CN117948535A - Plastic liner and preparation method and application thereof - Google Patents
Plastic liner and preparation method and application thereof Download PDFInfo
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- CN117948535A CN117948535A CN202211333814.8A CN202211333814A CN117948535A CN 117948535 A CN117948535 A CN 117948535A CN 202211333814 A CN202211333814 A CN 202211333814A CN 117948535 A CN117948535 A CN 117948535A
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- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 16
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
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- 230000004888 barrier function Effects 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 21
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 21
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 20
- 239000004952 Polyamide Substances 0.000 claims abstract description 17
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000003860 storage Methods 0.000 claims abstract description 15
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- 238000001175 rotational moulding Methods 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 10
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- 238000012360 testing method Methods 0.000 claims description 6
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
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- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000007789 gas Substances 0.000 abstract description 11
- 230000035939 shock Effects 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
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- 229920001778 nylon Polymers 0.000 description 20
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- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 6
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 6
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- 229920006097 Ultramide® Polymers 0.000 description 1
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Abstract
The invention relates to a plastic liner, a preparation method and application thereof, belonging to the technical field of high polymer materials. The plastic liner is of a multi-layer structure and sequentially comprises an outer layer, a barrier layer, an inner layer and a matrix layer from outside to inside; the material of the outer layer comprises polyamide, graphene or modified matter thereof and a thermoplastic agent; the material of the barrier layer comprises an ethylene-vinyl alcohol copolymer; the material of the inner layer comprises polyamide, graphene or modified matter thereof, and a thermoplastic agent; the material of the matrix layer comprises ethylene-tetrafluoroethylene copolymer; the plastic liner has higher barrier property to water, gas and hydrogen, the difference of barrier capability of each layer to hydrogen is not too large, meanwhile, the compatibility among the layers is good, the leakage of hydrogen is prevented, the plastic liner also has excellent low-temperature shock resistance, is suitable for the plastic liner of the high-pressure hydrogen cylinder with 70MPa, and can be applied to the plastic liner of the vehicle-mounted 70MPa high-pressure hydrogen storage cylinder.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a plastic liner, a preparation method and application thereof.
Background
Along with the current shortage of petroleum resources and global climate problems caused by carbon emission, hydrogen energy has the advantages of abundant resources, high combustion value, cleanness, reproducibility and the like, becomes a popular research and application object in secondary energy in more than ten years, and the country is also in line with a hydrogen energy layout policy, and the great heat of hydrogen energy also brings the rapid development trend of the hydrogen energy electric car industry and the rapid development of fuel cells and battery car technologies used by the hydrogen energy electric car industry, so that the breakthrough of the hydrogen storage technology is one of keys for breaking the limit of hydrogen energy application.
The high-pressure gaseous hydrogen storage technology is one of the most mainstream hydrogen storage modes at present, namely, hydrogen is compressed under high pressure (usually 35MPa or 70 MPa) and stored in a high-density gaseous form, so that large companies such as Virginia (FAURECIA) and the like have very mature IV type gas cylinder technology, and have deep research and application capability on IV type gas cylinders in China, such as Shenyang Stedder, beijing Tianhai industry, and epen automobiles, and the like, and the continuous development of the domestic IV type gas cylinder technology is marked, the technology is mature, and better hydrogen storage capability is used. The IV type bottle is used as one of hydrogen storage bottles, refers to a hydrogen storage bottle prepared by using thermoplastic plastics as a liner material, has the advantages of light weight, corrosion resistance, easy processing, low cost, high hydrogen storage density and the like compared with a III type bottle which is already mature in the market, has the pushing-out of a few experimental hydrogen fuel cell automobiles in Honda and Toyota in the world, and still has a certain application gap with common fuel vehicles.
The plastic liner of the IV-type gas cylinder is usually prepared from two materials, namely high-density polyethylene (HDPE) and Polyamide (PA), and the liner material has a certain blocking effect on hydrogen, but part of hydrogen still can be dissolved between materials in a high-pressure hydrogen storage environment, and the liner can bulge due to pressure difference in the pressurization and pressure release processes, so that the blocking performance of the plastic liner material on hydrogen needs to be improved by a modification method and the like. On the other hand, the temperature in the hydrogen storage bottle can be circulated at the temperature of-40 ℃ to 80 ℃ in the gas filling and discharging stage, and the high pressure and the temperature circulation can possibly cause collapse and even collapse of the inner container of the gas bottle in the material simulation, so that the low-temperature shock resistance of the plastic inner container is also required to be increased.
In chinese patent CN111645370B, a multilayer structure suitable for type iv bottles is proposed, in which EVOH is used to compensate for the hydrogen barrier property of the PA6 monolayer, and in which, for different cases of the outer layer and the inner layer resin, no masterbatch and resin blend are used to compensate for the barrier property of the PA6 layer, however, no optimization is performed on the low temperature performance. CN113124309a proposes a multilayer structure suitable for a type iv gas cylinder, where a transition layer between PA6 and EVOH is used to ensure effective bonding between different layers, however, no optimization is made for the low temperature performance of the material, and the barrier and low temperature performance cannot be achieved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a plastic liner. In particular to a plastic liner, a preparation method and application thereof. The plastic liner has a multi-layer structure and has excellent hydrogen barrier property and low-temperature shock resistance.
The invention discloses a plastic liner and a preparation method thereof, wherein the plastic liner has a multi-layer structure and comprises an outer layer, a barrier layer, an inner layer and a matrix layer; the outer layer and the inner layer both comprise polyamide, graphene and modified matters thereof, and components including thermoplastic agents; the barrier layer is ethylene-vinyl alcohol copolymer; the matrix layer is ethylene-tetrafluoroethylene copolymer. The plastic liner can be prepared by adopting a rotational molding process and feeding for multiple times. The plastic liner has higher barrier property to water, gas and hydrogen, the difference of barrier capability of each layer to hydrogen is not too large, meanwhile, the compatibility among the layers is good, the leakage of hydrogen is prevented, the plastic liner also has excellent low-temperature shock resistance, is suitable for the plastic liner of the high-pressure hydrogen cylinder with 70MPa, and can be applied to the plastic liner of the vehicle-mounted 70MPa high-pressure hydrogen storage cylinder.
One of the purposes of the invention is to provide a plastic liner which has a multi-layer structure and can comprise an outer layer, a barrier layer, an inner layer and a matrix layer;
The thickness ratio of the outer layer, the barrier layer, the inner layer, and the matrix layer may be (1-5): (1-2): (1-5): (0.3-1), preferably (1-2.5): (1-1.6): (1-2.5): (0.3-0.8), more preferably (1-1.5): (1-1.5): (1-1.5): (0.4-0.5). The thickness units may be millimeters. For example, the specific thickness may be 1.2 mm, 1.1 mm, 1.2 mm, 0.4 mm for the outer layer, the barrier layer, the inner layer and the matrix layer in that order.
In a specific implementation, the plastic liner can comprise an outer layer, a barrier layer, an inner layer and a matrix layer from outside to inside in sequence.
Wherein,
The material of the outer layer may comprise components including polyamide, graphene or modifications thereof, and thermoplastic;
wherein the mass ratio of the polyamide to the graphene or the modified matter thereof to the thermoplastic agent can be (90-100): (1-2.5): (3-30), preferably (95-100): (1.25-2): (3-15), more preferably (95-100): (1.25-1.75): (5-10).
The material of the barrier layer can comprise ethylene-vinyl alcohol copolymer (EVOH), so that the barrier performance is ensured, and certain bonding force between the barrier layer and the inner layer and the outer layer is maintained; preferably, the ethylene-vinyl alcohol copolymer may have a melting point of 160 to 180℃and a vinyl content of 32 to 48%, and may have a melt flow index of 6 to 12g/10min under test conditions of 310℃and 1.6 kg. The ethylene-vinyl alcohol copolymer in the barrier layer material is a material with good barrier property in common polymers, but has poor mechanical property and processing property, so that the EVOH is protected by the resin of the inner layer and the outer layer, the problem of the aspect of EVOH is solved, and the ethylene-vinyl alcohol copolymer can be better combined with the resin of the outer layer and the inner layer.
The material of the inner layer may comprise polyamide, graphene or its modified substance, and thermoplastic agent; in the material of the inner layer, the mass ratio of the polyamide to the graphene or the modified matter thereof to the thermoplastic agent can be (90-100): (1-2.5): (5-30), preferably (95-100): (1.25-2): (6-20), more preferably (95-100): (1.25-1.75): (10-15).
The preparation method of the materials of the outer layer and the inner layer adopts a method commonly used in the field, and specifically comprises the following steps: and (3) melting and blending components comprising polyamide, graphene or modified matter thereof and a thermoplastic agent, extruding, and granulating. Blending equipment commonly used in the art, such as single screw extruders, twin screw extruders, and the like, may be employed.
The material of the matrix layer may comprise ethylene-tetrafluoroethylene copolymer (ETFE). Preferably, the ethylene-tetrafluoroethylene copolymer may have a melting point of 250 to 280℃and a melt flow index of 10 to 15g/10min under test conditions of 310℃and 1.6 kg. The matrix layer is used as the low temperature resistant layer, contains the ETFE material, can exert the excellent impact resistance of the ETFE material at low temperature to a certain extent, greatly enhances the integral impact resistance of the liner material, and has a certain degree of barrier capability to hydrogen.
Wherein, in the material of the outer layer and/or the material of the inner layer,
The polyamide can comprise any one or more of nylon 6 (PA 6), nylon 66 (PA 66) and nylon 12 (PA 12), has higher impact resistance and hydrogen barrier property, and also provides a layer of protection for the barrier layer. Preferably, the polyamide may be PA6 and/or PA66.
According to the invention, the graphene or the modified graphene is added in the inner layer and the outer layer of the plastic inner container, so that the blocking capability of the inner layer material and the outer layer material to hydrogen can be improved, and the inner container is prevented from layering and collapsing due to overlarge hydrogen blocking capability difference among the multi-layer materials in the alternating process of high temperature and low pressure.
The graphene and the modified product thereof are sheet-shaped.
The graphene modifier can be at least one of carboxyl, hydroxyl, anhydride, amino, amido, imide and derivative groups thereof introduced into graphene; the preferred graphene modifier can be selected from at least one of amino, hydroxyl and derivative group modified graphene;
Preferably, the method comprises the steps of,
The preparation method of the graphene modified substance can comprise the following steps:
The graphene is subjected to surface organic modification treatment by glycidol, organic quaternary ammonium salt, organic quaternary phosphonium salt, anionic surfactant or coupling agent to obtain the graphene modified substance, and carboxyl, hydroxyl, carboxyl, anhydride, hydroxyl, amino, amido, imide, derivative groups thereof and the like are introduced into the graphene. The graphene modified substance can be better dispersed in nylon. Preferred modified graphene includes at least one of amine groups, hydroxyl groups, and groups derived therefrom.
According to the invention, the thermoplastic agent is added into the inner layer and the outer layer of the plastic inner container, so that the blocking capability of the inner layer and the outer layer material to hydrogen can be further improved by increasing the intermolecular hydrogen bonding effect, and the bonding capability between the inner layer and the outer layer and the blocking layer or the matrix layer can be increased, so that better compatibility is realized.
The thermoplastic may comprise a component a and/or a component b;
The component a can be at least one selected from glycol, glycerol, pentaerythritol, sorbitol, mannitol, xylitol, and/or,
The component b can be at least one selected from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol;
preferably, the thermoplastic comprises a component a and a component b; more preferably, the mass ratio of the a component and the b component may be (75 to 90): (10-3).
The tensile strength of the plastic liner can be more than or equal to 55MPa, the hydrogen permeability coefficient is less than or equal to 5 multiplied by 10 -15cm3·cm/(cm2 s & Pa, and the notch impact strength at 40 ℃ exceeds 45J/m.
The second purpose of the invention is to provide a preparation method of the plastic liner, which is characterized in that the plastic liner can be prepared by adopting a rotational molding process.
Wherein, the material of the matrix layer can be combined with the inner layer by rotational molding or spraying.
Specifically, the preparation method of the plastic liner can comprise the following steps:
(1) Performing first rotational molding on the outer layer material to form an outer layer;
(2) Performing second rotational molding on the barrier layer material to form a barrier layer in the outer layer;
(3) Performing third rotational molding on the inner layer material to form an inner layer in the barrier layer;
(4) Fourth rotational molding of the matrix layer material is carried out to form a matrix layer in the inner layer; wherein, the matrix layer material can also be combined with the inner layer through a spraying mode.
Wherein,
The conditions of the first rotational molding can comprise the temperature of 300-320 ℃ and the time of 20-40 min;
And/or the number of the groups of groups,
The conditions of the second rotational molding can comprise the temperature of 260-280 ℃ and the time of 50-70 min;
And/or the number of the groups of groups,
The conditions of the third rotational molding can comprise the temperature of 300-320 ℃ and the time of 20-40 min;
And/or the number of the groups of groups,
The fourth rotational molding condition can comprise the temperature of 290-310 ℃ and the time of 30-50 min.
It is a further object of the present invention to provide the use of a plastic liner according to one of the objects of the present invention or a plastic liner produced by a method according to the second object of the present invention, preferably in a hydrogen storage bottle.
The plastic liner has higher barrier property to hydrogen, water vapor and the like, has higher low-temperature shock resistance, and can be suitable for products such as 70MPa high-pressure hydrogen cylinder plastic liners and the like.
The plastic liner of the invention is prepared by optimizing the thickness ratio of each layer, and the proper thickness of each layer can achieve the aim of considering the hydrogen barrier property and the low-temperature shock resistance of the material.
Compared with the traditional blow molding and injection molding, the rotational molding method for the plastic liner of the high-pressure hydrogen storage bottle has the advantages of low cost, uniform thickness, variable wall thickness, no seam, raw material saving and the like, and the plastic liner is prepared by sequentially performing rotational molding on each layer of material by feeding materials for multiple times and optimizing the technological parameters by carrying out the regulation and control on the processing technological parameters of each layer of material, such as the rotation speed ratio of a main shaft and a secondary shaft, the heating time and temperature, the cooling mode and time and the like.
Compared with the prior art, the invention has the following beneficial effects:
The plastic liner has higher barrier property to water vapor and hydrogen, the difference of barrier capability of each layer to hydrogen is not excessive, meanwhile, the compatibility among the layers is good, the leakage of hydrogen is prevented, and meanwhile, the ETFE is adopted as a matrix layer, so that the overall low-temperature shock resistance of the material can be better improved, and the plastic liner is suitable for high-pressure hydrogen storage bottle plastic liners, for example, 70MPa high-pressure hydrogen bottle plastic liners.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a schematic cross-sectional view of a plastic liner of the present invention.
Wherein 1-outer layer, 2-barrier layer, 3-inner layer, 4-matrix layer
Fig. 1 is a schematic cross-sectional structure of a plastic liner of the present invention, which is a multi-layer structure, wherein 1 is an outer layer of the plastic liner, 2 is a barrier layer of the plastic liner, 3 is an inner layer of the plastic liner, 4 is a matrix layer of the plastic liner, and the multi-layer structure is adopted to integrate the advantages of the materials of the layers, and improve the hydrogen permeation resistance and impact resistance of the plastic liner through synergistic effect.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Raw material source
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
The main raw material sources used in the examples are as follows:
PA6: the brand Ultramid 8231 HS of Basoff, germany;
graphene modification: amino modified graphene, pioneer nanometer company, brand XF005-3, platy;
The preparation method of the materials (modified nylon particles) of the inner layer and the outer layer comprises the following steps: thermoplastic, extrusion, pelletization were performed using a PolyLab HAAKETM Rheomex OS PTW co-rotating twin-screw extruder (screw diameter 16mm, l/d=40) from thermo fisher technologies, usa. The powder feeder attached to the extruder was calibrated to feed the PA6 nylon feed stock into the twin screw at a feed rate of 820g/hr. Based on 100 parts by mass of nylon raw material, graphene modifier (1.5 parts by mass) and thermoplastic agent (10 parts by mass of thermoplastic agent, which is a mixture, wherein the mass ratio of sorbitol to diethylene glycol is 85:4.5) are added into an extruder through a feed inlet, and the feeding rate is 80g/hr. After passing through the screw, the mixture is cut into modified nylon particles with the diameter of about 3mm by a granulator, and the modified nylon particles are collected and packaged for standby.
EVOH: colali corporation, brand C109A;
ETFE: dupont, usa, tefzel 2195.
Test equipment and method adopted in the embodiment:
tensile properties were measured using an Instron 5567 from Instron corporation, usa, with tensile strength and elongation at break measured as ASTM D638;
The impact property is tested by adopting XJ-50Z of the Dewar company, and the test standard of the notch impact strength of the cantilever beam is ASTM D256;
The gas permeability was measured by VAC-V2 from Jinan blue light company, and the gas permeability coefficient was measured in GB/T1038.
Example 1
The preparation steps are as follows, according to the thicknesses of the different layers in table 1:
(1) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an outer layer, performing rotational molding for 30min, and cooling to 80 ℃;
(2) Adding EVOH resin into a die, rotating the main shaft at 5-10 rpm, rotating the auxiliary shaft at 2-5 rpm, performing rotational molding at 260 ℃ to obtain a barrier layer, performing rotational molding for 50min, and cooling to 80 ℃;
(3) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an inner layer, performing rotational molding for 40min, and cooling to 65 ℃;
(4) And (3) adding ETFE resin into the mold, rotating the main shaft at 5-10 rpm, rotating the auxiliary shaft at 2-5 rpm, performing rotational molding at 300 ℃ to obtain a matrix layer, performing rotational molding for 40min, cooling to 65 ℃ by air cooling, and demolding to obtain the plastic liner.
Example 2
The preparation steps are as follows, according to the thicknesses of the different layers in table 1:
(1) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an outer layer, performing rotational molding for 30min, and cooling to 80 ℃;
(2) Adding EVOH resin into a die, rotating the main shaft at 5-10 rpm, rotating the auxiliary shaft at 2-5 rpm, performing rotational molding at 260 ℃ to obtain a barrier layer, performing rotational molding for 50min, and cooling to 80 ℃;
(3) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an inner layer, performing rotational molding for 40min, and cooling to 65 ℃;
(4) And (3) adding ETFE resin into the mold, rotating the main shaft at 5-10 rpm, rotating the auxiliary shaft at 2-5 rpm, performing rotational molding at 300 ℃ to obtain a matrix layer, performing rotational molding for 40min, cooling to 65 ℃ by air cooling, and demolding to obtain the plastic liner.
Example 3
The remaining steps were prepared according to the thicknesses of the different layers in table 1 as follows:
(1) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an outer layer, performing rotational molding for 30min, and cooling to 80 ℃;
(2) Adding EVOH resin into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 260 ℃ to obtain a barrier layer, performing rotational molding for 50min, and cooling to 80 ℃;
(3) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an inner layer, performing rotational molding for 40min, and cooling to 65 ℃;
(4) And (3) adding ETFE resin into the mold, rotating the main shaft at 5-10 rpm, rotating the auxiliary shaft at 2-5 rpm, performing rotational molding at 300 ℃ to obtain a matrix layer, performing rotational molding for 40min, cooling to 65 ℃ by air cooling, and demolding to obtain the plastic liner.
Example 4
The remaining steps were prepared according to the thicknesses of the different layers in table 1 as follows:
(1) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an outer layer, performing rotational molding for 30min, and cooling to 80 ℃;
(2) Adding EVOH resin into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 260 ℃ to obtain a barrier layer, performing rotational molding for 50min, and cooling to 80 ℃;
(3) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an inner layer, performing rotational molding for 40min, and cooling to 65 ℃;
(4) And (3) adding ETFE resin into the mold, rotating the main shaft at 5-10 rpm, rotating the auxiliary shaft at 2-5 rpm, performing rotational molding at 300 ℃ to obtain a matrix layer, performing rotational molding for 40min, cooling to 65 ℃ by air cooling, and demolding to obtain the plastic liner.
Example 5
The remaining steps were prepared according to the thicknesses of the different layers in table 1 as follows:
(1) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an outer layer, performing rotational molding for 30min, and cooling to 80 ℃;
(2) Adding EVOH resin into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 260 ℃ to obtain a barrier layer, performing rotational molding for 50min, and cooling to 80 ℃;
(3) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an inner layer, performing rotational molding for 40min, and cooling to 65 ℃;
(4) And (3) adopting ETFE resin to spray the inner liner, rotating and solidifying the inner liner in a solidifying furnace for 15min at 300 ℃ after finishing the spraying, cooling to 65 ℃, and demoulding to obtain the finished product.
Comparative example 1
The preparation steps are as follows, according to the thicknesses of the different layers in table 1:
(1) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an outer layer, performing rotational molding for 30min, and cooling to 80 ℃;
(2) Adding EVOH resin into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 260 ℃ to obtain a barrier layer, performing rotational molding for 50min, and cooling to 80 ℃;
(3) Adding modified nylon particles into a die, rotating the main shaft at 5-10 rpm, rotating the auxiliary shaft at 2-5 rpm, performing rotational molding at 310 ℃ to obtain an inner layer, performing rotational molding for 40min, cooling to 65 ℃ by air cooling, and demolding.
Comparative example 2
The preparation steps are as follows, according to the thicknesses of the different layers in table 1:
(1) Adding modified nylon particles into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 310 ℃ to obtain an outer layer, performing rotational molding for 30min, and cooling to 80 ℃;
(2) Adding modified EVOH resin into a die, wherein the rotation speed of a main shaft is 5-10 rpm, the rotation speed of a secondary shaft is 2-5 rpm, performing rotational molding at the temperature of 260 ℃ to obtain a barrier layer, performing rotational molding for 50min, and cooling to 80 ℃;
(3) Adding modified nylon particles into a die, rotating the main shaft at 5-10 rpm, rotating the auxiliary shaft at 2-5 rpm, performing rotational molding at 310 ℃ to obtain an inner layer, performing rotational molding for 40min, cooling to 65 ℃ by air cooling, and demolding.
Table 1 (Unit mm)
TABLE 2 Performance test results
As can be seen from Table 2, the tensile strength of the plastic liner prepared by the embodiment of the application is more than or equal to 55MPa, the hydrogen permeability coefficient is less than or equal to 5 multiplied by 10 -15cm3·cm/(cm2 s.s.Pa, the notch impact strength at 40 ℃ exceeds 45J/m, and the plastic liner has excellent hydrogen barrier property and low-temperature impact resistance. Neither comparative example 1 lacking a matrix layer nor comparative example 2 having an excessively thick matrix layer can have tensile strength at low temperature and room temperature.
Claims (14)
1. A plastic liner, characterized in that:
The plastic liner is of a multi-layer structure and comprises an outer layer, a barrier layer, an inner layer and a matrix layer;
the material of the matrix layer comprises ethylene-tetrafluoroethylene copolymer;
Preferably, the ethylene-tetrafluoroethylene copolymer has a melting point of 250-280 ℃ and a melt flow index of 10-15 g/10min under test conditions of 310 ℃ and 1.6 kg.
2. The plastic liner of claim 1, wherein:
The thickness ratio of the outer layer, the barrier layer, the inner layer and the matrix layer is (1-5): (1-2): (1-5): (0.3-1), preferably (1-2.5): (1-1.6): (1-2.5): (0.3 to 0.8), more preferably (1 to 1.5): (1-1.5): (1-1.5): (0.4-0.5).
3. The plastic liner of claim 1, wherein:
The tensile strength of the plastic liner is more than or equal to 55MPa, the hydrogen permeability coefficient is less than or equal to 5 multiplied by 10 -15cm3·cm/(cm2 s & Pa, and the notch impact strength at 40 ℃ is more than 45J/m.
4. A plastic liner according to any one of claims 1 to 3, wherein:
The material of the outer layer comprises polyamide, graphene or a modified matter thereof and a thermoplastic agent;
the mass ratio of the polyamide to the graphene or the modified matter thereof to the thermoplastic agent is (90-100): (1-2.5): (3-30), preferably (95-100): (1.25-2): (3-15), more preferably (95-100): (1.25-1.75): (5-10).
5. A plastic liner according to any one of claims 1 to 3, wherein:
The material of the barrier layer comprises an ethylene-vinyl alcohol copolymer; preferably, the ethylene-vinyl alcohol copolymer has a melting point of 160-180 ℃ and a vinyl content of 32-48% and a melt flow index of 6-12 g/10min under test conditions of 310 ℃ and 1.6 kg.
6. A plastic liner according to any one of claims 1 to 3, wherein:
The material of the inner layer comprises polyamide, graphene or a modified matter thereof and a thermoplastic agent;
The mass ratio of the polyamide to the graphene or the modified matter thereof to the thermoplastic agent is (90-100): (1-2.5): (5-30), preferably (95-100): (1.25-2): (6-20), more preferably (95-100): (1.25-1.75): (10-15).
7. A plastic liner according to claim 4 or 6, wherein,
The material of the outer layer and/or the material of the inner layer,
The polyamide is at least one selected from nylon 6, nylon 66 and nylon 12.
8. A plastic liner according to claim 4 or 6, wherein:
the material of the outer layer and/or the material of the inner layer,
The graphene modifier is prepared by introducing at least one of carboxyl, hydroxyl, anhydride, amino, amido, imide and derivative groups thereof into graphene; the preferred graphene modifier is at least one of amino, hydroxyl and derivative groups modified graphene.
9. A plastic liner according to claim 4 or 6, wherein:
the material of the outer layer and/or the material of the inner layer,
The thermoplastic agent comprises a component a and/or a component b;
The component a is at least one selected from glycol, glycerol, pentaerythritol, sorbitol, mannitol and xylitol, and/or,
The component b is at least one selected from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol;
Preferably, the thermoplastic comprises a component a and a component b; more preferably, the mass ratio of the component a to the component b is (75-90): (10-3).
10. The method of manufacturing a plastic liner according to any one of claims 1 to 9, characterized in that: the plastic liner is prepared by adopting a rotational molding process.
11. The method for manufacturing a plastic liner according to claim 10, wherein:
the material of the matrix layer is combined with the inner layer by rotational molding or spraying.
12. The method for manufacturing a plastic liner according to claim 10, comprising the steps of:
(1) Performing first rotational molding on the outer layer material to form an outer layer;
(2) Performing second rotational molding on the barrier layer material to form a barrier layer in the outer layer;
(3) Performing third rotational molding on the inner layer material to form an inner layer in the barrier layer;
(4) And performing fourth rotational molding on the matrix layer material to form a matrix layer on the inner layer.
13. The method for manufacturing a plastic liner according to claim 12, wherein:
The conditions of the first rotational molding include that the temperature is 300-320 ℃ and the time is 20-40 min;
And/or the number of the groups of groups,
The conditions of the second rotational molding include that the temperature is 260-280 ℃ and the time is 50-70 min;
And/or the number of the groups of groups,
The third rotational molding condition comprises that the temperature is 300-320 ℃ and the time is 20-40 min;
And/or the number of the groups of groups,
The fourth rotational molding condition comprises the temperature of 290-310 ℃ and the time of 30-50 min.
14. Use of a plastic liner according to any one of claims 1 to 9 or a plastic liner made according to the method of any one of claims 10 to 13, preferably in a hydrogen storage bottle.
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