] (8) providing a fifth monomer solution and a sixth monomer solution, wherein the fifth monomer solution comprises a fifth monomer and a catalyst, and the sixth monomer solution comprises a sixth monomer and an activator, and the fifth monomer and the sixth monomer are lactams; or, the fifth monomer solution comprises an epoxy resin matrix, and the sixth monomer solution comprises an epoxy resin curing agent; and uniformly mixing the fifth monomer solution and the sixth monomer solution to obtain a third raw material solution;

[0028] (9) uniformly attaching the third raw material liquid to the surface of the glass fiber or carbon fiber;

[0029] (10) Winding the glass fiber or carbon fiber attached with the third raw material liquid onto the composite of the inner layer, the middle layer and the water-soluble preform, winding one or more layers of the glass fiber or carbon fiber from the inside to the outside, and heating the glass fiber or carbon fiber wound on the water-soluble preform at the same time, so that the fifth monomer and the sixth monomer on the surface of the glass fiber or carbon fiber react to form polyamide, or the epoxy resin matrix and the epoxy resin curing agent on the surface of the glass fiber or carbon fiber react to form epoxy resin, thereby obtaining a composite of the fiber composite material wound bottle and the water-soluble preform;

[0030] (11) The water-soluble preform in the composite of the fiber composite material wound bottle and the water-soluble preform is removed by washing with water to obtain a fiber composite material wound bottle.

[0031] In one or more embodiments, in step (1), the water-soluble preform is made of a water-soluble inorganic salt by sintering or melt infusion, and the water-soluble inorganic salt is selected from one or more of potassium carbonate, sodium chloride, potassium chloride, potassium nitrate, copper chloride and calcium chloride.

[0032] In one or more embodiments, the first monomer, the second monomer, the third monomer, the fourth monomer, the fifth monomer, and the sixth monomer are each independently selected from one or more of caprolactam, capryllactam, enantholactam, and laurolactam.

[0033] In one or more embodiments, the catalyst in the first monomer solution, the catalyst in the third monomer solution, and the catalyst in the fifth monomer solution are each independently selected from one or more of sodium caprolactam, potassium caprolactam, sodium hydroxide, sodium ethoxide, sodium methoxide, sodium hydride, and metallic sodium.

[0034] In one or more embodiments, in the first monomer solution, the third monomer solution, and the fifth monomer solution, the mass of the catalyst is 0.1-1% of the mass of the first monomer, the third monomer, or the fifth monomer.

[0035] In one or more embodiments, the active agent in the second monomer solution, the active agent in the fourth monomer solution, and the active agent in the sixth monomer solution are each independently selected from one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, biscaprolactam-based diisocyanate, acetyl caprolactam, and benzoyl chloride.

[0036] In one or more embodiments, in the second monomer solution, the fourth monomer solution and the sixth monomer solution, the mass of the active agent is 0.1-1% of the mass of the second monomer, the fourth monomer or the sixth monomer.

[0037] In one or more embodiments, in the fifth monomer solution, the epoxy resin matrix is ​​selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate and aliphatic epoxy resin.

[0038] In one or more embodiments, in the sixth monomer solution, the epoxy resin curing agent is selected from one or more of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, acetic anhydride, hexanoic anhydride, succinic anhydride, cyclohexanecarboxylic anhydride, aniline and meta-phenylenediamine.

[0039] In one or more embodiments, in step (3), step (6) and step (9), the raw material liquid is attached to the fiber surface by injection, the injection speed is 0.1-0.6 g / s, and the temperature of the raw material liquid during injection is 80-180°C.

[0040] In one or more embodiments, step (4), step (7) and step (10) have one or more of the following features:

[0041] The winding is done by using a CNC four-axis fully automatic cylindrical winding machine;

[0042] Winding speed is 0.2-0.9m / s;

[0043] The winding tension when winding the first layer of fibers in the inner layer, middle layer or outer layer is 60-70N, and the winding tension decreases by 2.5-5N layer by layer from the inside to the outside;

[0044] The heating temperature is 140-180℃. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 Schematic diagram of the structure of a composite body of a fiber composite material wrapped around a bottle and a water-soluble preform in some embodiments of the present invention. DETAILED DESCRIPTION

[0046] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0047] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0048] Herein, “comprising”, “including”, “containing” and similar terms encompass the meanings of “consisting essentially of” and “consisting of”. For example, when “A comprises B and C” is disclosed herein, “A consists essentially of B and C” and “A consists of B and C” should be deemed to be disclosed herein.

[0049] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are only for brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0050] In this document, unless otherwise specified, percentage refers to mass percentage and ratio refers to mass ratio.

[0051] Herein, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all substitutes, improvements and equivalents of the methods and materials described in the present invention can be included in the scope limited by the claims.

[0052] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0053] The fiber composite wrapped bottle of the present invention comprises an inner layer, an intermediate layer and an outer layer from the inside to the outside. The intermediate layer is closely attached to the inner layer, and the outer layer is closely attached to the intermediate layer. In some embodiments, the fiber composite wrapped bottle of the present invention consists of an inner layer, an intermediate layer and an outer layer. Herein, unless otherwise specified, the inner layer, the intermediate layer and the outer layer refer to the inner layer, the intermediate layer and the outer layer of the fiber composite wrapped bottle of the present invention, respectively.

[0054] In the fiber composite material wrapped bottle of the present invention, the fibers contained in the inner layer are nylon fibers, the fibers contained in the middle layer are carbon fibers, and the fibers contained in the outer layer are glass fibers or carbon fibers. The most important function of the inner layer is gas barrier. The use of nylon fibers with better compatibility with the resin can more effectively reduce the gap between the resin and the fibers and reduce gas leakage; the middle layer uses the largest amount of carbon fibers for the purpose of weight reduction; the outer layer uses glass fibers or carbon fibers to maximize the compression resistance of the product.

[0055] The inner layer of the fiber composite wrapped bottle of the present invention is composed of a nylon fiber composite layer. A nylon fiber composite layer is composed of a layer of wound nylon fibers and a resin matrix. In some embodiments, the inner layer of the fiber composite wrapped bottle of the present invention is composed of at least two nylon fiber composite layers from the inside to the outside.

[0056] Preferably, the inner layer of the fiber composite wrapped bottle of the present invention consists of 4-10 layers, such as 5 layers, 6 layers, 7 layers, 8 layers, and 9 layers of nylon fiber composite material layers from the inside to the outside. Controlling the number of nylon fiber composite material layers in the inner layer within the above range can achieve a balance between the gas barrier performance, cost and weight of the product.

[0057] In the present invention, a layer of fibers contains only one filament in the thickness direction, except for the fiber intersection points caused by the change of fiber winding direction.

[0058] In the present invention, the nylon fiber is a continuous nylon fiber (i.e., nylon filament), such as nylon 6 filament or nylon 66 filament. The nylon fiber used in the present invention may be a nylon fiber commonly used for winding bottles. The fineness of the nylon fiber is preferably 420-3000D, such as 1000D, 2000D, and the number of holes is preferably 24-96F, such as 36F, 48F, 72F. It is understood that the number of holes in the nylon fiber of 24-96F means that one nylon filament is twisted by 24-96 nylon monofilaments. The nylon fiber is preferably a raw yarn, such as nylon 6 raw yarn or nylon 66 raw yarn.

[0059] In the inner layer of the present invention, the nylon fibers in the innermost nylon fiber composite material layer (i.e., the first nylon fiber composite material layer) are preferably arranged in the form of hoop winding, and the nylon fibers in the two adjacent nylon fiber composite material layers are preferably arranged in the form of hoop winding and spiral winding, respectively. The present invention adopts a combination of multiple winding methods, which can improve the comprehensive strength of the composite material, and help stabilize the position of the fibers, and prevent undesirable phenomena such as fiber dislocation and sliding during processing. In the present invention, the winding angle of the hoop winding is 90°, and the winding angle of the spiral winding is 15-45°. Preferably, in the nylon fiber composite material layer in which the nylon fibers are arranged in the form of spiral winding, the winding angle of the nylon fibers in the outer nylon fiber composite material layer is greater than the winding angle of the nylon fibers in the inner nylon fiber composite material layer, that is, the winding angle of the nylon fibers increases layer by layer from the inside to the outside.

[0060] In the present invention, the resin matrix of the nylon fiber composite material layer, the carbon fiber composite material layer and the glass fiber composite material layer comprises a resin and an optional additive. The additive may include a stabilizer. In some embodiments, the resin matrix consists of a resin and an additive (e.g., a stabilizer).

[0061] In the inner layer of the present invention, the resin contained in the resin matrix of the nylon fiber composite material layer includes polyamide. In some preferred embodiments, in the inner layer, the resin contained in the resin matrix of the nylon fiber composite material layer is polyamide. The present invention uses polyamide in the resin matrix of the nylon fiber composite material layer as the inner layer, which is beneficial to improve the adhesion between the resin and the nylon fiber, reduce the gap between the resin and the fiber, and reduce gas overflow. At the same time, the high polymerization rate of lactam can greatly shorten the post-curing time of traditional materials and greatly improve production efficiency; polyamide is a thermoplastic resin, compared with traditional thermosetting resins, it can be completely recycled after the product reaches its service life, and does not cause environmental pollution.

[0062] The polyamide suitable for the present invention is preferably a polyamide polymerized from lactam. Compared with other polyamide monomers, the present invention uses lactam to polymerize polyamide, which has the following advantages: fast molding speed, can directly prepare wrapped bottle products; low raw material melt viscosity, good fiber wettability; low overall cost. Available lactams include one or more selected from butyrolactam, valerolactam, caprolactam, enantholactam, capryllactam, nonanolactam, decanolactam, undecanolactam, laurolactam, etc. Preferably, the present invention uses a polyamide polymerized from lactam by anionic ring-opening.

[0063] The nylon fiber content of the inner layer of the fiber composite material wound bottle of the present invention is preferably 60-70wt%, such as 62wt%, 65wt%, 68wt%. If the nylon fiber content is too low, the performance of the wound bottle cannot meet the requirements; if the nylon fiber content is too high, the wettability of the resin to the nylon fiber will be affected.

[0064] The middle layer of the fiber composite wrapped bottle of the present invention is composed of a carbon fiber composite layer. A carbon fiber composite layer is composed of a layer of wound carbon fiber and a resin matrix. In some embodiments, the middle layer of the fiber composite wrapped bottle of the present invention is composed of at least 2 carbon fiber composite layers from the inside to the outside.

[0065] Preferably, the middle layer of the fiber composite wrapped bottle of the present invention is composed of 7-11 layers, such as 8 layers, 9 layers, and 10 layers of carbon fiber composite material layers from the inside to the outside. Controlling the number of carbon fiber composite material layers in the middle layer within the above range is conducive to achieving a balance between product strength, cost and weight. In some embodiments, the number of carbon fiber composite material layers in the middle layer is greater than the number of nylon fiber composite material layers in the inner layer, and the number of carbon fiber composite material layers in the middle layer is greater than the number of carbon fiber composite material layers or glass fiber composite material layers in the outer layer, which is conducive to reducing the weight of the wrapped bottle while ensuring its compressive resistance.

[0066] In the present invention, the carbon fiber is a continuous carbon fiber (i.e., carbon fiber filament). The carbon fiber suitable for the present invention may be the carbon fiber commonly used for winding bottles. The surface of the carbon fiber is preferably coated with a sizing agent, such as a vinyl ester or polyamide sizing agent. The sizing agent can protect the surface activity of the carbon fiber, improve the bonding force between the carbon fiber and the resin, and prevent the generation of fuzz. The sizing agent suitable for the present invention may be an epoxy resin, polyurethane, polyvinyl pyrrolidone, polyamide, polyimide, phenoxy resin, etc. The coating amount of the sizing agent on the carbon fiber surface (the ratio of the mass of the sizing agent to the total mass of the fiber) may be 0.3-1.2wt%, for example 0.5wt%, 0.7wt%, 1wt%.

[0067] In the middle layer of the present invention, the carbon fibers in the innermost carbon fiber composite material layer (i.e., the first carbon fiber composite material layer) are preferably arranged in the form of hoop winding, and the carbon fibers in the two adjacent carbon fiber composite material layers are preferably arranged in the form of hoop winding and spiral winding, respectively. Preferably, in the carbon fiber composite material layer in which the carbon fibers are arranged in the form of spiral winding, the winding angle of the carbon fibers in the outer carbon fiber composite material layer is greater than the winding angle of the carbon fibers in the inner carbon fiber composite material layer, that is, the winding angle of the carbon fibers increases layer by layer from the inside to the outside.

[0068] In the intermediate layer of the present invention, the resin contained in the resin matrix of the carbon fiber composite material layer includes polyamide. In some preferred embodiments, in the intermediate layer, the resin contained in the resin matrix of the carbon fiber composite material layer is polyamide.

[0069] The carbon fiber content of the middle layer of the fiber composite material wound bottle of the present invention is preferably 60-70wt%, such as 62wt%, 65wt%, 68wt%. If the carbon fiber content is too low, the performance of the wound bottle cannot meet the requirements; if the carbon fiber content is too high, it will affect the wettability of the resin to the carbon fiber.

[0070] The outer layer of the fiber composite wrapped bottle of the present invention is composed of a glass fiber composite layer or a carbon fiber composite layer. A layer of glass fiber composite layer is composed of a layer of wound glass fiber and a resin matrix. A layer of carbon fiber composite layer is composed of a layer of wound carbon fiber and a resin matrix. In some embodiments, the outer layer of the fiber composite wrapped bottle of the present invention is composed of at least 2 layers of glass fiber composite layers or carbon fiber composite layers from the inside to the outside.

[0071] Preferably, the outer layer of the fiber composite wrapped bottle of the present invention consists of 4-10 layers, such as 5 layers, 6 layers, 7 layers, 8 layers, or 9 layers of glass fiber composite layers or carbon fiber composite layers from the inside to the outside. Controlling the number of glass fiber composite layers or carbon fiber composite layers in the outer layer within the aforementioned range is conducive to achieving a balance between product strength, cost, and quality.

[0072] The glass fiber suitable for the present invention may be a glass fiber commonly used for winding bottles.

[0073] In the outer layer of the present invention, the glass fibers or carbon fibers in the innermost glass fiber composite material layer (i.e., the first glass fiber composite material layer) or the innermost carbon fiber composite material layer (i.e., the first carbon fiber composite material layer) are preferably arranged in the form of circumferential winding, and the glass fibers or carbon fibers in the two adjacent glass fiber composite material layers or carbon fiber composite material layers are preferably arranged in the form of circumferential winding and spiral winding, respectively. Preferably, in the glass fiber composite material layer or carbon fiber composite material layer in which the glass fibers or carbon fibers are arranged in the form of spiral winding, the winding angle of the glass fibers or carbon fibers in the outer glass fiber composite material layer or carbon fiber composite material layer is greater than the winding angle of the glass fibers or carbon fibers in the inner glass fiber composite material layer or carbon fiber composite material layer, that is, the winding angle of the glass fibers or carbon fibers increases layer by layer from the inside to the outside.

[0074] In the outer layer of the present invention, the resin contained in the resin matrix of the glass fiber composite material layer or the carbon fiber composite material layer comprises polyamide or epoxy resin. In some preferred embodiments, in the outer layer, the resin contained in the resin matrix of the glass fiber composite material layer or the carbon fiber composite material layer is polyamide or epoxy resin.

[0075] In the present invention, the resin in the resin matrix of the carbon fiber composite material layer in the middle layer is preferably polyamide, and the resin in the resin matrix of the carbon fiber composite material layer in the outer layer is preferably polyamide or epoxy resin.

[0076] In some embodiments, the present invention uses polyamide in the resin matrix of the middle layer and / or outer layer, which has a high polymerization rate and can significantly shorten the post-curing time of traditional materials, greatly improving production efficiency. Polyamide is a thermoplastic resin, and compared with traditional thermosetting resins, it can be completely recycled after the product reaches its service life without causing environmental pollution.

[0077] The epoxy resin suitable for the present invention is preferably formed by cross-linking and curing an epoxy resin matrix and an epoxy resin curing agent. Compared with other thermosetting monomers, the epoxy resin used in the present invention has the following advantages: high resin strength, good weather resistance, and strong solvent corrosion resistance. Available epoxy resin matrices include one or more selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate and aliphatic epoxy resin. Available epoxy resin curing agents include one or more selected from hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, acetic anhydride, caproic anhydride, succinic anhydride, cyclohexanecarboxylic anhydride, aniline and m-phenylenediamine.

[0078] The glass fiber or carbon fiber content of the outer layer of the fiber composite material wound bottle of the present invention is preferably 60-70wt%, such as 62wt%, 65wt%, 68wt%. If the glass fiber or carbon fiber content is too low, the performance of the wound bottle cannot meet the requirements; if the glass fiber or carbon fiber content is too high, it will affect the wettability of the resin to the carbon fiber.

[0079] In the present invention, the total number of nylon fiber composite material layers in the inner layer, carbon fiber composite material layers in the middle layer, and glass fiber composite material layers or carbon fiber composite material layers in the outer layer is 22-28. The total number of layers is determined based on the comprehensive cost and actual use. If the number of layers is too low, the product strength is insufficient, and if the number of layers is high, the cost is high and the product weight is also higher.

[0080] In some embodiments, the middle layer and the outer layer of the fiber composite wrapped bottle of the present invention are both composed of carbon fiber composite layers, and any or specific one or more carbon fiber composite layers can be regarded as the middle layer, and the remaining one or more carbon fiber composite layers can be regarded as the outer layer, provided that the carbon fiber composite layer serving as the middle layer or the outer layer meets the description of any embodiment of this invention.

[0081] In the present invention, the resin matrix of the nylon fiber composite material layer, the carbon fiber composite material layer and the glass fiber composite material layer preferably contain a stabilizer to improve its aging resistance. Stabilizers suitable for the present invention include but are not limited to hindered phenol antioxidants (such as antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 608), phosphite antioxidants (such as antioxidant V76-P, antioxidant 168), thioester antioxidants (such as antioxidant DSTDP, antioxidant DLTDP), etc. In the resin matrix, the mass of the stabilizer is preferably 0.3-1.5wt% of the total mass of the resin matrix, such as 0.6wt%, 0.9wt%, 1.2wt%. In a preferred embodiment, the stabilizers used in the present invention include hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants. In the resin matrix, the masses of the hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants are preferably 0.1-0.5wt% of the total mass of the resin matrix, for example 0.2wt%, 0.3wt%, 0.4wt%, respectively.

[0082] The fiber composite material wrapped bottle of the present invention can be obtained by sequentially forming an inner layer, an intermediate layer and an outer layer of the fiber composite material wrapped bottle on the surface of the water-soluble preform from the inside to the outside. Figure 1 The fiber composite material is wound around a composite of a bottle and a water-soluble preform, and then washed with water to remove the water-soluble preform in the composite.

[0083] In a preferred embodiment, the method for preparing a fiber composite material wrapped bottle of the present invention comprises the following steps:

[0084] (1) providing a water-soluble preform;

[0085] (2) providing a first monomer solution and a second monomer solution, wherein the first monomer solution comprises a first monomer and a catalyst, and the second monomer solution comprises a second monomer and an activator, and the first monomer solution and the second monomer solution are mixed uniformly to obtain a first raw material solution;

[0086] (3) uniformly attaching the first raw material liquid to the surface of the nylon fiber;

[0087] (4) winding the nylon fiber attached with the first raw material liquid onto the water-soluble preform, winding one or more layers of nylon fiber from the inside to the outside, and heating the nylon fiber wound on the water-soluble preform so that the first monomer and the second monomer on the surface of the nylon fiber react to form polyamide, thereby obtaining a composite body of the fiber composite material wound around the inner layer of the bottle and the water-soluble preform;

[0088] (5) providing a third monomer solution and a fourth monomer solution, wherein the third monomer solution comprises a third monomer and a catalyst, and the fourth monomer solution comprises a fourth monomer and an activator, and the third monomer solution and the fourth monomer solution are uniformly mixed to obtain a second raw material solution;

[0089] (6) uniformly attaching the second raw material liquid to the surface of the carbon fiber;

[0090] (7) Winding the carbon fiber attached with the second raw material liquid onto the composite of the inner layer and the water-soluble preform, winding one or more layers of carbon fiber from the inside to the outside, and heating the carbon fiber wound on the composite so that the third monomer and the fourth monomer on the surface of the carbon fiber react to form polyamide, thereby obtaining a composite of the fiber composite material wound around the bottle inner layer, the middle layer and the water-soluble preform;

[0091] (8) providing a fifth monomer solution and a sixth monomer solution, wherein the fifth monomer solution comprises a fifth monomer and a catalyst, and the sixth monomer solution comprises a sixth monomer and an activator; or, the fifth monomer solution comprises an epoxy resin matrix, and the sixth monomer solution comprises an epoxy resin curing agent; and uniformly mixing the fifth monomer solution and the sixth monomer solution to obtain a third raw material solution;

[0092] (9) uniformly attaching the third raw material liquid to the surface of the glass fiber or carbon fiber;

[0093] (10) Winding glass fibers or carbon fibers to which the third raw material liquid is attached onto a composite of the inner layer, the middle layer, and the water-soluble preform, winding one or more layers of glass fibers or carbon fibers from the inside out, and heating the glass fibers or carbon fibers wound on the composite to react the fifth monomer and the sixth monomer on the surface of the glass fibers or carbon fibers to form polyamide, or to react the epoxy resin matrix and the epoxy resin curing agent on the surface of the glass fibers or carbon fibers to form epoxy resin, thereby obtaining a composite of a fiber composite material wound around a bottle and a water-soluble preform;

[0094] (11) The water-soluble preform in the composite of the fiber composite material wound bottle and the water-soluble preform is removed by washing with water to obtain a fiber composite material wound bottle.

[0095] Composite material winding technology requires the use of a preform for shaping. The preform used in the present invention is a water-soluble preform, which can be removed by washing with water at the end. Preferably, the preform used in the present invention is a water-soluble inorganic salt preform, which can be made by high-temperature sintering or melt infusion of a water-soluble inorganic salt. Available water-soluble inorganic salts include one or more selected from potassium carbonate, sodium chloride, potassium chloride, potassium nitrate, copper chloride, calcium chloride, etc. In some embodiments, the water-soluble preform is made by melting and infusing 55±5wt% of potassium chloride, 35±5wt% of potassium nitrate, and 10±5wt% of sodium chloride, which account for 55±5wt% of the total mass of the preform, into a mold at 800°C and cooled to room temperature. The preform is preferably dried before use to remove moisture.

[0096] In the present invention, the first monomer and the second monomer may be the same or different. The first monomer and the second monomer may react to form a polyamide under the action of a catalyst and an activator. In some embodiments, the first monomer and the second monomer are lactams, for example, the first monomer and the second monomer may each be selected from one or more of butyrolactam, valerolactam, caprolactam, enantholactam, capryllactam, nonanolactam, caprolactam, undecanolactam, laurolactam, etc.

[0097] The first monomer solution comprises the first monomer and a catalyst. In some embodiments, the first monomer solution is composed of the first monomer and a catalyst, or is composed of the first monomer, a catalyst and an additive (such as a stabilizer). In the first monomer solution, the mass of the catalyst can be 0.1-1% of the mass of the first monomer, such as 0.2%, 0.5%. In the present invention, the catalyst can be a catalyst for catalyzing an amide condensation reaction or lactam polymerization, such as a catalyst for catalyzing anionic ring-opening polymerization of lactams. Available catalysts include one or more selected from sodium caprolactam, potassium caprolactam, sodium hydroxide, sodium ethoxide, sodium methoxide, sodium hydride, metallic sodium, etc.

[0098] The second monomer solution comprises the second monomer and an activating agent. In some embodiments, the second monomer solution is composed of the second monomer and the activating agent, or is composed of the second monomer, the activating agent and an additive (such as a stabilizer). In the second monomer solution, the mass of the activating agent can be 0.1-1% of the mass of the second monomer, such as 0.2%, 0.5%. In the present invention, the effect of the activating agent is to shorten the polymerization induction period and increase the polymerization rate. Available activating agents include one or more selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, dicaprolactam diisocyanate, acetyl caprolactam, benzoyl chloride, etc.

[0099] In the present invention, before mixing the first monomer solution and the second monomer solution, the first monomer solution and the second monomer solution are preferably dried to remove moisture. In some embodiments, the first monomer solution and the second monomer solution are vacuum dehydrated at 80-160° C., for example, 100° C., 120° C., 140° C. The first monomer solution and the second monomer solution can be stored in two solution storage tanks, respectively.

[0100] When the first monomer solution and the second monomer solution are mixed, the mass ratio of the first monomer solution and the second monomer solution can be 1:10 to 10:1, for example, 1:2, 1:1, 2:1. The mixing ratio of the first monomer solution and the second monomer solution can be determined according to the content of the catalyst in the first monomer solution, the content of the activator in the second monomer solution, and the target content of the catalyst and the activator in the first raw material solution. The first monomer solution and the second monomer solution can be accurately metered by a metering pump and mixed in a static mixer.

[0101] In the present invention, before the first raw material liquid is attached to the surface of the nylon fiber, the nylon fiber is preferably subjected to a heating and drying treatment, the drying temperature may be 100-140° C., such as 110° C., 120° C., 130° C., and the drying time may be 1-5 min., such as 2 min., 3 min., 4 min. A continuous fiber drying box may be used for the heating and drying treatment.

[0102] In the present invention, the first raw material liquid can be attached to the nylon fiber by injection. The injection speed is preferably 0.1-0.6g / s, such as 0.15g / s, 0.2g / s, 0.3g / s, 0.4g / s, 0.5g / s. The temperature of the first raw material liquid during injection is preferably 80-180°C, such as 100°C, 120°C, 140°C, 160°C. In the present invention, controlling the injection speed and the temperature of the raw material liquid during injection within the aforementioned range is conducive to allowing the polyamide monomer to attach to the fiber in an appropriate amount, controlling the fiber content in the fiber composite material layer within the range of 60-70wt%, and improving the fluidity of the raw material liquid and the wettability to the fiber.

[0103] After the first raw material liquid is evenly attached to the surface of the nylon fiber, the nylon fiber is quickly wound onto the water-soluble parison. A CNC four-axis fully automatic cylindrical winding machine can be used for winding. During winding, the nylon fiber needs to be in a heated dry environment, and the heating temperature is preferably 140-180°C, for example, 160°C, so that the first monomer and the second monomer attached to the nylon fiber react to form polyamide. In some embodiments, the equipment used for winding is a CNC four-axis fully automatic cylindrical winding machine. During winding, the barrel of the CNC four-axis fully automatic cylindrical winding machine is placed as a whole in a dry environment of 140-180°C.

[0104] In the present invention, when preparing the inner layer, it is preferred to use a circumferential winding method (winding angle of 90°) when winding the first layer of nylon fibers (i.e., the innermost layer of nylon fibers), and it is preferred to use a circumferential winding method (winding angle of 90°) and a spiral winding method (winding angle of 15-45°) when winding the two adjacent layers of nylon fibers. In some embodiments, the winding angle of the first layer of nylon fibers is 15-20°, for example, 16°, 18°. Preferably, when winding in a spiral winding method, the winding angle of the nylon fibers in the outer layer is greater than the winding angle of the nylon fibers in the inner layer, that is, the winding angle increases layer by layer from the inside to the outside. In some embodiments, when winding in a spiral winding method, the winding angle of the n+2th layer of nylon fibers is 1-20° greater than the winding angle of the nth layer of nylon fibers. In some embodiments, the winding angle of the outermost layer of nylon fibers wound in a spiral winding method is 40-45°, for example, 41°, 43°. The winding speed is preferably 0.2-0.9 m / s, such as 0.4 m / s and 0.6 m / s. The initial winding tension (the tension when winding the first layer of nylon fibers) is preferably 60-70 N, such as 62 N, 65 N, and 68 N. The winding tension decreases by 2.5-5 N layer by layer from the inside to the outside (that is, when winding two adjacent layers of nylon fibers, the tension when winding the outer layer of nylon fibers is 2.5-5 N lower than the tension when winding the inner layer of nylon fibers). Setting the winding tension in the above manner helps to reduce the internal stress of the product and improve the product's load-bearing capacity.

[0105] In the present invention, a heating temperature of 140-180° C. and a winding speed of 0.2-0.9 m / s during fiber winding are beneficial to increasing the polymerization rate, so that the polymerization is completed quickly during the winding process, thereby improving production efficiency.

[0106] In the present invention, the third monomer and the fourth monomer may be the same or different. The third monomer and the fourth monomer may react to form polyamide under the action of a catalyst and an activator. In some embodiments, the third monomer and the fourth monomer are lactams, such as the third monomer and the fourth monomer may each be selected from one or more of butyrolactam, valerolactam, caprolactam, enantholactam, capryllactam, nonanolactam, caprolactam, undecanolactam, laurolactam, etc. The third monomer and the first monomer may be the same or different. The fourth monomer and the second monomer may be the same or different.

[0107] The third monomer solution comprises a third monomer and a catalyst. In some embodiments, the third monomer solution is composed of a third monomer and a catalyst, or is composed of a third monomer, a catalyst and an additive (e.g., a stabilizer). In the third monomer solution, the mass of the catalyst can be 0.1-1% of the mass of the third monomer, such as 0.2%, 0.5%. The third monomer solution and the first monomer solution can be the same or different.

[0108] The fourth monomer solution comprises a fourth monomer and an active agent. In some embodiments, the fourth monomer solution is composed of a fourth monomer and an active agent, or is composed of a fourth monomer, an active agent and an additive (e.g., a stabilizer). In the fourth monomer solution, the mass of the active agent can be 0.1-1% of the mass of the fourth monomer, such as 0.2%, 0.5%. The fourth monomer solution and the second monomer solution can be the same or different.

[0109] In the present invention, before mixing the third monomer solution and the fourth monomer solution, the third monomer solution and the fourth monomer solution are preferably dried to remove moisture. In some embodiments, the third monomer solution and the fourth monomer solution are vacuum dehydrated at 80-160° C., for example, 100° C., 120° C., 140° C. The third monomer solution and the fourth monomer solution can be stored in two solution storage tanks, respectively.

[0110] When mixing the third monomer solution and the fourth monomer solution, the mass ratio of the third monomer solution and the fourth monomer solution can be 1:10 to 10:1, for example 1:2, 1:1, 2:1. The mixing ratio of the third monomer solution and the fourth monomer solution can be determined according to the content of the catalyst in the third monomer solution, the content of the activating agent in the fourth monomer solution, and the target content of the catalyst and the activating agent in the second raw material solution. The third monomer solution and the fourth monomer solution can be accurately measured by a metering pump and mixed in a static mixer. The second raw material solution and the first raw material solution can be the same or different.

[0111] In the present invention, the carbon fiber to be coated with the raw material liquid is preferably a carbon fiber with a sizing agent coated on the surface. Before the second raw material liquid is attached to the surface of the carbon fiber, the carbon fiber is preferably subjected to a heating and drying treatment, and the drying temperature may be 120-160°C, such as 130°C, 140°C, 150°C, and the drying time may be 1-5min, such as 2min, 3min, 4min. A continuous fiber drying box may be used for the heating and drying treatment.

[0112] In the present invention, the second raw material liquid can be attached to the carbon fiber by injection. The injection speed is preferably 0.1-0.6 g / s, such as 0.15 g / s, 0.2 g / s, 0.3 g / s, 0.4 g / s, 0.5 g / s. The temperature of the second raw material liquid during injection is preferably 80-180°C, such as 100°C, 120°C, 140°C, 160°C.

[0113] After the second raw material liquid is evenly attached to the surface of the carbon fiber, the carbon fiber is quickly wound onto the composite of the inner layer of the fiber composite material winding bottle and the water-soluble preform. A CNC four-axis fully automatic cylindrical winding machine can be used for winding. During winding, the carbon fiber needs to be in a heated dry environment, and the heating temperature is preferably 140-180°C, so that the third monomer and the fourth monomer attached to the carbon fiber react to form polyamide. In some embodiments, the equipment used for winding is a CNC four-axis fully automatic cylindrical winding machine. During winding, the barrel of the CNC four-axis fully automatic cylindrical winding machine is placed as a whole in a dry environment of 140-180°C.

[0114] In the present invention, when preparing the middle layer, it is preferred to use a circumferential winding method (winding angle of 90°) when winding the first layer of carbon fiber (i.e., the innermost layer of carbon fiber), and it is preferred to use a circumferential winding method (winding angle of 90°) and a spiral winding method (winding angle of 15-45°) when winding two adjacent layers of carbon fiber. In some embodiments, the winding angle of the first layer of carbon fiber is 15-20°, for example, 16°, 18°. Preferably, when winding in a spiral winding manner, the winding angle of the outermost carbon fiber is greater than the winding angle of the innermost carbon fiber, that is, the winding angle increases layer by layer from the inside to the outside. In some embodiments, when winding in a spiral winding manner, the winding angle of the n+2th layer of carbon fiber is 1-20° greater than the winding angle of the nth layer of carbon fiber. In some embodiments, the winding angle of the outermost layer of carbon fiber wound in a spiral winding manner is 40-45°, for example, 41°, 43°. The winding speed is preferably 0.2-0.9m / s, for example, 0.4m / s, 0.6m / s. The initial winding tension (the tension when winding the first layer of carbon fiber) is preferably 60-70N, for example 62N, 65N, 68N, and the winding tension decreases by 2.5-5N layer by layer from the inside to the outside (that is, when winding two adjacent layers of carbon fiber, the tension when winding the outer layer of carbon fiber is 2.5-5N lower than the tension when winding the inner layer of carbon fiber).

[0115] In the present invention, the fifth monomer and the sixth monomer may be the same or different. The fifth monomer and the sixth monomer may react to generate polyamide under the action of a catalyst and an activator. In some embodiments, the fifth monomer and the sixth monomer are lactams, for example, the fifth monomer and the sixth monomer may each be selected from one or more of butyrolactam, valerolactam, caprolactam, enantholactam, capryllactam, nonanolactam, caprolactam, undecanolactam, laurolactam, etc. The fifth monomer and the first monomer may be the same or different. The sixth monomer and the second monomer may be the same or different. In some embodiments, the fifth monomer solution comprises the fifth monomer and a catalyst. In some embodiments, the fifth monomer solution is composed of the fifth monomer and a catalyst, or is composed of the fifth monomer, a catalyst and an additive (such as a stabilizer). In the fifth monomer solution, the mass of the catalyst may be 0.1-1% of the mass of the fifth monomer, for example 0.2%, 0.5%. The fifth monomer solution and the first monomer solution may be the same or different.

[0116] In some embodiments, the sixth monomer solution comprises a sixth monomer and an active agent. In some embodiments, the sixth monomer solution consists of a sixth monomer and an active agent, or consists of a sixth monomer, an active agent and an additive (e.g., a stabilizer). In the sixth monomer solution, the mass of the active agent may be 0.1-1% of the mass of the sixth monomer, such as 0.2%, 0.5%. The sixth monomer solution and the second monomer solution may be the same or different.

[0117] In some embodiments, the fifth monomer solution comprises an epoxy resin matrix, and the sixth monomer solution comprises an epoxy resin curing agent, and the epoxy resin matrix and the epoxy resin curing agent can undergo a crosslinking reaction to cure to form an epoxy resin. The epoxy resin matrix and epoxy resin curing agent applicable to the present invention are as described above. In some embodiments, the fifth monomer solution is composed of an epoxy resin matrix, or is composed of an epoxy resin matrix and an additive (e.g., a stabilizer). In some embodiments, the sixth monomer solution is composed of an epoxy resin curing agent, or is composed of an epoxy resin curing agent and an additive (e.g., a stabilizer).

[0118] In the present invention, before mixing the fifth monomer solution and the sixth monomer solution, the fifth monomer solution and the sixth monomer solution are preferably dried to remove moisture. In some embodiments, the fifth monomer solution and the sixth monomer solution are vacuum dehydrated at 80-160° C., for example, 100° C., 120° C., 140° C. The fifth monomer solution and the sixth monomer solution can be stored in two solution storage tanks, respectively.

[0119] When the fifth monomer solution and the sixth monomer solution are mixed, the mass ratio of the fifth monomer solution and the sixth monomer solution can be 1:10 to 10:1, for example 1:2, 1:1, 2:1. The mixing ratio of the fifth monomer solution and the sixth monomer solution can be determined according to the content of the catalyst in the fifth monomer solution, the content of the activator in the sixth monomer solution, and the target content of the catalyst and the activator in the third raw material solution, or according to the content of the epoxy resin matrix in the fifth monomer solution and the content of the epoxy resin curing agent in the sixth monomer solution. The fifth monomer solution and the sixth monomer solution can be accurately measured by a metering pump and mixed in a static mixer. The third raw material solution and the first raw material solution can be the same or different.

[0120] In the present invention, the carbon fiber to be coated with the raw material liquid is preferably a carbon fiber with a sizing agent coated on the surface. Before the third raw material liquid is attached to the surface of the carbon fiber, the carbon fiber is preferably subjected to a heating and drying treatment, and the drying temperature may be 120-160° C., such as 130° C., 140° C., 150° C., and the drying time may be 1-5 min, such as 2 min, 3 min, 4 min. A continuous fiber drying box may be used for the heating and drying treatment.

[0121] In the present invention, the third raw material liquid can be attached to the glass fiber or carbon fiber by injection. The injection speed is preferably 0.1-0.6 g / s, such as 0.15 g / s, 0.2 g / s, 0.3 g / s, 0.4 g / s, 0.5 g / s. The temperature of the third raw material liquid during injection is preferably 80-180°C, such as 100°C, 120°C, 140°C, 160°C.

[0122] After the third raw material liquid is evenly attached to the surface of the glass fiber or carbon fiber, the glass fiber or carbon fiber is quickly wound onto the composite of the inner layer, the middle layer and the water-soluble preform of the fiber composite material winding bottle. A CNC four-axis fully automatic cylindrical winding machine can be used for winding. During winding, the glass fiber or carbon fiber needs to be in a heated dry environment, and the heating temperature is preferably 140-180°C, so that the fifth monomer and the sixth monomer attached to the glass fiber or carbon fiber react to form polyamide, or the epoxy resin matrix and the epoxy resin curing agent attached to the glass fiber or carbon fiber react to form epoxy resin. In some embodiments, the equipment used for winding is a CNC four-axis fully automatic cylindrical winding machine. During winding, the barrel of the CNC four-axis fully automatic cylindrical winding machine is placed in a dry environment of 140-180°C as a whole.

[0123] In the present invention, when preparing the outer layer, it is preferred to use a circumferential winding method (winding angle of 90°) when winding the first layer of glass fiber or carbon fiber (i.e., the innermost layer of glass fiber or carbon fiber), and preferably use a circumferential winding method (winding angle of 90°) and a spiral winding method (winding angle of 15-45°) when winding two adjacent layers of glass fiber or carbon fiber. In some embodiments, the winding angle of the first layer of glass fiber or carbon fiber is 15-20°, for example, 16°, 18°. Preferably, when winding in a spiral winding method, the winding angle of the glass fiber or carbon fiber of the outer layer is greater than the winding angle of the glass fiber or carbon fiber of the inner layer, that is, the winding angle increases layer by layer from the inside to the outside. In some embodiments, when winding in a spiral winding method, the winding angle of the n+2th layer of glass fiber or carbon fiber is 1-20° greater than the winding angle of the nth layer of glass fiber or carbon fiber. In some embodiments, the winding angle of the outermost layer of glass fiber or carbon fiber wound in a spiral winding method is 40-45°, for example, 41°, 43°. The winding speed is preferably 0.2-0.9 m / s, such as 0.4 m / s and 0.6 m / s. The initial winding tension (the tension when winding the first layer of carbon fiber) is preferably 60-70 N, such as 62 N, 65 N, and 68 N, and the winding tension decreases by 2.5-5 N layer by layer from the inside to the outside (that is, when winding two adjacent layers of glass fiber or carbon fiber, the tension when winding the outer layer of glass fiber or carbon fiber is 2.5-5 N lower than the tension when winding the inner layer of glass fiber or carbon fiber).

[0124] In the present invention, additives (such as stabilizers) can be added to the first monomer solution, the second monomer solution, the first raw material solution, the third monomer solution, the fourth monomer solution, the second raw material solution, the fifth monomer solution, the sixth monomer solution and / or the third raw material solution, so that the resin matrix of the inner layer, the middle layer and / or the outer layer of the fiber composite material wrapped bottle contains the additive (such as stabilizer).

[0125] After the winding molding is completed, the water-soluble preform can be completely removed by water washing. The water washing can be carried out under high temperature and high pressure conditions, for example, water washing can be carried out at 100±20°C and 2±0.5MPa to remove the water-soluble preform.

[0126] The present invention has the following beneficial effects:

[0127] 1. Since the main resin raw materials used in the present invention are produced in large quantities by the petrochemical industry, their prices are significantly lower than those of resin raw materials prepared by traditional fine chemicals. Therefore, the cost of the fiber composite material wrapped bottle product of the present invention is significantly lower than that of existing products;

[0128] 2. The present invention uses lactam as a polymerization monomer, which has a high polymerization rate, can greatly shorten the post-curing time of traditional materials and greatly improve production efficiency;

[0129] 3. The polyamide resin used in the present invention is a thermoplastic resin. Compared with the traditional thermosetting resin, it can be completely recycled after the product reaches its service life and does not cause environmental pollution;

[0130] 4. The present invention uses in-situ polymerization technology of polyamide materials, combines the actual needs of different layers of the wrapped bottle, and uses different fiber materials to form the inner layer, middle layer and outer layer of the wrapped bottle to prepare a thermoplastic linerless hydrogen storage bottle with high strength, high inter-layer bonding strength, high preparation efficiency and effective recycling.

[0131] The fiber composite material wrapped bottle of the present invention can be applied to hydrogen storage cylinders of hydrogen energy batteries, storage and transportation devices (tanks) of various high-pressure gases, and the like.

[0132] The present invention will be described below in the form of specific examples. It should be understood that these examples are merely illustrative and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise stated, conventional methods, reagents and materials in the art. The raw material compounds in the examples can all be purchased through commercial routes.

[0133] The nylon fiber used in the embodiment is a continuous nylon 6 raw yarn with a fineness of 420D and a pore number of 48F. Before use, it is heated and dried in a continuous fiber drying box at a drying temperature of 120° C. and a drying time of 2 minutes.

[0134] The carbon fiber used in the embodiment is a continuous carbon fiber with 0.5 wt % polyvinyl pyrrolidone sizing agent coated on the surface. Before use, it is heated and dried in a continuous fiber drying oven at a drying temperature of 140° C. for 2 minutes.

[0135] The stabilizer used in the example is a mixture of antioxidant 1010, antioxidant 168 and antioxidant DSTDP in a mass ratio of 1:1:1.

[0136] Example 1

[0137] In this embodiment, a fiber composite material wrapped bottle is prepared by the following steps:

[0138] (1) providing a water-soluble preform;

[0139] (2) mixing caprolactam and sodium caprolactam in a mass ratio of 100:0.5 to obtain monomer solution A, which is stored in tank A; mixing caprolactam and toluene diisocyanate in a mass ratio of 100:0.5 to obtain monomer solution B, which is stored in tank B; vacuum dehydrating the solutions in tanks A and B at 120° C., adding monomer solution A and monomer solution B in a mass ratio of 1:1 to a static mixer by a metering pump and mixing them thoroughly, adding a stabilizer to obtain a raw material solution A, wherein the mass fraction of the stabilizer in the raw material solution A is 1 wt %;

[0140] (3) The raw material liquid A is uniformly injected onto the nylon fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 100° C.;

[0141] (4) The nylon fiber attached with the raw material liquid A is quickly wound onto the water-soluble preform. The equipment used is a CNC four-axis fully automatic cylindrical winding machine. The cylinder of the equipment is placed in a dry environment at 160°C. A total of 9 layers of nylon fiber are wound on the entire can body of the preform from the inside to the outside. The odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a circumferential manner with a winding angle of 90° and a winding speed of 0.5 m / s. The even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a circumferential manner with a winding angle of 90° and a winding speed of 0.5 m / s. The spiral winding method is used, the winding angles of the second, fourth, sixth and eighth layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.5 m / s, the winding tension of the first layer is 65 N, and the winding tensions of the second, third, fourth, fifth, sixth, seventh, eighth and ninth layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N and 33 N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of an inner layer and a water-soluble preform;

[0142] (5) The raw material liquid A is uniformly injected onto the carbon fiber to be wound, the injection speed is 0.15 g / s, and the temperature of the raw material liquid during injection is 100 °C;

[0143] (6) The carbon fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (4), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160°C; 9 layers of carbon fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop winding manner, with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral winding manner. The winding method is as follows: the winding angles of the 2nd, 4th, 6th and 8th layers are 15°, 25°, 35° and 45° respectively; the winding speed is 0.5 m / s; the winding tension of the 1st layer is 65 N; the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th and 9th layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N and 33 N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of an inner layer, an intermediate layer and a water-soluble preform;

[0144] (7) The raw material liquid A is uniformly injected onto the glass fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 100° C.;

[0145] (8) The glass fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (6), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160° C.; 9 layers of glass fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a circumferential manner, with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral manner. The winding angles of the second, fourth, sixth and eighth layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.5 m / s, the winding tension of the first layer is 65 N, and the winding tensions of the second, third, fourth, fifth, sixth, seventh, eighth and ninth layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N and 33 N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of a fiber composite material wound bottle and a water-soluble preform;

[0146] (9) The water-soluble preform in the composite is removed by washing at 100° C. and 2 MPa to obtain a fiber composite material wrapped bottle, wherein the inner layer nylon fiber content is 60-70wt%, the middle layer carbon fiber content is 60-70wt%, and the outer layer glass fiber content is 60-70wt%.

[0147] Example 2

[0148] In this embodiment, a fiber composite material wrapped bottle is prepared by the following steps:

[0149] (1) providing a water-soluble preform;

[0150] (2) capryllactam and sodium ethoxide are mixed in a mass ratio of 100:0.1 to obtain a monomer solution A, which is stored in a tank A; capryllactam and acetyl caprolactam are mixed in a mass ratio of 100:0.1 to obtain a monomer solution B, which is stored in a tank B; the solutions in tanks A and B are vacuum dehydrated at 90° C., and monomer solution A and monomer solution B are added to a static mixer in a mass ratio of 1:1 by a metering pump and fully mixed, and a stabilizer is added to obtain a raw material solution A, wherein the mass fraction of the stabilizer in the raw material solution A is 1 wt %;

[0151] (3) The raw material liquid A is uniformly injected onto the nylon fiber to be wound, the injection speed is 0.2 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0152] (4) The nylon fiber attached with the raw material liquid A is quickly wound onto the water-soluble preform. The equipment used is a CNC four-axis fully automatic cylindrical winding machine. The cylinder of the equipment is placed in a dry environment at 140°C. A total of 9 layers of nylon fiber are wound on the entire can body of the preform from the inside to the outside. The odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop winding manner with a winding angle of 90° and a winding speed of 0.2 m / s. The even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral winding manner. Winding method: the winding angles of the 2nd, 4th, 6th and 8th layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.2m / s, the winding tension of the 1st layer is 60N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th and 9th layers are 57.5N, 55N, 52.5N, 50N, 47.5N, 45N, 42.5N and 40N respectively; during the winding process, caprylic acid amide is polymerized into polycaprylic acid amide to obtain a composite of an inner layer and a water-soluble preform;

[0153] (5) The raw material liquid A is uniformly injected onto the carbon fiber to be wound, the injection speed is 0.1 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0154] (6) The carbon fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (4), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 140° C.; 9 layers of carbon fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop winding manner, the winding angle is 90°, and the winding speed is 0.2 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral winding manner. The winding angles of the 2nd, 4th, 6th and 8th layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.2m / s, the winding tension of the 1st layer is 60N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th and 9th layers are 57.5N, 55N, 52.5N, 50N, 47.5N, 45N, 42.5N and 40N respectively; during the winding process, caprylic acid amide is polymerized into polycaprylic acid amide to obtain a composite of an inner layer, an intermediate layer and a water-soluble preform;

[0155] (7) The raw material liquid A is uniformly injected onto the glass fiber to be wound, the injection speed is 0.2 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0156] (8) The glass fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (6), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 140° C.; 9 layers of glass fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop winding manner, the winding angle is 90°, and the winding speed is 0.2 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral winding manner, and the 9th layers are wound in a spiral winding manner. The winding angles of the 2nd, 4th, 6th and 8th layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.2 m / s, the winding tension of the 1st layer is 60 N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th and 9th layers are 57.5 N, 55 N, 52.5 N, 50 N, 47.5 N, 45 N, 42.5 N and 40 N respectively; during the winding process, caprylic acid amide is polymerized into polycaprylic acid amide to obtain a composite of a fiber composite material wound bottle and a water-soluble preform;

[0157] (9) The water-soluble preform in the composite is removed by washing at 100° C. and 2 MPa to obtain a fiber composite material wrapped bottle, wherein the inner layer nylon fiber content is 60-70wt%, the middle layer carbon fiber content is 60-70wt%, and the outer layer glass fiber content is 60-70wt%.

[0158] Example 3

[0159] In this embodiment, a fiber composite material wrapped bottle is prepared by the following steps:

[0160] (1) providing a water-soluble preform;

[0161] (2) mixing enantholactam and sodium hydroxide at a mass ratio of 100:1 to obtain a monomer solution A, which is stored in a tank A; mixing enantholactam and benzoyl chloride at a mass ratio of 100:1 to obtain a monomer solution B, which is stored in a tank B; vacuum dehydrating the solutions in tanks A and B at 80° C., adding monomer solution A and monomer solution B to a static mixer at a mass ratio of 1:1 by a metering pump and fully mixing, adding a stabilizer to obtain a raw material solution A, wherein the mass fraction of the stabilizer in the raw material solution A is 1 wt %;

[0162] (3) The raw material liquid A is uniformly injected onto the nylon fiber to be wound, the injection speed is 0.6 g / s, and the temperature of the raw material liquid during injection is 120° C.;

[0163] (4) The nylon fiber attached with the raw material liquid A is quickly wound onto the water-soluble preform. The equipment used is a CNC four-axis fully automatic cylindrical winding machine. The cylinder of the equipment is placed in a dry environment at 180°C. A total of 9 layers of nylon fiber are wound on the entire can body of the preform from the inside to the outside. The odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a circumferential manner with a winding angle of 90° and a winding speed of 0.9 m / s. The even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a circumferential manner with a winding angle of 90° and a winding speed of 0.9 m / s. The spiral winding method is adopted, the winding angles of the second, fourth, sixth and eighth layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.9 m / s, the winding tension of the first layer is 70 N, and the winding tensions of the second, third, fourth, fifth, sixth, seventh, eighth and ninth layers are 65 N, 60 N, 55 N, 50 N, 45 N, 40 N, 35 N and 30 N respectively; during the winding process, enantholactam is polymerized into polyenantholactam to obtain a composite of an inner layer and a water-soluble preform;

[0164] (5) The raw material liquid A is uniformly injected onto the carbon fiber to be wound, the injection speed is 0.2 g / s, and the temperature of the raw material liquid during injection is 120°C;

[0165] (6) The carbon fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (4), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 180°C; 9 layers of carbon fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop winding manner, with a winding angle of 90° and a winding speed of 0.9 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral winding manner. Winding method: the winding angles of the 2nd, 4th, 6th and 8th layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.9m / s, the winding tension of the 1st layer is 70N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th and 9th layers are 65N, 60N, 55N, 50N, 45N, 40N, 35N and 30N respectively; during the winding process, enantholactam is polymerized into polyenantholactam to obtain a composite of an inner layer, an intermediate layer and a water-soluble preform;

[0166] (7) The raw material liquid A is uniformly injected onto the carbon fiber to be wound, the injection speed is 0.2 g / s, and the temperature of the raw material liquid during injection is 120° C.;

[0167] (8) The carbon fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (6), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 180°C; 9 layers of carbon fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop winding manner, with a winding angle of 90° and a winding speed of 0.9 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral winding manner. The winding angles of the second, fourth, sixth and eighth layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.9 m / s, the winding tension of the first layer is 70 N, and the winding tensions of the second, third, fourth, fifth, sixth, seventh, eighth and ninth layers are 65 N, 60 N, 55 N, 50 N, 45 N, 40 N, 35 N and 30 N respectively; during the winding process, enanthocyanate is polymerized into polyenanthocyanate to obtain a composite of a fiber composite material wound bottle and a water-soluble preform;

[0168] (9) The water-soluble preform in the composite is removed by washing at 100° C. and 2 MPa to obtain a fiber composite material wrapped bottle, wherein the inner layer nylon fiber content is 60-70wt%, the middle layer carbon fiber content is 60-70wt%, and the outer layer carbon fiber content is 60-70wt%.

[0169] Example 4

[0170] In this embodiment, a fiber composite material wrapped bottle is prepared by the following steps:

[0171] (1) providing a water-soluble preform;

[0172] (2) mixing caprolactam and sodium caprolactam in a mass ratio of 100:0.5 to obtain monomer solution A, which is stored in tank A; mixing caprolactam and toluene diisocyanate in a mass ratio of 100:0.5 to obtain monomer solution B, which is stored in tank B; vacuum dehydrating the solutions in tanks A and B at 120° C., adding monomer solution A and monomer solution B in a mass ratio of 1:1 to a static mixer by a metering pump and mixing them thoroughly, adding a stabilizer to obtain a raw material solution A, wherein the mass fraction of the stabilizer in the raw material solution A is 1 wt %;

[0173] (3) The raw material liquid A is uniformly injected onto the nylon fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0174] (4) The nylon fiber attached with the raw material liquid A is quickly wound onto the water-soluble preform. The equipment used is a CNC four-axis fully automatic cylindrical winding machine. The cylinder of the equipment is placed in a dry environment at 160°C. A total of 10 layers of nylon fiber are wound on the entire can body of the preform from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a circumferential manner with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, 8th, and 10th layers) are wound in a spiral manner. The winding angles of the second, fourth, sixth, eighth and tenth layers are 15°, 23°, 30°, 38° and 45° respectively, the winding speed is 0.5 m / s, the winding tension of the first layer is 65 N, and the winding tensions of the second, third, fourth, fifth, sixth, seventh, eighth, ninth and tenth layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N, 33 N and 30 N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of an inner layer and a water-soluble preform;

[0175] (5) The raw material liquid A is uniformly injected onto the carbon fiber to be wound, the injection speed is 0.15 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0176] (6) The carbon fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (4), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the barrel of the equipment is placed in a dry environment at 160°C; 7 layers of carbon fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, and 7th layers) are wound in a hoop winding manner, the winding angle is 90°, and the winding speed is 0.5 m / s; the even-numbered layers (the 2nd, 4th, and 6th layers) are wound in a spiral winding manner, the winding angles of the 2nd, 4th, and 6th layers are 15°, 30°, and 45°, respectively, the winding speed is 0.5 m / s, the winding tension of the 1st layer is 65N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, and 7th layers are 61N, 57N, 53N, 49N, 45N, and 41N, respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of an inner layer, an intermediate layer, and a water-soluble preform;

[0177] (7) The raw material liquid A is uniformly injected onto the glass fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0178] (8) The glass fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (6), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160° C.; 10 layers of glass fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop manner, with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, 8th, and 10th layers) are wound in a spiral manner, and the 2nd, 3rd, 5th, 7th, and 9th layers are wound in a spiral manner. The winding angles of the 4th, 6th, 8th and 10th layers are 15°, 23°, 30°, 38° and 45° respectively, the winding speed is 0.5 m / s, the winding tension of the 1st layer is 65 N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th, 9th and 10th layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N, 33 N and 30 N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of a fiber composite material wound bottle and a water-soluble preform;

[0179] (9) The water-soluble preform in the composite is removed by washing at 100° C. and 2 MPa to obtain a fiber composite material wrapped bottle, wherein the inner layer nylon fiber content is 60-70wt%, the middle layer carbon fiber content is 60-70wt%, and the outer layer glass fiber content is 60-70wt%.

[0180] Example 5

[0181] In this embodiment, a fiber composite material wrapped bottle is prepared by the following steps:

[0182] (1) providing a water-soluble preform;

[0183] (2) mixing caprolactam and sodium caprolactam in a mass ratio of 100:0.5 to obtain monomer solution A, which is stored in tank A; mixing caprolactam and toluene diisocyanate in a mass ratio of 100:0.5 to obtain monomer solution B, which is stored in tank B; vacuum dehydrating the solutions in tanks A and B at 120° C., adding monomer solution A and monomer solution B in a mass ratio of 1:1 to a static mixer by a metering pump and mixing them thoroughly, adding a stabilizer to obtain a raw material solution A, wherein the mass fraction of the stabilizer in the raw material solution A is 1 wt %;

[0184] (3) The raw material liquid A is uniformly injected onto the nylon fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0185] (4) The nylon fiber attached with the raw material liquid A is quickly wound onto the water-soluble preform. The equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160°C; 4 layers of nylon fiber are wound on the entire can body of the preform from the inside to the outside, wherein the odd-numbered layers (the first and third layers) are wound in a circumferential manner, with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the second and fourth layers) are wound in a spiral manner, with the winding angles of the second and fourth layers being 20° and 40°, respectively, and the winding speed being 0.5 m / s. The winding tension of the first layer is 65N, and the winding tensions of the second, third, and fourth layers are 60N, 55N, and 50N, respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of the inner layer and the water-soluble preform;

[0186] (5) The raw material liquid A is uniformly injected onto the carbon fiber to be wound, the injection speed is 0.15 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0187] (6) The carbon fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (4), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160°C; 11 layers of carbon fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, 9th, and 11th layers) are wound in a hoop winding manner, with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, 8th, and 10th layers) are wound in a spiral winding manner, with the 2nd, 4th, and 8th layers being wound in a spiral winding manner. The winding angles of the 6th, 8th and 10th layers are 15°, 23°, 30°, 37° and 45° respectively, the winding speed is 0.5m / s, the winding tension of the 1st layer is 65N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th, 9th, 10th and 11th layers are 62N, 59N, 56N, 53N, 50N, 47N, 43N, 40N, 37N and 36N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of an inner layer, an intermediate layer and a water-soluble preform;

[0188] (7) The raw material liquid A is uniformly injected onto the glass fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0189] (8) The glass fiber attached with the raw material liquid A is quickly wound onto the composite body obtained in step (6), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the barrel of the equipment is placed in a dry environment at 160°C; 4 layers of glass fiber are wound from the inside to the outside, wherein the odd-numbered layers (the first and third layers) are wound in a hoop-winding manner, the winding angle is 90°, and the winding speed is 0.5 m / s, and the even-numbered layers (the second and fourth layers) are wound in a spiral manner, the winding angles of the second and fourth layers are 20° and 40° respectively, the winding speed is 0.5 m / s, the winding tension of the first layer is 65N, and the winding tensions of the second, third and fourth layers are 60N, 55N and 50N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite body of a fiber composite material wound bottle and a water-soluble preform;

[0190] (9) The water-soluble preform in the composite is removed by washing at 100° C. and 2 MPa to obtain a fiber composite material wrapped bottle, wherein the inner layer nylon fiber content is 60-70wt%, the middle layer carbon fiber content is 60-70wt%, and the outer layer glass fiber content is 60-70wt%.

[0191] Example 6

[0192] In this embodiment, a fiber composite material wrapped bottle is prepared by the following steps:

[0193] (1) providing a water-soluble preform;

[0194] (2) mixing caprolactam and sodium caprolactam in a mass ratio of 100:0.5 to obtain monomer solution A, which is stored in tank A; mixing caprolactam and toluene diisocyanate in a mass ratio of 100:0.5 to obtain monomer solution B, which is stored in tank B; vacuum dehydrating the solutions in tanks A and B at 120° C., adding monomer solution A and monomer solution B in a mass ratio of 1:1 to a static mixer by a metering pump and mixing them thoroughly, adding a stabilizer to obtain a raw material solution A, wherein the mass fraction of the stabilizer in the raw material solution A is 1 wt %;

[0195] (3) The raw material liquid A is uniformly injected onto the nylon fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0196] (4) The nylon fiber attached with the raw material liquid A is quickly wound onto the water-soluble preform. The equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160°C. A total of 9 layers of nylon fiber are wound on the entire can body of the preform from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a circumferential manner with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral manner, with the winding angles of the 2nd, 4th, 6th, and 8th layers all being 30° and the winding speed being 0.5 m / s. The winding tension of the 1st layer is 65N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, and 8th layers are 61N, 57N, 53N, 49N, 45N, 41N, 37N, and 33N, respectively. During the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of the inner layer and the water-soluble preform.

[0197] (5) The raw material liquid A is uniformly injected onto the carbon fiber to be wound, the injection speed is 0.15 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0198] (6) The carbon fiber attached with the raw material liquid A is rapidly wound onto the composite obtained in step (4), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the barrel of the equipment is placed in a dry environment at 160°C; 9 layers of carbon fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop winding manner, the winding angle is 90°, and the winding speed is 0.5 m / s; the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral winding manner, the winding angles of the 2nd, 4th, 6th, and 8th layers are all 30°, the winding speed is 0.5 m / s, the winding tension of the 1st layer is 65N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, and 8th layers are 61N, 57N, 53N, 49N, 45N, 41N, 37N, and 33N, respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of an inner layer, an intermediate layer, and a water-soluble preform;

[0199] (7) The raw material liquid A is uniformly injected onto the glass fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0200] (8) The glass fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (6), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160° C.; 9 layers of glass fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a circumferential manner, with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral manner. The winding angles of the second, fourth, sixth and eighth layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.5 m / s, the winding tension of the first layer is 65 N, and the winding tensions of the second, third, fourth, fifth, sixth, seventh, eighth and ninth layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N and 33 N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of a fiber composite material wound bottle and a water-soluble preform;

[0201] (9) The water-soluble preform in the composite is removed by washing at 100° C. and 2 MPa to obtain a fiber composite material wrapped bottle, wherein the inner layer nylon fiber content is 60-70wt%, the middle layer carbon fiber content is 60-70wt%, and the outer layer glass fiber content is 60-70wt%.

[0202] Example 7

[0203] In this embodiment, a fiber composite material wrapped bottle is prepared by the following steps:

[0204] (1) providing a water-soluble preform;

[0205] (2) mixing caprolactam and sodium caprolactam in a mass ratio of 100:0.5 to obtain monomer solution A, which is stored in tank A; mixing caprolactam and toluene diisocyanate in a mass ratio of 100:0.5 to obtain monomer solution B, which is stored in tank B; vacuum dehydrating the solutions in tanks A and B at 120° C., adding monomer solution A and monomer solution B in a mass ratio of 1:1 to a static mixer by a metering pump and mixing them thoroughly, adding a stabilizer to obtain a raw material solution A, wherein the mass fraction of the stabilizer in the raw material solution A is 1 wt %;

[0206] (3) The raw material liquid A is uniformly injected onto the nylon fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0207] (4) The nylon fiber attached with the raw material liquid A is quickly wound onto the water-soluble preform. The equipment used is a CNC four-axis fully automatic cylindrical winding machine. The cylinder of the equipment is placed in a dry environment at 160°C. A total of 9 layers of nylon fiber are wound on the entire can body of the preform from the inside to the outside. The odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a circumferential manner with a winding angle of 90° and a winding speed of 0.5 m / s. The even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a circumferential manner with a winding angle of 90° and a winding speed of 0.5 m / s. The spiral winding method is used, the winding angles of the second, fourth, sixth and eighth layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.5 m / s, the winding tension of the first layer is 65 N, and the winding tensions of the second, third, fourth, fifth, sixth, seventh, eighth and ninth layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N and 33 N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of an inner layer and a water-soluble preform;

[0208] (5) The raw material liquid A is uniformly injected onto the carbon fiber to be wound, the injection speed is 0.15 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0209] (6) The carbon fiber attached with the raw material liquid A is quickly wound onto the composite obtained in step (4), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160°C; 9 layers of carbon fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop winding manner, with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral winding manner. The winding method is as follows: the winding angles of the 2nd, 4th, 6th and 8th layers are 15°, 25°, 35° and 45° respectively; the winding speed is 0.5 m / s; the winding tension of the 1st layer is 65 N; the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th and 9th layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N and 33 N respectively; during the winding process, caprolactam is polymerized into polycaprolactam to obtain a composite of an inner layer, an intermediate layer and a water-soluble preform;

[0210] (7) using bisphenol A epoxy resin as monomer solution C and methyl hexahydrophthalic anhydride as monomer solution D, storing them in tanks C and D respectively, and vacuum dehydrating them at 120° C.; adding monomer solution C and monomer solution D to a static mixer at a mass ratio of 1:1 by a metering pump, and mixing them thoroughly; adding a stabilizer to obtain a raw material solution B, wherein the mass fraction of the stabilizer in the raw material solution B is 1 wt %;

[0211] (8) The raw material liquid B is uniformly injected onto the glass fiber to be wound, the injection speed is 0.4 g / s, and the temperature of the raw material liquid during injection is 130° C.;

[0212] (9) The glass fiber attached with the raw material liquid B is quickly wound onto the composite obtained in step (6), and the equipment used is a CNC four-axis fully automatic cylindrical winding machine, and the cylinder of the equipment is placed in a dry environment at 160° C.; 9 layers of glass fiber are wound from the inside to the outside, wherein the odd-numbered layers (the 1st, 3rd, 5th, 7th, and 9th layers) are wound in a hoop manner, with a winding angle of 90° and a winding speed of 0.5 m / s, and the even-numbered layers (the 2nd, 4th, 6th, and 8th layers) are wound in a spiral manner, and the 2nd, 3rd, 5th, 7th, and 9th layers are wound in a spiral manner. The winding angles of the 4th, 6th and 8th layers are 15°, 25°, 35° and 45° respectively, the winding speed is 0.5 m / s, the winding tension of the first layer is 65 N, and the winding tensions of the 2nd, 3rd, 4th, 5th, 6th, 7th, 8th and 9th layers are 61 N, 57 N, 53 N, 49 N, 45 N, 41 N, 37 N and 33 N respectively; during the winding process, the bisphenol A type epoxy resin is cross-linked and cured by methyl hexahydrophthalic anhydride to obtain epoxy resin, and a composite of a fiber composite material wound bottle and a water-soluble preform is obtained;

[0213] (10) The water-soluble preform in the composite is removed by washing at 100° C. and 2 MPa to obtain a fiber composite material wrapped bottle, wherein the inner layer nylon fiber content is 60-70wt%, the middle layer carbon fiber content is 60-70wt%, and the outer layer glass fiber content is 60-70wt%.

Claims

1. A fiber composite material wrapped bottle, characterized in that: The fiber composite wrapped bottle comprises an inner layer, an intermediate layer and an outer layer from the inside to the outside, the inner layer is composed of one or more nylon fiber composite layers from the inside to the outside, the intermediate layer is composed of one or more carbon fiber composite layers from the inside to the outside, and the outer layer is composed of one or more glass fiber composite layers or carbon fiber composite layers from the inside to the outside; wherein, a nylon fiber composite layer is composed of a layer of wound nylon fiber and a resin matrix, a carbon fiber composite layer is composed of a layer of wound carbon fiber and a resin matrix, and a glass fiber composite layer is composed of a layer of wound glass fiber and a resin matrix, the resin in the resin matrix of the nylon fiber composite layer and the carbon fiber composite layer in the intermediate layer is polyamide, and the resin in the resin matrix of the carbon fiber composite layer and the glass fiber composite layer in the outer layer is polyamide or epoxy resin, the polyamide is formed by polymerization of lactam, and the epoxy resin is formed by cross-linking and curing of an epoxy resin matrix with an epoxy resin curing agent.

2. The fiber composite material wrapped bottle according to claim 1, characterized in that: The fiber composite material wrapped bottle has one or more of the following features: The inner layer is composed of 4 to 10 layers of nylon fiber composite material from the inside to the outside; The middle layer is composed of 7 to 11 layers of carbon fiber composite material from the inside to the outside; The outer layer is composed of 4 to 10 layers of glass fiber composite material layers or carbon fiber composite material layers from the inside to the outside; In the inner layer, the nylon fibers in the innermost nylon fiber composite material layer are arranged in a hoop-wound form, and the nylon fibers in the two adjacent nylon fiber composite material layers are arranged in a hoop-wound form and a spiral-wound form, respectively, the winding angle of the hoop-wound form is 90°, the winding angle of the spiral-wound form is 15-45°, and the winding angle of the nylon fibers in each nylon fiber composite material layer in which the nylon fibers are arranged in a spiral-wound form increases layer by layer from the inside to the outside; In the middle layer, the carbon fibers in the innermost carbon fiber composite material layer are arranged in a circumferential winding form, and the carbon fibers in the two adjacent carbon fiber composite material layers are arranged in a circumferential winding form and a spiral winding form, respectively, the winding angle of the circumferential winding is 90°, the winding angle of the spiral winding is 15-45°, and the winding angle of the carbon fibers in each carbon fiber composite material layer in which the carbon fibers are arranged in a spiral winding form increases layer by layer from the inside to the outside; In the outer layer, the glass fibers in the innermost glass fiber composite material layer or the carbon fibers in the innermost carbon fiber composite material layer are arranged in a circumferential winding form, and the glass fibers in two adjacent glass fiber composite material layers or the carbon fibers in two adjacent carbon fiber composite material layers are arranged in a circumferential winding and a spiral winding form, respectively. The winding angle of the circumferential winding is 90°, and the winding angle of the spiral winding is 15-45°. The winding angle of the glass fibers in each glass fiber composite material layer where the glass fibers are arranged in a spiral winding form or the winding angle of the carbon fibers in each carbon fiber composite material layer where the carbon fibers are arranged in a spiral winding form increases layer by layer from the inside to the outside.

3. The fiber composite material wrapped bottle according to claim 1, characterized in that: The fiber composite material wrapped bottle has one or more of the following features: The lactam is selected from one or more of butyrolactam, valerolactam, caprolactam, enantholactam, capryllactam, nonanolactam, decanolactam, undecanolactam and laurolactam; The epoxy resin matrix is ​​selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate and aliphatic epoxy resin; The epoxy resin curing agent is selected from one or more of hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, acetic anhydride, caproic anhydride, succinic anhydride, cyclohexanecarboxylic anhydride, aniline and m-phenylenediamine; The resin matrices of the nylon fiber composite material layer, the carbon fiber composite material layer and the glass fiber composite material layer contain stabilizers, and the stabilizers include hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants, the mass of the stabilizers is 0.3-1.5wt% of the mass of the resin matrix, and the mass of the hindered phenol antioxidants, the phosphite antioxidants and the thioester antioxidants is 0.1-0.5wt% of the mass of the resin matrix respectively; The nylon fiber is nylon 6 fiber or nylon 66 fiber, the fineness of the nylon fiber is 420-3000D, and the number of pores is 24-96F; The surface of the carbon fiber is coated with a vinyl ester or polyamide sizing agent.

4. The fiber composite material wrapped bottle according to claim 1, characterized in that: The nylon fiber content of the inner layer is 60-70wt%, the carbon fiber content of the middle layer is 60-70wt%, and the glass fiber or carbon fiber content of the outer layer is 60-70wt%.

5. The fiber composite material wrapped bottle according to claim 1, characterized in that: The total number of nylon fiber composite material layers in the inner layer, carbon fiber composite material layers in the middle layer, and glass fiber composite material layers or carbon fiber composite material layers in the outer layer is 22-28 layers.

6. A method for preparing a fiber composite material wrapped bottle according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: (1) providing a water-soluble preform; (2) providing a first monomer solution and a second monomer solution, wherein the first monomer solution comprises a first monomer and a catalyst, and the second monomer solution comprises a second monomer and an activator, and the first monomer and the second monomer are lactams, and the first monomer solution and the second monomer solution are uniformly mixed to obtain a first raw material solution; (3) uniformly attaching the first raw material liquid to the surface of the nylon fiber; (4) winding the nylon fiber to which the first raw material liquid is attached onto the water-soluble preform, winding one or more layers of the nylon fiber from the inside out, and heating the nylon fiber wound on the water-soluble preform so that the first monomer and the second monomer on the surface of the nylon fiber react to form polyamide, thereby obtaining a composite of the inner layer and the water-soluble preform; (5) providing a third monomer solution and a fourth monomer solution, wherein the third monomer solution comprises a third monomer and a catalyst, and the fourth monomer solution comprises a fourth monomer and an activator, and the third monomer and the fourth monomer are lactams, and uniformly mixing the third monomer solution and the fourth monomer solution to obtain a second raw material solution; (6) uniformly attaching the second raw material liquid to the surface of the carbon fiber; (7) Winding the carbon fiber attached with the second raw material liquid onto the composite of the inner layer and the water-soluble preform, winding one or more layers of carbon fiber from the inside to the outside, and heating the carbon fiber wound on the water-soluble preform so that the third monomer and the fourth monomer on the surface of the carbon fiber react to form polyamide, thereby obtaining a composite of the fiber composite material wound around the bottle inner layer, the middle layer and the water-soluble preform; (8) providing a fifth monomer solution and a sixth monomer solution, wherein the fifth monomer solution comprises a fifth monomer and a catalyst, and the sixth monomer solution comprises a sixth monomer and an activator, and the fifth monomer and the sixth monomer are lactams; or, the fifth monomer solution comprises an epoxy resin matrix, and the sixth monomer solution comprises an epoxy resin curing agent; and uniformly mixing the fifth monomer solution and the sixth monomer solution to obtain a third raw material solution; (9) uniformly attaching the third raw material liquid to the surface of the glass fiber or carbon fiber; (10) Winding the glass fiber or carbon fiber attached with the third raw material liquid onto the composite of the inner layer, the middle layer and the water-soluble preform, winding one or more layers of the glass fiber or carbon fiber from the inside to the outside, and heating the glass fiber or carbon fiber wound on the water-soluble preform at the same time, so that the fifth monomer and the sixth monomer on the surface of the glass fiber or carbon fiber react to form polyamide, or the epoxy resin matrix and the epoxy resin curing agent on the surface of the glass fiber or carbon fiber react to form epoxy resin, thereby obtaining a composite of the fiber composite material wound bottle and the water-soluble preform; (11) The water-soluble preform in the composite of the fiber composite material wound bottle and the water-soluble preform is removed by washing with water to obtain a fiber composite material wound bottle.

7. The method according to claim 6, characterized in that In step (1), the water-soluble preform is made of a water-soluble inorganic salt by sintering or melt infusion, and the water-soluble inorganic salt is selected from one or more of potassium carbonate, sodium chloride, potassium chloride, potassium nitrate, copper chloride and calcium chloride.

8. The method according to claim 6, characterized in that The method has one or more of the following features: The first monomer, the second monomer, the third monomer, the fourth monomer, the fifth monomer and the sixth monomer are each independently selected from one or more of caprolactam, capryllactam, enantholactam and laurolactam; The catalyst in the first monomer solution, the catalyst in the third monomer solution and the catalyst in the fifth monomer solution are each independently selected from one or more of sodium caprolactam, potassium caprolactam, sodium hydroxide, sodium ethoxide, sodium methoxide, sodium hydride and metallic sodium; In the first monomer solution, the third monomer solution and the fifth monomer solution, the mass of the catalyst is 0.1-1% of the mass of the first monomer, the third monomer or the fifth monomer; The active agent in the second monomer solution, the active agent in the fourth monomer solution and the active agent in the sixth monomer solution are each independently selected from one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, dicaprolactam-based diisocyanate, acetyl caprolactam and benzoyl chloride; In the second monomer solution, the fourth monomer solution and the sixth monomer solution, the mass of the active agent is 0.1-1% of the mass of the second monomer, the fourth monomer or the sixth monomer.

9. The method according to claim 6, characterized in that In step (3), step (6) and step (9), the raw material liquid is attached to the fiber surface by injection, the injection speed is 0.1-0.6g / s, and the temperature of the raw material liquid during injection is 80-180°C.

10. The method according to claim 6, characterized in that Step (4), step (7) and step (10) have one or more of the following characteristics: The winding is done by using a CNC four-axis fully automatic cylindrical winding machine; Winding speed is 0.2-0.9m / s; The winding tension when winding the first layer of fibers in the inner layer, middle layer or outer layer is 60-70N, and the winding tension decreases by 2.5-5N layer by layer from the inside to the outside; The heating temperature is 140-180℃.

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