CN115785508A - Hydrogen storage bottle composite material and preparation method thereof - Google Patents
Hydrogen storage bottle composite material and preparation method thereof Download PDFInfo
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- CN115785508A CN115785508A CN202211519158.0A CN202211519158A CN115785508A CN 115785508 A CN115785508 A CN 115785508A CN 202211519158 A CN202211519158 A CN 202211519158A CN 115785508 A CN115785508 A CN 115785508A
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- hydrogen storage
- resin
- storage bottle
- cpvc
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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Abstract
The invention provides a hydrogen storage bottle composite material, which consists of CPVC resin and PVDC resin; the hydrogen storage bottle composite material is used as a material of any layer of the inner container of the hydrogen storage bottle; the hydrogen storage bottle composite material is prepared by the following method: forming a bottle body structure by the CPVC resin through an injection molding method, then coating the PVDC resin on the inner surface or the outer surface of the bottle body structure formed by the CPVC resin, drying and curing to obtain the CPVC/CPVC composite material. In the invention, PVDC resin is coated on the inner surface or the outer surface of a bottle body structure formed by CPVC resin, and the sealing property is obviously superior to nylon and HDPE although the sealing property does not reach aluminum materials; furthermore, the compatibility of the PVDC resin and the CPVC resin is improved by adding the silane coupling agent, so that the sealing property of the PVDC resin and the CPVC resin is greatly improved, and the sealing property of the PVDC resin is close to that of an aluminum material.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a hydrogen storage bottle composite material and a preparation method thereof.
Background
The high-pressure hydrogen storage cylinder is mainly used for storing high-pressure gaseous hydrogen, has many advantages of low cost, high safety and the like compared with low-temperature liquid hydrogen storage and utilization of hydrogen storage materials along with the current shortage of petroleum resources and global climate problems caused by carbon emission, and is particularly widely applied to the field of new energy hydrogen fuel cell automobiles.
The hydrogen storage density of the hydrogen storage cylinder is a key factor for restricting the driving mileage of a hydrogen fuel automobile, and taking a commonly used 70Mpa hydrogen storage cylinder as an example, the hydrogen storage density of a composite material lining of the hydrogen storage cylinder can be improved by more than half compared with that of a metal lining, so that the hydrogen storage cylinder is the main development direction of the vehicle-mounted hydrogen storage cylinder. However, the modulus and strength of the composite material lining of the hydrogen storage bottle are low, when fibers are wound on the outer surface of the composite material lining of the hydrogen storage bottle, low-pressure explosion easily occurs on the composite material lining of the hydrogen storage bottle in the using process, and the mechanical property of the composite material high-pressure hydrogen storage bottle can be influenced by the number of wound layers of the fibers.
From the viewpoint of gas permeability, the bottle body made of aluminum foil has the smallest gas permeability and the best barrier property. CPVC is consistent with PVC, and the VI type hydrogen storage bottle liners on the market at present are generally made of HDPE and more nylon. The material selected for aluminum is preferable from the viewpoint of sealing, but the thermal conductivity of the metal is greatly different from that of the hydrogen storage cylinder composite, and the influence of temperature change on the material during hydrogen gas charging/discharging needs to be considered.
Based on the situation, the invention provides a hydrogen storage bottle composite material, a preparation method thereof and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a hydrogen storage bottle composite material, a preparation method thereof and a preparation method thereof.
In order to achieve the above objects, the present invention provides a hydrogen storage bottle composite comprised of a CPVC resin and a PVDC resin; the hydrogen storage bottle composite material is used as a material of any layer of the inner container of the hydrogen storage bottle; the hydrogen storage bottle composite material is prepared by the following method: forming a bottle body structure by the CPVC resin through an injection molding method, then coating the PVDC resin on the inner surface or the outer surface of the bottle body structure formed by the CPVC resin, drying and curing to obtain the CPVC/CPVC composite material.
Preferably, the chlorine content of the CPVC resin is 65% or more.
In one embodiment, the CPVC resin is Norway CIN-0202, and the chlorine content is 66.0-67.0%.
The CPVC resin with high chlorine content is required to be used, so that on one hand, the Vicat softening temperature of the CPVC resin can be increased to be more than 100 ℃, and the heat stability is favorably improved; on the other hand, the subsequent drying and curing temperature can be ensured not to cause the softening of the CPVC resin, thereby causing the deformation of the bottle body.
Preferably, the PVDC resin is a PVDC resin emulsion;
in one embodiment, the PVDC resin emulsion is suwei a 586, usa.
Preferably, the PVDC resin is coated in an amount of 60 to 70g/m 2 。
Preferably, the thickness of the hydrogen storage cylinder composite is 3-5mm.
Preferably, the hydrogen storage bottle composite material further comprises a silane coupling agent, and the dosage of the silane coupling agent is 0.05-0.1 time of the weight part of the PVDC resin.
Preferably, the silane coupling agent is a chloro silane coupling agent, and comprises one of chloromethyltrimethylsilane, chloromethyldimethylchlorosilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane and 3-chloropropyltrimethoxysilane.
In one embodiment, the chlorosilane is chloromethyltrimethylsilane, CAS number 2344-80-1, product number SCA-C01H.
The invention also provides a preparation method of the hydrogen storage bottle composite material, which comprises the following steps:
(1) Mixing silane coupling agent and liquid PVDC resin at 150-200 rpm for 10-15 min for later use;
(2) Adding CPVC resin into a mould, injection molding at the temperature of 170-175 ℃, cooling to room temperature by air cooling, and demoulding;
(3) And (2) coating the liquid PVDC resin mixed in the step (1) on the inner surface of the CPVC resin, drying at 90-95 ℃ for 1-2 min, and curing the dried composite material at 35-40 ℃ for 3-4 d to obtain the CPVC resin.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention applies that PVDC resin is coated on the inner surface or the outer surface of the bottle body structure formed by CPVC resin, although the sealing performance does not reach aluminum material, the sealing performance is obviously better than nylon and HDPE; furthermore, the compatibility of the PVDC resin and the CPVC resin is improved by adding the silane coupling agent, so that the sealing property of the PVDC resin and the CPVC resin is greatly improved, and the sealing property of the PVDC resin is close to that of an aluminum material.
2. The raw materials of the invention are sufficient in China and proper in price, so that the large-scale production of the invention is not limited by too high cost; meanwhile, the preparation method is simple, the total production cost is low, and the industrial large-scale production is facilitated.
Detailed Description
Example 1
The preparation steps are as follows:
(1) Mixing chloromethyl trimethylsilane and liquid PVDC resin at 150rpm for 15min for later use; the using amount of the silane coupling agent is 0.05 times of the weight part of the PVDC resin;
(2) Adding 200g of CPVC resin into a mould, injection molding at the temperature of 170 ℃, cooling to room temperature by air cooling, and demoulding;
(3) Coating the mixed liquid PVDC resin in the step (1) on the inner surface of the CPVC resin, wherein the coating weight is 60g/m 2 And then drying at 90 ℃ for 2min, and curing the dried composite material at 35 ℃ for 4d to obtain the composite material.
The thickness of the obtained bottle body was measured to be 3mm.
Example 2
The preparation steps are as follows:
(1) Mixing chloromethyl trimethylsilane and liquid PVDC resin at 200rpm for 10min for later use; the dosage of the silane coupling agent is 0.1 time of the weight part of the PVDC resin;
(2) Adding 250g of CPVC resin into a mould, injection molding at 175 ℃, cooling by air cooling to room temperature, and demoulding;
(3) Coating the mixed liquid PVDC resin in the step (1) on the inner surface of the CPVC resin, wherein the coating amount is 65g/m 2 And then drying at 95 ℃ for 1min, and curing the dried composite material at 40 ℃ for 3d to obtain the composite material.
The thickness of the obtained bottle body was measured to be 3mm.
Example 3
The preparation steps are as follows:
(1) Mixing chloromethyl trimethylsilane and liquid PVDC resin at 200rpm for 15min for later use; the dosage of the silane coupling agent is 0.1 time of the weight part of the PVDC resin;
(2) Adding 300g of CPVC resin into a mould, injection molding at 175 ℃, cooling by air cooling to room temperature, and demoulding;
(3) Coating the liquid PVDC resin mixed in the step (1) on the inner surface of the CPVC resin, wherein the coating amount is 70g/m 2 And then drying at 95 ℃ for 2min, and curing the dried composite material at 40 ℃ for 4d to obtain the composite material.
The thickness of the obtained bottle body is 0.3mm through detection.
Comparative example 1
Unlike example 1, the procedure of example 1 was followed except that no silane coupling agent was used, and the preparation procedure was as follows:
(1) Stirring the liquid PVDC resin at 150rpm for 15min for later use;
(2) Adding 200g of CPVC resin into a mould, injection molding at the temperature of 170 ℃, cooling to room temperature by air cooling, and demoulding;
(3) Coating the liquid PVDC resin in the step (1) on the inner surface of the CPVC resin, wherein the coating amount is 60g/m 2 And then drying at 90 ℃ for 2min, and curing the dried composite material at 35 ℃ for 4d to obtain the composite material.
The thickness of the obtained bottle body was measured to be 3mm.
Comparative examples 2 to 6
Comparative examples 2 to 6 are prepared into bottles with the thickness of 3mm by respectively taking nylon 66, HDPE, CPVC, PVC and aluminum foil as materials; wherein the aluminum foil is used as the material to prepare a bottle body with the thickness of 0.4 mm.
Comparative examples 7 to 9
KH560, KH570 and KH580 are used as silane coupling agents, and the preparation method is the same as that of example 1, and the preparation steps are as follows:
(1) Mixing a silane coupling agent and liquid PVDC resin at 150rpm for 15min for later use; the dosage of the silane coupling agent is 0.05 times of the weight of the PVDC resin;
(2) Adding 200g of CPVC resin into a mould, injection molding at the temperature of 170 ℃, cooling to room temperature by air cooling, and demoulding;
(3) Coating the mixed liquid PVDC resin in the step (1) on the inner surface of the CPVC resin, wherein the coating weight is 60g/m 2 And then drying at 90 ℃ for 2min, and curing the dried composite material at 35 ℃ for 4d to obtain the composite material.
The thickness of the obtained bottle body was measured to be 3mm.
Example 4 Performance testing
The bottles prepared in example 1 and comparative example 1 were tested for sealability and tested for gas permeability with helium and oxygen gas having a kinetic diameter close to that of hydrogen gas, the aerodynamic diameter: helium (0.26 nm) < hydrogen (0.289 nm) < oxygen (0.346 nm). Gas transmission in cm 3 /(m 2 24 h.0.1 MPa). The test results are shown in Table 1.
TABLE 1 Performance test results
The foregoing description of specific exemplary embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A hydrogen storage bottle composite, wherein the hydrogen storage bottle composite is comprised of CPVC resin and PVDC resin; the hydrogen storage bottle composite material is used as a material of any layer of the inner container of the hydrogen storage bottle; the hydrogen storage bottle composite material is prepared by the following method: the CPVC resin is formed into a bottle body structure by an injection molding method, the PVDC resin is then applied to the interior or exterior surface of the bottle structure formed from the CPVC resin, drying and curing to obtain the product.
2. The hydrogen storage bottle composite of claim 1, wherein said CPVC resin has a chlorine content of 65% or more.
3. The hydrogen storage bottle composite of claim 1, wherein the PVDC resin is a liquid-type PVDC resin.
4. The hydrogen storage cylinder composite material according to claim 1, wherein the coating amount of the PVDC resin is 60 to 70g/m 2 。
5. The hydrogen storage cylinder composite of claim 1, wherein the thickness of the hydrogen storage cylinder composite is 0.3 to 0.5mm.
6. The hydrogen storage bottle composite according to claim 1, further comprising a silane coupling agent in an amount of 0.05 to 0.1 times the weight of the PVDC resin.
7. The hydrogen storage bottle composite as claimed in claim 6, wherein the silane coupling agent is a chloro silane coupling agent.
8. The hydrogen storage bottle composite material as claimed in claim 7, wherein the chloro-silane coupling agent comprises one of chloromethyltrimethylsilane, chloromethyldimethylchlorosilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, and 3-chloropropyltrimethoxysilane.
9. The hydrogen storage bottle composite of claim 8, the chloro-silane being chloromethyltrimethylsilane.
10. A method of making the hydrogen storage cylinder composite of claim 1, comprising the steps of:
(1) Mixing silane coupling agent and liquid PVDC resin at 150-200 rpm for 10-15 min for later use;
(2) Adding CPVC resin into a mould, injection molding at the temperature of 170-175 ℃, cooling to room temperature by air cooling, and demoulding;
(3) And (2) coating the liquid PVDC resin mixed in the step (1) on the inner surface of the CPVC resin, drying at 90-95 ℃ for 1-2 min, and curing the dried composite material at 35-40 ℃ for 3-4 d to obtain the CPVC resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211519158.0A CN115785508A (en) | 2022-11-30 | 2022-11-30 | Hydrogen storage bottle composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211519158.0A CN115785508A (en) | 2022-11-30 | 2022-11-30 | Hydrogen storage bottle composite material and preparation method thereof |
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| CN115785508A true CN115785508A (en) | 2023-03-14 |
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| CN202211519158.0A Pending CN115785508A (en) | 2022-11-30 | 2022-11-30 | Hydrogen storage bottle composite material and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5978241A (en) * | 1982-07-16 | 1984-05-07 | ノ−ドソン・コ−ポレ−シヨン | Plastic substrate and method and apparatus for coating substrate with high polymer |
| JPH08238667A (en) * | 1995-03-03 | 1996-09-17 | Toppan Printing Co Ltd | Vessel, manufacture thereof and preform |
| CN1176173A (en) * | 1996-09-03 | 1998-03-18 | 大赛璐化学工业株式会社 | Barrier composite films and method for producing the same |
| JP2001200159A (en) * | 1999-11-10 | 2001-07-24 | Shin Etsu Chem Co Ltd | Molded product of hydrogen storage composite and method for producing the same |
| CN103934942A (en) * | 2014-04-21 | 2014-07-23 | 淄博中南塑胶有限公司 | Production technology of PVC/PVDC (polyvinyl chloride/polyvinyl dichloride) composite sheet |
| CN113881150A (en) * | 2021-11-04 | 2022-01-04 | 江苏金材科技有限公司 | Hydrogen storage bottle material with high polymer material inner container and preparation method thereof |
| CN113881163A (en) * | 2021-10-31 | 2022-01-04 | 江苏金材科技有限公司 | Plastic for hydrogen storage pressure container and preparation method thereof |
-
2022
- 2022-11-30 CN CN202211519158.0A patent/CN115785508A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5978241A (en) * | 1982-07-16 | 1984-05-07 | ノ−ドソン・コ−ポレ−シヨン | Plastic substrate and method and apparatus for coating substrate with high polymer |
| JPH08238667A (en) * | 1995-03-03 | 1996-09-17 | Toppan Printing Co Ltd | Vessel, manufacture thereof and preform |
| CN1176173A (en) * | 1996-09-03 | 1998-03-18 | 大赛璐化学工业株式会社 | Barrier composite films and method for producing the same |
| JP2001200159A (en) * | 1999-11-10 | 2001-07-24 | Shin Etsu Chem Co Ltd | Molded product of hydrogen storage composite and method for producing the same |
| CN103934942A (en) * | 2014-04-21 | 2014-07-23 | 淄博中南塑胶有限公司 | Production technology of PVC/PVDC (polyvinyl chloride/polyvinyl dichloride) composite sheet |
| CN113881163A (en) * | 2021-10-31 | 2022-01-04 | 江苏金材科技有限公司 | Plastic for hydrogen storage pressure container and preparation method thereof |
| CN113881150A (en) * | 2021-11-04 | 2022-01-04 | 江苏金材科技有限公司 | Hydrogen storage bottle material with high polymer material inner container and preparation method thereof |
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