An impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder, a highly flame-retardant plastic liner gas cylinder and a preparation method thereof

Abstract

The present application discloses an impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder, a highly flame-retardant plastic liner gas cylinder and a preparation method thereof, and belongs to the technical field of preparing plastic liner gas cylinders. The impregnation slurry includes 80-100 parts of water-based epoxy resin, 10-15 parts of flame retardant aids, 20-25 parts of ethanol and 1-2 parts of curing agent by weight, and the flame retardant aid is prepared by heating and refluxing reaction of monomer A and tris(2,3-dichloropropyl) phosphate in a molar ratio of (3-4):1. The flame retardant aid added in the impregnation slurry can participate in the curing of epoxy resin, so it can form a dense flame retardant network with epoxy resin, improve the flame retardant properties of the plastic liner gas cylinder, and improve the safety of use of the plastic liner gas cylinder.

Description

Technical Field

[0001] The present application relates to an impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder, a highly flame-retardant plastic liner gas cylinder and a preparation method thereof, and belongs to the technical field of plastic liner gas cylinder preparation. Background Art

[0002] On-board high-pressure hydrogen storage cylinders are important components of hydrogen fuel cell vehicles. They are the basis for ensuring stable driving of the vehicle. At present, plastic liner full-fiber wrapped cylinders are gradually replacing the original high-pressure hydrogen storage containers due to their advantages such as light weight, large capacity, and high pressure resistance, and are widely used in hydrogen fuel cell vehicles.

[0003] The preparation of the current plastic liner fiber fully wound plastic liner gas cylinder is mainly divided into two steps. The first step is to use the substrate to prepare the plastic liner, which mainly plays a sealing role. The second step is to impregnate the carbon fiber in the impregnation slurry and wind it to the outside of the formed plastic liner to form a fiber winding layer, which mainly plays a protective and sealing role. Therefore, the plastic liner gas cylinder is a combination of the plastic liner and the fiber winding layer. Since the fiber winding layer is set on the outermost side, the fiber winding layer is more important to the protective performance of the plastic liner.

[0004] At present, in order to meet the functional requirements of plastic liner gas cylinders, researchers add functional additives to the impregnation slurry in the hope of obtaining multi-faceted protection. For example, in order to improve the safety of use, the impregnation slurry in patent CN112303478A is a medium-temperature curing epoxy flame retardant resin to obtain a fire-resistant and flame-retardant plastic liner gas cylinder. However, the medium-temperature curing epoxy flame retardant resin recorded therein is a mixture of epoxy resin and flame retardant. In this way, the flame retardant, as an additive that does not participate in the reaction, can have a certain flame retardant effect, but the flame retardant is prone to uneven distribution and poor bonding with the epoxy resin, so the flame retardant effect of the plastic liner gas cylinder is not good. If the ignition point is in an area where the flame retardant is less distributed, there is still a risk of explosive fire. Summary of the invention

[0005] In order to solve the above problems, an impregnation slurry for preparing highly flame-retardant plastic liner gas cylinders is provided. The flame retardant additive added to the impregnation slurry can participate in the curing of the epoxy resin, thereby forming a dense flame retardant network with the epoxy resin, thereby improving the flame retardant properties of the plastic liner gas cylinders and improving the safety of use of the plastic liner gas cylinders.

[0006] According to one aspect of the present application, there is provided an impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder, which comprises, by weight, 80-100 parts of an aqueous epoxy resin, 10-15 parts of a flame retardant additive, 20-25 parts of ethanol and 1-2 parts of a curing agent, wherein the flame retardant additive is prepared by heating and refluxing a monomer A and tris(2,3-dichloropropyl) phosphate in a molar ratio of (3-4):1, and the structural formula of the monomer A is as follows:

[0007]

[0008] wherein R1 is selected from an unsubstituted alkyl group or a halogen-substituted alkyl group containing 3 to 6 carbon atoms.

[0009] The flame retardant additive is prepared by reacting monomer A and tri(2,3-dichloropropyl) phosphate. Tri(2,3-dichloropropyl) phosphate contains three branches on the phosphate ester, and each branch carries two chlorine atoms. Due to the existence of steric effect, after monomer A reacts with a chlorine atom on one of the branches to form a quaternary ammonium salt, it is difficult for the other chlorine atom to react with monomer A. Therefore, under the above molar ratio, it can be ensured that tri(2,3-dichloropropyl) phosphate carries a quaternary ammonium salt combined with a chlorine atom and a chlorine atom on the three branches of the phosphate ester, wherein the chlorine atom can increase the flame retardancy of the formed fiber winding layer, and the quaternary ammonium salt formed by the monomer A and the chlorine atom can give the fiber winding layer antibacterial properties, and can also improve the flame retardancy of the flame retardant additive. Due to the reaction between monomer A and tris(2,3-dichloropropyl) phosphate, the flame retardant additive contains excess amino groups, which can react with the epoxy resin and act as a cross-linking agent for the epoxy resin to form a dense and uniform fiber winding layer, thereby improving the flame retardant ability and flame retardant uniformity of the plastic liner gas cylinder.

[0010] Under the above impregnation slurry ratio, water-based epoxy resin is used as the main body and ethanol is used as a cosolvent to promote the dissolution and dispersion of the flame retardant additive, thereby improving the dispersion uniformity of the slurry, and then improving the reaction uniformity of the flame retardant additive and the water-based epoxy resin in the fiber winding layer. The amount of the curing agent added is relatively small, in order to supplement the cross-linking curing effect of the flame retardant additive. Therefore, the flame retardant additive and the curing agent work together to cure the epoxy resin, improve the density of the epoxy resin cross-linking network, and then improve the sealing of the plastic liner gas cylinder.

[0011] Since monomer A contains a benzene ring group, it can be introduced into the epoxy resin cross-linked network through a flame retardant additive to improve the durability of the fiber winding layer and reduce the thermal expansion coefficient of the fiber winding layer, thereby reducing the deformation resistance of the plastic liner gas cylinder and improving the bonding between the fiber winding layer and the plastic liner. Monomer A also contains two ester groups, which can improve the compatibility with epoxy resin, thereby improving the toughness of the fiber winding layer, reducing its deformation under long-term inflation and deflation, and extending the service life of the plastic liner gas cylinder. At the same time, after the flame retardant additive prepared from monomer A of this structure reacts with the epoxy resin, it can improve the overall flatness and density of the fiber winding layer, thereby reducing hydrogen leakage.

[0012] Optionally, R1 is selected from halogen-substituted alkyl groups containing 3 to 6 carbon atoms.

[0013] The R1 structure can affect the performance of the flame retardant additive. The present application adopts a halogen-substituted alkyl group, which can further improve the flame retardant properties of the flame retardant additive. At the same time, it can also avoid introducing a large sterically hindered group into the flame retardant additive, reduce the steric effect, and thus increase the reaction activity of monomer A with tris(2,3-dichloropropyl) phosphate, so as to increase the yield of the flame retardant additive and reduce the production cost of the flame retardant additive.

[0014] In addition, since the flame retardant additive can act as the cross-linking point of the epoxy resin through the amino group, the number of carbon atoms contained in R1 will affect the length of monomer A. Therefore, the number of its carbon atoms is related to the density of the epoxy resin cross-linking network. If the number of carbon atoms is too small, the cross-linking points are too dense, the toughness of the fiber winding layer is insufficient, and it is easy to crack during inflation and deflation. If the number of carbon atoms is too large, the density of the fiber winding layer is poor, which increases the hydrogen leakage.

[0015] Optionally, p-nitrobenzoyl chloride, monomer B and triethylamine are reacted to obtain an intermediate, the intermediate is then reacted with stannous chloride dihydrate, and then an alkaline solution is added to adjust to a weak alkalinity, and after treatment, monomer A is obtained;

[0016] The monomer B is selected from at least one of 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-chloro-1,3-propylene glycol, 2-chloro-1,3-butanediol, and 2,2-dichloro-1,5-pentanediol.

[0017] The above different monomers B form R1 structures, and monomers A with different R1 structures are obtained by changing the type of monomer B. The above preparation method is simple, and the yield of the obtained monomer A is high, thereby reducing the production cost of the plastic liner gas cylinder.

[0018] Optionally, the molar ratio of p-nitrobenzoyl chloride, monomer B and triethylamine is 1:(2-3):(2-3), the reaction temperature is 20-30° C., and the reaction time is 8-10 h.

[0019] Optionally, the molar ratio of the intermediate to stannous chloride dihydrate is 1:(1.5-3), the reaction temperature is 50-70°C, and the reaction time is 15-20h.

[0020] Optionally, p-nitrobenzoyl chloride is prepared by reacting p-nitrobenzoic acid and thionyl chloride in a molar ratio of 1:(2.5-3) at 60-70° C. for 10-12 h.

[0021] According to another aspect of the present application, a method for preparing a highly flame-retardant plastic liner gas cylinder is provided, comprising the following steps:

[0022] (1) Using PA11 as a substrate, a plastic liner is obtained by rotational molding, and a bottle mouth is reserved at the top of the plastic liner;

[0023] (2) The carbon fiber is impregnated into the impregnation slurry according to any one of claims 1 to 5 to obtain an impregnated fiber, the impregnated fiber is wound around the outside of the plastic liner, heated and cured to form a fiber winding layer, and a bottle mouth joint is installed at the bottle mouth.

[0024] In the above preparation method, carbon fiber is impregnated in an impregnation slurry and then wrapped around a plastic liner, so that the impregnation slurry and carbon fiber can form a fiber winding layer with good flame retardant properties on the outside of the plastic liner, thereby improving the flame retardant properties and safety of the plastic liner gas cylinder.

[0025] Optionally, the amount of the carbon fiber impregnated with resin is 20wt%-30wt%.

[0026] Optionally, the fiber winding layer has a thickness of 25-30 mm.

[0027] Optionally, the plastic liner includes an inner layer and an outer layer, the outer layer is arranged on the outside of the inner layer, the impregnated fibers are wound to the outside of the outer layer, and a layer of impregnating slurry is applied on the outer surface of the outer layer before the impregnated fibers are wound.

[0028] Due to the production process of the plastic liner, there may be small micropores on the outer surface of the outer layer. Applying a layer of impregnation slurry on the outer surface of the outer layer before winding the impregnated fiber can wet the surface of the plastic liner and improve the compatibility with the impregnated fiber, so that the plastic liner and the fiber winding layer are tightly wound, thereby improving the bonding strength between the two and avoiding delamination of the plastic liner gas cylinder.

[0029] Optionally, the thickness of the inner layer is 2.5-3 mm, and the thickness of the outer layer is 2.5-3 mm.

[0030] Optionally, the inner layer comprises 80-100 parts of PA11, 10-20 parts of EVOH, 5-8 parts of polyisocyanate and 2-5 parts of plasticizer, and the outer layer comprises 80-100 parts of PA11, 10-20 parts of epoxy resin, 1 part of curing agent, 2-5 parts of plasticizer and 1-3 parts of catalyst, by weight.

[0031] The inner layer uses PA11 as the base material, which has good processing performance when compounded with polyisocyanate and EVOH. EVOH itself can improve the hydrogen permeability resistance of the inner layer of the liner, and polyisocyanate can form a cross-linked network, which is closely combined with EVOH, thereby improving the density of the inner layer and forming the first line of defense to protect hydrogen. The outer layer uses PA11 as the base material, which is consistent with the base material in the inner layer, which can improve the bonding between the outer layer and the inner layer and avoid stratification of the plastic liner. The outer layer contains epoxy resin and curing agent. During the processing of the outer layer and the inner layer, the epoxy resin and polyisocyanate can form a cross-linked network respectively, and the cross-linked network can be interspersed on the bonding surface of the inner layer and the outer layer, increasing the connection strength between the inner layer and the outer layer, and improving the mechanical properties and deformation resistance of the plastic liner.

[0032] Preferably, the outer layer also includes 1 part of flame retardant additive. The flame retardant additive is also added to the outer layer. During the preparation of the outer layer, it can also be combined with the curing agent to cure the epoxy resin to obtain a plastic liner matrix in which PA11 and epoxy resin reinforce each other, thereby improving the flame retardancy and mechanical strength of the plastic liner.

[0033] According to another aspect of the present application, a highly flame-retardant plastic liner gas cylinder prepared by the method for preparing a highly flame-retardant plastic liner gas cylinder as described in any of the above items is provided.

[0034] The beneficial effects of this application include but are not limited to:

[0035] 1. The present application discloses an impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder. The monomer and tri(2,3-dichloropropyl) phosphate are reacted to obtain a flame retardant additive that can participate in the curing of the epoxy resin, so that the flame retardant additive is evenly distributed in the epoxy resin cross-linking network and acts as a cross-linking point, thereby improving the flame retardancy and sealing properties of the fiber winding layer.

[0036] 2. The impregnation slurry used in the present application for preparing highly flame-retardant plastic liner gas cylinders contains phosphate groups and chlorine atoms in the flame retardant additives, which can enhance its flame retardant effect. The benzene ring structure contained in it can improve the durability of the fiber winding layer, and the ester structure improves the toughness with the epoxy resin. The above effects synergistically improve the service life of the plastic liner gas cylinder.

[0037] 3. The present application is used to prepare highly flame-retardant plastic liner gas cylinders, and the overall peripheral flame retardancy uniformity is good, which can protect the plastic liner gas cylinders for a long time, improve the safety of the use of plastic liner gas cylinders and reduce the leakage of hydrogen. DETAILED DESCRIPTION

[0038] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0039] Unless otherwise specified, the raw materials in the examples and comparative examples of the present application were purchased through commercial channels.

[0040] The curing agent in the present application can be any one or more of an alkaline curing agent and an acidic curing agent, and the plasticizer and catalyst can also be selected from existing plasticizers and catalysts in the prior art. The specific types of the above curing agent, plasticizer and catalyst do not constitute a limitation to the present application. In the following examples, diethylenetriamine is used as a curing agent, dibutyl phthalate is used as a plasticizer, and dibutyltin dilaurate is used as a catalyst.

[0041] Unless otherwise specified, the methods used in the examples and comparative examples of the present application are conventional methods in the prior art. The solvents used may be methanol, ethanol, DMF, DMSO, ethyl acetate, chloroform, dichloromethane, acetone, etc. The type of solvent used does not limit the reaction process, so in the following examples and comparative examples, appropriate solvents can be selected according to the properties of the raw materials and actual needs.

[0042] Example 1

[0043] This embodiment relates to a method for preparing a flame retardant additive, which comprises the following steps:

[0044] 1) adding p-nitrobenzoic acid and thionyl chloride in a molar ratio of 1:(2.5-3) to a solvent, reacting at 60-70° C. for 10-12 h, and removing excess thionyl chloride under reduced pressure to obtain p-nitrobenzoyl chloride;

[0045] 2) dissolving p-nitrobenzoyl chloride in a solvent to obtain a solution A, dissolving monomer B and triethylamine in a solvent to obtain a solution B, wherein the molar ratio of p-nitrobenzoyl chloride, monomer B and triethylamine is 1:(2-3):(2-3), adding solution B dropwise to solution A at room temperature, reacting at 20-30° C. for 8-10 hours, filtering, washing and drying to obtain an intermediate;

[0046] 3) adding the intermediate and stannous chloride dihydrate in a molar ratio of 1:(1.5-3) to a solvent, reacting at 50-70° C. for 15-20 hours, then adding 5% sodium bicarbonate solution to adjust the solution to alkalinity, filtering, separating, distilling under reduced pressure, and drying to obtain monomer A;

[0047] 4) Monomer A and tris(2,3-dichloropropyl) phosphate in a molar ratio of (3-4):1 are placed in a solvent, heated under reflux for 20-24 hours to obtain the obtained product, and then distilled under reduced pressure, extracted, and dried to obtain the obtained product.

[0048] The monomer B is selected from at least one of 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-chloro-1,3-propylene glycol, 2-chloro-1,3-butanediol and 2,2-dichloro-1,5-pentanediol.

[0049] According to the above method, flame retardant additives 1#-5# and comparative flame retardant additive D1# were prepared. The specific preparation method is as follows:

[0050] Flame retardant additive 1#

[0051] 1) adding p-nitrobenzoic acid and thionyl chloride in a molar ratio of 1:2.5 to a solvent, reacting at 70° C. for 10 h, and removing excess thionyl chloride under reduced pressure to obtain p-nitrobenzoyl chloride;

[0052] 2) dissolving p-nitrobenzoyl chloride in a solvent to obtain a solution A, dissolving 1,6-hexanediol and triethylamine in a solvent to obtain a solution B, wherein the molar ratio of p-nitrobenzoyl chloride, 1,6-hexanediol and triethylamine is 1:3:2, and adding the solution B dropwise to the solution A at room temperature, and then reacting at 20° C. for 10 hours, filtering, washing and drying to obtain an intermediate;

[0053] 3) adding the intermediate and stannous chloride dihydrate in a molar ratio of 1:1.5 to a solvent, reacting at 50° C. for 20 hours, then adding 5% sodium bicarbonate solution to adjust the solution to alkalinity, filtering, separating, distilling under reduced pressure, and drying to obtain monomer A;

[0054] 4) Monomer A and tris(2,3-dichloropropyl) phosphate in a molar ratio of 3:1 are placed in a solvent, heated under reflux for 24 hours to obtain the obtained product, and then the obtained product is obtained by vacuum distillation, extraction, and drying.

[0055] Flame retardant additive 2#

[0056] 1) adding p-nitrobenzoic acid and thionyl chloride in a molar ratio of 1:3 to a solvent, reacting at 60° C. for 12 h, and removing excess thionyl chloride under reduced pressure to obtain p-nitrobenzoyl chloride;

[0057] 2) dissolving p-nitrobenzoyl chloride in a solvent to obtain a solution A, dissolving 1,3-propylene glycol and triethylamine in a solvent to obtain a solution B, wherein the molar ratio of p-nitrobenzoyl chloride, 1,3-propylene glycol and triethylamine is 1:2:3, and adding the solution B dropwise to the solution A at room temperature, and then reacting at 30° C. for 8 hours, filtering, washing and drying to obtain an intermediate;

[0058] 3) adding the intermediate and stannous chloride dihydrate in a molar ratio of 1:3 to a solvent, reacting at 70° C. for 15 h, then adding 5% sodium bicarbonate solution to adjust the solution to alkalinity, filtering, separating, distilling under reduced pressure, and drying to obtain monomer A;

[0059] 4) Monomer A and tris(2,3-dichloropropyl) phosphate in a molar ratio of 4:1 are placed in a solvent, heated under reflux for 20 hours to obtain the product, and then distilled under reduced pressure, extracted, and dried to obtain the product.

[0060] Flame retardant additive 3#

[0061] 1) adding p-nitrobenzoic acid and thionyl chloride in a molar ratio of 1:2.5 to a solvent, reacting at 65° C. for 12 h, and removing excess thionyl chloride under reduced pressure to obtain p-nitrobenzoyl chloride;

[0062] 2) dissolving p-nitrobenzoyl chloride in a solvent to obtain a solution A, dissolving 1,5-pentanediol and triethylamine in a solvent to obtain a solution B, wherein the molar ratio of p-nitrobenzoyl chloride, 1,5-pentanediol and triethylamine is 1:3:3, and adding solution B dropwise to solution A at room temperature, and then reacting at 25° C. for 8 hours, filtering, washing and drying to obtain an intermediate;

[0063] 3) adding the intermediate and stannous chloride dihydrate in a molar ratio of 1:2.5 to a solvent, reacting at 60° C. for 18 h, then adding 5% sodium bicarbonate solution to adjust the solution to alkalinity, filtering, separating, distilling under reduced pressure, and drying to obtain monomer A;

[0064] 4) Monomer A and tris(2,3-dichloropropyl) phosphate in a molar ratio of 4:1 are placed in a solvent, heated under reflux for 22 hours to react, and then distilled under reduced pressure, extracted, and dried to obtain the obtained product.

[0065] Flame retardant additive 4#

[0066] The difference between the flame retardant additive 4# and the flame retardant additive 3# is that 2,2-dichloro-1,5-pentanediol is used to replace 1,5-pentanediol, and the rest is the same as the flame retardant additive 3#.

[0067] Flame retardant additive 5#

[0068] The difference between the flame retardant additive 5# and the flame retardant additive 3# is that 2-chloro-1,3-propanediol is used to replace 1,5-pentanediol, and the rest is the same as the flame retardant additive 3#.

[0069] Comparison of flame retardant additive D1#

[0070] The difference between the comparative flame retardant additive D1# and the flame retardant additive 3# is that the molar ratio of monomer A to tris(2,3-dichloropropyl) phosphate is 2:1, and the rest is the same as the flame retardant additive 3#.

[0071] Example 2

[0072] This embodiment relates to a method for preparing a highly flame-retardant plastic liner gas cylinder, comprising the following steps:

[0073] (1) Using PA11 as a substrate, a plastic liner is obtained by rotational molding, and a bottle mouth is reserved at the top of the plastic liner;

[0074] (2) The carbon fiber is impregnated into the impregnation slurry according to any one of claims 1 to 5 to obtain an impregnated fiber, the impregnated fiber is wound around the outside of the plastic liner, heated and cured to form a fiber winding layer, and a bottle mouth joint is installed at the bottle mouth.

[0075] According to the above preparation method, a plastic liner gas cylinder 1#- is prepared, and the specific preparation is as follows:

[0076] Plastic liner gas cylinder 1#

[0077] (1) 80 parts of PA11, 10 parts of epoxy resin, 1 part of curing agent, 2 parts of plasticizer and 1 part of catalyst were mixed, and the mixture was rotationally molded at 230° C. to obtain an outer layer with a thickness of 2.5 mm. 80 parts of PA11, 10 parts of EVOH, 5 parts of polyisocyanate and 2 parts of plasticizer were weighed, mixed and added to the outer layer, and rotationally molded at 230° C. to obtain an inner layer with a thickness of 2.5 mm, thereby obtaining a plastic liner, and a bottle mouth was reserved at the top of the plastic liner;

[0078] (2) 80 parts of water-based epoxy resin, 10 parts of flame retardant additive 1#, 20 parts of ethanol and 1 part of curing agent are mixed to obtain an impregnation slurry, and carbon fiber is impregnated in the slurry to obtain impregnated fiber, the impregnation amount of carbon fiber is 20wt%, the impregnated fiber is wound around the outside of the plastic liner, and heated and cured at 120°C for 4 hours to form a fiber winding layer with a thickness of 30mm, and a bottle mouth joint is installed at the bottle mouth to obtain the product.

[0079] Plastic liner gas cylinder 2#

[0080] (1) 100 parts of PA11, 20 parts of epoxy resin, 1 part of curing agent, 5 parts of plasticizer and 3 parts of catalyst are mixed, and the mixture is rotationally molded at 230° C. to obtain an outer layer with a thickness of 3 mm. 100 parts of PA11, 20 parts of EVOH, 8 parts of polyisocyanate and 5 parts of plasticizer are weighed, mixed and added to the outer layer, and rotationally molded at 230° C. to obtain an inner layer with a thickness of 3 mm, thereby obtaining a plastic liner, and a bottle mouth is reserved at the top of the plastic liner;

[0081] (2) 100 parts of water-based epoxy resin, 15 parts of flame retardant additive 2#, 25 parts of ethanol and 2 parts of curing agent are mixed to obtain an impregnation slurry, and carbon fiber is impregnated in the slurry to obtain impregnated fiber, the impregnation amount of carbon fiber is 30wt%, the impregnated fiber is wound around the outside of the plastic liner, and after heating and curing at 120°C for 4 hours, a fiber winding layer with a thickness of 25mm is formed, and a bottle mouth joint is installed at the bottle mouth to obtain the product.

[0082] Plastic liner gas bottle 3#

[0083] (1) Same as plastic liner gas cylinder 2#;

[0084] (2) 90 parts of water-based epoxy resin, 13 parts of flame retardant additive 3#, 25 parts of ethanol and 1 part of curing agent are mixed to obtain an impregnation slurry, and carbon fiber is impregnated in the slurry to obtain impregnated fiber, the impregnation amount of carbon fiber is 25wt%, the impregnated fiber is wound around the outside of the plastic liner, and heated and cured at 120°C for 4 hours to form a fiber winding layer with a thickness of 25mm, and a bottle mouth joint is installed at the bottle mouth to obtain the product.

[0085] Plastic liner gas cylinder 4#

[0086] The difference between this plastic liner gas cylinder and plastic liner gas cylinder 3# is that flame retardant additive 4# is used to replace flame retardant additive 3#, and the rest is the same as plastic liner gas cylinder 3#.

[0087] Plastic liner gas cylinder 5#

[0088] The difference between this plastic liner gas cylinder and plastic liner gas cylinder 3# is that flame retardant additive 5# is used to replace flame retardant additive 3#, and the rest is the same as plastic liner gas cylinder 3#.

[0089] Plastic liner gas bottle 6#

[0090] The difference between this plastic liner gas cylinder and plastic liner gas cylinder 3# is that before the impregnated fiber is wound, a layer of impregnating slurry is applied on the outside of the plastic liner, and the coating thickness is less than 0.2mm. The rest is the same as plastic liner gas cylinder 3#.

[0091] Plastic liner gas cylinder 7#

[0092] The difference between this plastic liner gas cylinder and plastic liner gas cylinder 3# is that the outer layer of the plastic liner also contains 1 part of flame retardant additive 3#, and the rest is the same as plastic liner gas cylinder 3#.

[0093] Compare plastic liner gas bottle D1#

[0094] The difference between this comparative plastic liner gas cylinder and plastic liner gas cylinder 3# is that comparative flame retardant additive D1# is used to replace flame retardant additive 3#, and the rest is the same as plastic liner gas cylinder 3#.

[0095] Comparison of plastic liner gas bottle D2#

[0096] The difference between the plastic liner gas cylinder and plastic liner gas cylinder 3# in this comparison is that tri(2,3-dichloropropyl) phosphate is used to replace the flame retardant additive 3#, and the rest is the same as plastic liner gas cylinder 3#.

[0097] Test Example 1

[0098] The hydrogen permeability coefficient of the gas cylinders prepared in the above embodiments and comparative examples was tested with reference to GB / T42610-2023; the fatigue life test of the gas cylinders was performed with reference to GB / T42612-2023. In the peel strength test, the gas cylinders were cut into strips with a width of 150 mm × 200 mm, and the plastic liner and the fiber winding layer were pre-peeled 50 mm along the length direction. The sample was placed in an environment with a temperature of 23±2°C and a relative humidity of 50±5% for 4 days, and the two ends of the peeled part of the sample were clamped on the upper and lower clamps of the tensile testing machine, respectively, so that the peeled part of the sample was in a vertical state and the unpeeled part was in a horizontal state. The testing machine was turned on for peeling, and the test speed was set to 100 mm / min, and its peel strength was calculated.

[0099] The specific test results are shown in Table 1 below:

[0100] Table 1

[0101]

[0102] Test Example 2

[0103] The sample prepared in the above Example 2 was cut into 10×10 cm and subjected to a fire resistance test. The sample was exposed to the flame of an oil pan for 60 seconds to observe whether the sample burned. If there was a flame in the plastic liner gas cylinder, the flame extinguishing time was observed after the fire source was removed. The test results are shown in Table 2.

[0104] Table 2

[0105]

[0106] The plastic liner gas cylinder prepared in the above Example 2 was tested for corrosion resistance and aging resistance. The above plastic liner gas cylinder can meet the corrosion resistance and aging resistance requirements of hydrogen cylinders in the industry.

[0107] The above is only the embodiment of the present application, and the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application can have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.

Claims

1. An impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder, characterized in that: The invention comprises 80-100 parts of waterborne epoxy resin, 10-15 parts of flame retardant additive, 20-25 parts of ethanol and 1-2 parts of curing agent by weight. The flame retardant additive is prepared by heating and refluxing monomer A and tris(2,3-dichloropropyl) phosphate in a molar ratio of (3-4):

1. The structural formula of the monomer A is as follows: wherein R1 is selected from an unsubstituted alkyl group or a halogen-substituted alkyl group containing 3 to 6 carbon atoms.

2. The impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder according to claim 1, characterized in that: The R1 is selected from halogen-substituted alkyl groups containing 3 to 6 carbon atoms.

3. The impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder according to claim 1, characterized in that: p-Nitrobenzoyl chloride, monomer B and triethylamine react to obtain an intermediate, the intermediate reacts with stannous chloride dihydrate, and then an alkaline solution is added to adjust to weak alkalinity, and monomer A is obtained after treatment; The monomer B is selected from at least one of 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-chloro-1,3-propylene glycol, 2-chloro-1,3-butanediol, and 2,2-dichloro-1,5-pentanediol.

4. The impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder according to claim 3, characterized in that: The molar ratio of p-nitrobenzoyl chloride, monomer B and triethylamine is 1:(2-3):(2-3), the reaction temperature is 20-30° C., and the reaction time is 8-10 hours.

5. The impregnation slurry for preparing a highly flame-retardant plastic liner gas cylinder according to claim 4, characterized in that: The molar ratio of the intermediate to stannous chloride dihydrate is 1:(1.5-3), the reaction temperature is 50-70° C., and the reaction time is 15-20 hours.

6. A method for preparing a highly flame-retardant plastic liner gas cylinder, characterized in that: The steps include: (1) Using PA11 as a substrate, a plastic liner is obtained by rotational molding, and a bottle mouth is reserved at the top of the plastic liner; (2) The carbon fiber is impregnated into the impregnation slurry according to any one of claims 1 to 5 to obtain an impregnated fiber, the impregnated fiber is wound around the outside of the plastic liner, heated and cured to form a fiber winding layer, and a bottle mouth joint is installed at the bottle mouth.

7. The method for preparing a highly flame-retardant plastic liner gas cylinder according to claim 6, characterized in that: The impregnation amount of the carbon fiber is 20wt%-30wt%.

8. The method for preparing a highly flame-retardant plastic liner gas cylinder according to claim 5, characterized in that: The thickness of the fiber winding layer is 25-30 mm.

9. The method for preparing a highly flame-retardant plastic liner gas cylinder according to claim 5, characterized in that: The plastic liner comprises an inner layer and an outer layer, wherein the outer layer is arranged on the outer side of the inner layer, and the impregnated fibers are wound around the outer side of the outer layer. Before the impregnated fibers are wound around, a layer of impregnated slurry is applied on the outer surface of the outer layer.

10. A highly flame-retardant plastic liner gas cylinder prepared by the method for preparing a highly flame-retardant plastic liner gas cylinder according to any one of claims 6 to 9.

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