阅读说明：本技术 一种纤维全缠绕储氢瓶塑料内胆及其成型方法 (Fiber fully-wound hydrogen storage bottle plastic inner container and forming method thereof ) 是由 华林 刘兆义 王辉 陈一哲 付爽 于 2020-05-26 设计创作，主要内容包括：一种纤维全缠绕储氢瓶塑料内胆及其成型方法,涉及储氢设备材料领域。纤维全缠绕储氢瓶塑料内胆包括内层、中间层和外层；以质量百分比计,内层由80～90％的聚酰胺-6及10～20％的内层母料组成；内层母料由88～94％的聚酰胺-6及阻隔剂、抗静电剂、抗氧剂及分散剂组成；中间层由乙烯-乙烯醇共聚物制成；外层由80～90％聚酰胺-6及10～20％外层母料组成：外层母料由79～89.5％的聚酰胺-6、阻隔剂、抗静电剂、抗氧剂、分散剂、光稳定剂及偶联剂组成。本申请提供的纤维全缠绕储氢瓶塑料内胆及其成型方法具有防渗透性能好,稳定性、气密性和抗氧化性强的优点。(A fiber fully-wound hydrogen storage bottle plastic liner and a forming method thereof relate to the field of hydrogen storage equipment materials. The fiber fully-wound hydrogen storage bottle plastic inner container comprises an inner layer, a middle layer and an outer layer; the inner layer consists of 80-90% of polyamide-6 and 10-20% of inner layer master batch in percentage by mass; the inner layer master batch consists of 88-94% of polyamide-6, a blocking agent, an antistatic agent, an antioxidant and a dispersing agent; the middle layer is made of ethylene-vinyl alcohol copolymer; the outer layer consists of 80-90% of polyamide-6 and 10-20% of outer layer master batch: the outer layer master batch consists of 79-89.5% of polyamide-6, a blocking agent, an antistatic agent, an antioxidant, a dispersing agent, a light stabilizer and a coupling agent. The fiber fully-wound hydrogen storage bottle plastic liner and the forming method thereof have the advantages of good anti-permeability performance, high stability, high air tightness and high oxidation resistance.)

1. A fiber fully-wound hydrogen storage bottle plastic liner is characterized by comprising an inner layer, a middle layer and an outer layer which are sequentially arranged from inside to outside;

wherein the inner layer consists of 80-90% of polyamide-6 and 10-20% of inner layer master batch in percentage by mass; the inner layer master batch is prepared from the following raw materials in percentage by mass: 88-94% of polyamide-6, 2.5-5% of a blocking agent, 1.5-3% of an antistatic agent, 0.5-1% of an antioxidant and 1.5-3% of a dispersant;

the intermediate layer is made of ethylene-vinyl alcohol copolymer;

the outer layer consists of 80-90% of polyamide-6 and 10-20% of outer layer master batch in percentage by mass; the outer layer master batch is prepared from the following raw materials in percentage by mass: 79-89.5% of polyamide-6, 2.5-5% of blocking agent, 1.5-3% of antistatic agent, 0.5-1% of antioxidant, 1.5-3% of dispersing agent, 1.5-3% of light stabilizer and 3-6% of coupling agent.

2. The plastic liner of a fiber-wrapped hydrogen storage bottle according to claim 1, wherein the blocking agent is modified hydrotalcite.

3. The plastic liner of fiber-wrapped hydrogen storage bottle according to claim 1, wherein the antistatic agent is a compound of an amine adduct of ethylene oxide.

4. The plastic liner for fiber-wrapped hydrogen storage bottles of claim 1, wherein said antioxidant is a mixture of pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] and phosphite.

5. The plastic liner of a fiber-wrapped hydrogen storage bottle according to claim 1, wherein the dispersant is a polyamide wax.

6. The plastic liner for fiber-wrapped hydrogen storage bottles of claim 1, wherein the light stabilizer is N, N-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide.

7. The plastic liner of a fiber-wrapped hydrogen storage bottle according to claim 1, wherein the coupling agent is a maleic anhydride-based polymer coupling agent.

8. The method for forming a plastic liner of a fiber-wrapped hydrogen storage bottle according to claim 1, comprising the steps of:

respectively adding the raw materials of the inner layer master batch and the raw materials of the outer layer master batch into an internal mixer for mixing according to the mass percentage, and conveying the mixture to a double-screw granulation device to respectively prepare the inner layer master batch and the outer layer master batch;

according to the mass percentage, the inner layer master batch, the corresponding polyamide-6, the ethylene-vinyl alcohol copolymer, the outer layer master batch and the corresponding polyamide-6 are respectively added into a mixer for mixing, and an inner layer hopper, a middle layer hopper and an outer layer hopper corresponding to the structure of a co-extruder unit are fused and plasticized in a machine head, then are compounded and extruded to form a multi-layer concentric composite parison, and then are blown to form a hollow plastic inner container structure.

9. The method for forming the plastic liner of the fully-wound fiber hydrogen storage bottle according to claim 8, wherein the mixing time in the mixer is 10-20 min.

10. The method for forming the plastic liner of the fully fiber-wrapped hydrogen storage bottle according to claim 8, wherein when the hollow plastic liner structure is formed by blowing, the blowing ratio is 2.5-6, the layer ratio is 3: 5: 5.

Technical Field

The application relates to the field of hydrogen storage equipment materials, in particular to a fiber fully-wound hydrogen storage bottle plastic inner container and a forming method thereof.

Background

The automobile industry is facing to energy structure optimization to meet the challenge of climate change, fuel cell automobiles as one of new energy vehicles undertake important missions, and safe, reliable and practical vehicle-mounted hydrogen storage technology is very important for marketization of hydrogen fuel cell automobiles.

The aluminum alloy used as the inner container material of the traditional hydrogen storage bottle cannot meet the technical development requirements of long endurance mileage and the like due to the defects of low hydrogen storage density, hydrogen brittleness and the like. Therefore, PA6 material with higher hydrogen storage density and lower cost is applied. Compared with aluminum alloy materials, the PA6 material has good comprehensive strength, stronger corrosion resistance and lower cost. However, the single layer PA6 has poor permeation resistance and cannot have high hydrogen gas barrier property, and needs to be subjected to composite modification.

Disclosure of Invention

The application aims to provide a fiber fully-wound hydrogen storage bottle plastic liner and a forming method thereof, and the liner has the advantages of good anti-permeability performance, and strong stability, air tightness and oxidation resistance.

The embodiment of the application is realized as follows:

the embodiment of the application provides a fiber fully-wound hydrogen storage bottle plastic liner, which comprises an inner layer, a middle layer and an outer layer which are sequentially arranged from inside to outside;

wherein the inner layer consists of 80-90% of polyamide-6 and 10-20% of inner layer master batch in percentage by mass; the inner layer master batch is prepared from the following raw materials in percentage by mass: 88-94% of polyamide-6, 2.5-5% of a blocking agent, 1.5-3% of an antistatic agent, 0.5-1% of an antioxidant and 1.5-3% of a dispersant;

the middle layer is made of ethylene-vinyl alcohol copolymer;

the outer layer consists of 80-90% of polyamide-6 and 10-20% of outer layer master batch in percentage by mass; the outer layer master batch is prepared from the following raw materials in percentage by mass: 79-89.5% of polyamide-6, 2.5-5% of blocking agent, 1.5-3% of antistatic agent, 0.5-1% of antioxidant, 1.5-3% of dispersing agent, 1.5-3% of light stabilizer and 3-6% of coupling agent.

In some alternative embodiments, the barrier agent is a modified hydrotalcite.

In some alternative embodiments, the antistatic agent is a complex of an oxirane amine adduct.

In some alternative embodiments, the antioxidant is a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and a phosphite.

In some alternative embodiments, the dispersant is a polyamide wax.

In some alternative embodiments, the light stabilizer is N, N-bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide.

In some alternative embodiments, the coupling agent is a maleic anhydride-based polymeric coupling agent.

The embodiment of the application also provides a forming method of the fiber fully-wound hydrogen storage bottle plastic liner, which comprises the following steps:

respectively adding the raw materials of the inner layer master batch and the raw materials of the outer layer master batch into an internal mixer for mixing according to the mass percentage, and conveying the mixture to a double-screw granulation device to respectively prepare the inner layer master batch and the outer layer master batch;

according to the mass percentage, the inner layer master batch, the corresponding polyamide-6, the ethylene-vinyl alcohol copolymer, the outer layer master batch and the corresponding polyamide-6 are respectively added into a mixer for mixing, and an inner layer hopper, a middle layer hopper and an outer layer hopper corresponding to the structure of a co-extruder unit are fused and plasticized in a machine head, then are compounded and extruded to form a multi-layer concentric composite parison, and then are blown to form a hollow plastic inner container structure.

In some optional embodiments, the mixing time in the mixer is 10 to 20 min.

In some optional embodiments, when the hollow plastic liner structure is formed by blowing, the blowing ratio is 2.5-6, the layer ratio is 3: 5: 5.

the beneficial effect of this application is: the plastic liner of the fiber fully-wound hydrogen storage bottle provided by the embodiment comprises an inner layer, a middle layer and an outer layer which are sequentially arranged from inside to outside; the inner layer consists of 80-90% of polyamide-6 and 10-20% of inner layer master batch in percentage by mass; the inner layer master batch is prepared from the following raw materials in percentage by mass: 88-94% of polyamide-6, 2.5-5% of a blocking agent, 1.5-3% of an antistatic agent, 0.5-1% of an antioxidant and 1.5-3% of a dispersant; the middle layer is made of ethylene-vinyl alcohol copolymer; the outer layer consists of 80-90% of polyamide-6 and 10-20% of outer layer master batch in percentage by mass; the outer layer master batch is prepared from the following raw materials in percentage by mass: 79-89.5% of polyamide-6, 2.5-5% of blocking agent, 1.5-3% of antistatic agent, 0.5-1% of antioxidant, 1.5-3% of dispersing agent, 1.5-3% of light stabilizer and 3-6% of coupling agent. The polyamide-6 is modified and then respectively used as an inner layer and an outer layer to prepare the plastic liner of the hydrogen storage bottle, wherein the inner layer is mainly used for determining the dimensional stability of a product and has the functions of enhancing hydrogen barrier property, antistatic property and aging resistance; the middle layer adopts ethylene-vinyl alcohol copolymer to play a role in high permeation resistance of a multilayer co-extrusion structure, so that hydrogen can be prevented from permeating into the hydrogen storage bottle, and external gas and the like can be prevented from permeating into the hydrogen storage bottle; the outer layer plays the effect of reinforcing hydrogen barrier property, antistatic properties, ageing resistance, improves the light stability and the surface adhesion nature of goods simultaneously. The application also provides a forming method of the plastic inner container of the fiber fully-wound hydrogen storage bottle, and the method has the advantages of simple operation, convenience in use and suitability for large-scale preparation.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The embodiment of the application provides a fiber fully-wound hydrogen storage bottle plastic liner, which comprises an inner layer, a middle layer and an outer layer which are sequentially arranged from inside to outside; wherein the inner layer consists of 80-90% of polyamide-6 and 10-20% of inner layer master batch in percentage by mass; the inner layer master batch is prepared from the following raw materials in percentage by mass: 88-94% of polyamide-6, 2.5-5% of a blocking agent, 1.5-3% of an antistatic agent, 0.5-1% of an antioxidant and 1.5-3% of a dispersant; the middle layer is made of ethylene-vinyl alcohol copolymer; the outer layer consists of 80-90% of polyamide-6 and 10-20% of outer layer master batch in percentage by mass; the outer layer master batch is prepared from the following raw materials in percentage by mass: 79-89.5% of polyamide-6, 2.5-5% of blocking agent, 1.5-3% of antistatic agent, 0.5-1% of antioxidant, 1.5-3% of dispersing agent, 1.5-3% of light stabilizer and 3-6% of coupling agent. Optionally, the blocking agent is modified hydrotalcite. Optionally, the antistatic agent is a compound of an oxirane amine adduct. Optionally, the antioxidant is a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and a phosphite ester. Optionally, the dispersant is a polyamide wax. Optionally, the light stabilizer is N, N-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide. Optionally, the coupling agent is a maleic anhydride polymer coupling agent.

The embodiment of the application also provides a forming method of the fiber fully-wound hydrogen storage bottle plastic liner, which comprises the following steps:

respectively adding the raw materials of the inner layer master batch and the raw materials of the outer layer master batch into an internal mixer for mixing according to the mass percentage, and conveying the mixture to a double-screw granulation device to respectively prepare the inner layer master batch and the outer layer master batch;

according to the mass percentage, the inner layer master batch, the corresponding polyamide-6, the ethylene-vinyl alcohol copolymer, the outer layer master batch and the corresponding polyamide-6 are respectively added into a mixer for mixing, and an inner layer hopper, a middle layer hopper and an outer layer hopper corresponding to the structure of a co-extruder unit are fused and plasticized in a machine head, then are compounded and extruded to form a multi-layer concentric composite parison, and then are blown to form a hollow plastic inner container structure. Optionally, the mixing time in the mixer is 10-20 min. Optionally, when the inflation forms hollow plastics inner bag structure, the inflation ratio is 2.5 ~ 6, and the layer ratio is 3: 5: 5.

the plastic liner of the fully-wound fiber hydrogen storage bottle provided by the embodiment is composed of an inner layer, an intermediate layer and an outer layer which are sequentially arranged from inside to outside, the inner layer is prepared by mixing inner layer master batch prepared from a blocking agent, an antistatic agent, an antioxidant and a dispersing agent with polyamide-6, the size stability of the product can be determined, and the effects of enhancing hydrogen blocking property, antistatic property and aging resistance are simultaneously achieved, the intermediate layer adopts an ethylene-vinyl alcohol copolymer to form a multi-layer co-extrusion structure with high permeation resistance, so that hydrogen can be prevented from permeating out of the hydrogen storage bottle, and external gas and the like can be prevented from permeating into the hydrogen storage bottle; the outer layer is prepared by mixing the outer layer master batch prepared from polyamide-6, a blocking agent, an antistatic agent, an antioxidant, a dispersing agent, a light stabilizer and a coupling agent with the polyamide-6, so that the effects of enhancing hydrogen blocking property, antistatic property and aging resistance can be achieved, and meanwhile, the light stability and surface adhesion of the product are improved; the polyamide wax is selected as a dispersing agent in the system, so that various auxiliary agents in the composite material system can be uniformly dispersed in the polyamide-6 resin, and the composite material can obtain balanced performance; the modified polyamide-6 material has excellent size stability, high air tightness, high antistatic property and high antioxidant performance after being formed, and the polyamide-6 composite material has good processing performance and low material cost, is used for producing the plastic liner of the hydrogen storage bottle, and has good market application prospect.

The forming method of the fiber fully-wound hydrogen storage bottle plastic liner provided by this embodiment is to add the raw materials of the inner layer master batch and the outer layer master batch into the internal mixer respectively, mix and granulate to obtain the inner layer master batch and the outer layer master batch, add the raw materials into the mixer respectively to mix, and compound, extrude and form a multilayer concentric composite parison after the inner layer hopper, the middle layer hopper and the outer layer hopper corresponding to the co-extruder unit structure are melted and plasticized in the machine head, and then form a hollow plastic liner structure by blowing, so that various additives in the composite material system are uniformly dispersed in the polyamide-6 resin to form the hydrogen storage bottle plastic liner with excellent dimensional stability, high air tightness, high antistatic property and high oxidation resistance.

The plastic liner of the fiber-wrapped hydrogen storage cylinder and the method for forming the same according to the present invention will be described in further detail with reference to the following examples.