阅读说明：本技术 用于制造压缩气体容器的方法 (Method for producing a compressed gas container ) 是由 D·兹格拉 P·迪金克 F·里特辛格 M·哈特尔 于 2019-08-26 设计创作，主要内容包括：本发明的主题是一种用于制造压缩气体容器的方法、所述压缩气体容器尤其是用于运输和储存液态气体或天然气的压缩气体容器。(The subject of the invention is a method for producing a compressed gas container, in particular for transporting and storing liquid gas or natural gas.)

1. A method for manufacturing a compressed gas container having a storage volume for a gas under pressure and an envelope enclosing the storage volume, wherein the envelope comprises a liner in contact with the storage volume and at least partially at least one second layer applied to the liner, wherein the method comprises the method steps of:

a) providing:

i) the inner lining is arranged on the outer side of the inner lining,

ii) a curable epoxy resin matrix, and

iii) a reinforcing fiber, wherein the reinforcing fiber is a fiber,

b) loading the curable epoxy resin matrix onto reinforcing fibers, wherein the curable epoxy resin matrix has a temperature in the range of 15 to 50 ℃,

c) winding, laying or applying the reinforcing fibers onto a liner for forming the second layer,

d) curing the second layer at a temperature in the range of 70 to 140 ℃;

characterized in that the curable epoxy resin matrix has a viscosity in the range of 200 to 1000mPa · s at a temperature in the range of 40 to 50 ℃ for a period of at least 48 hours.

2. The process according to claim 1, characterized in that the curable epoxy resin matrix has a temperature in the range of 20 to 50 ℃, preferably in the range of 25 to 50 ℃, preferably in the range of 30 to 50 ℃, particularly preferably in the range of 40 to 50 ℃ in process step b).

3. The method according to at least one of the preceding claims, characterized in that the epoxy resin matrix is loaded onto the reinforcing fibers such that the second layer has a thickness of between 50: 50 to 80: a weight ratio of reinforcing fibers to epoxy resin matrix in the range of 20.

4. The method according to at least one of the preceding claims, characterized in that the epoxy resin matrix has a viscosity of 300 to 900 mPa-s, especially 400 to 800 mPa-s, especially 400 to 700 mPa-s at 40 ℃ at a temperature in the range of 40 to 50 ℃.

5. The method according to at least one of the preceding claims, characterized in that the second layer is cured at a temperature in the range of 70 to 120 ℃.

6. The method of at least one of the preceding claims, wherein the epoxy resin matrix comprises:

i) at least one epoxy resin having at least one epoxy group,

ii) at least one reactive diluent of the group of glycidyl ethers,

iii) at least one curing agent, especially a liquid curing agent, especially a cyanamide-containing curing agent.

7. The method of at least one of the preceding claims, wherein the epoxy resin matrix before curing has an average epoxide equivalent weight value in the range of 100 to 250 g/eq.

8. The method according to claim 6, characterized in that the epoxy resin is selected from the group of difunctional epoxy resins and/or the epoxy resin has an average epoxide equivalent value of 150 to 200 g/eq.

9. The process according to claim 7, characterized in that the reactive diluent is selected from the group of difunctional glycidyl ethers and/or the glycidyl ethers have an average epoxide equivalent value of 100 to 200 g/eq.

10. Method according to at least one of the preceding claims, characterized in that the reinforcement fibres are selected from the group of carbon fibres, glass fibres, aramid fibres and basalt fibres.

11. Method according to at least one of the preceding claims, characterized in that the reinforcing fibres are provided in the form of filaments, threads, yarns, woven fabrics, knits or knits.

12. The method of at least one of the preceding claims, wherein the liner is a thermoplastic liner or a metal liner.

Technical Field

The subject of the invention is a method for producing compressed gas containers, in particular for transporting and storing liquid gas or natural gas, and in particular for producing compressed gas containers of type II or III or IV.

Background

Pressure vessels for transporting liquid, compressed gas, for example compressed natural gas, are assigned to different classes or are classified into different types with regard to their authorization as transport vessels. Common to these types is that the compressed gas container is cylindrical and has one or two or more or fewer dome-shaped ends.

Type I compressed gas containers comprise a hollow body made entirely of metal, typically aluminum or steel. This type I is inexpensive, but has a higher weight compared to other types of compressed gas containers due to its material and structural form. Such type I compressed gas containers are widely used and are used, in particular, for marine transport.

A type II compressed gas container comprises a thin cylindrical intermediate section formed of metal with domed ends, the so-called end dome, which is likewise made of metal. The cylindrical intermediate section between the end domes is reinforced with a composite sleeve, a so-called composite material. The composite wrap is typically made of glass or carbon filaments impregnated with a polymer matrix. The end dome is not reinforced. In type II pressure vessels, the metal liner carries about 50% of the stress generated by the internal pressure of the gas being conveyed. The remaining stress is received by the composite material.

Type III compressed gas containers comprise a hollow body made entirely of metal, usually aluminum. The hollow body, also called the lining, is, unlike type II, completely reinforced and is therefore also reinforced on the end dome with the composite material. The stresses in the type III vessel are almost completely transferred to the composite sleeve. The liner itself carries only a small portion of the load.

Type III compressed gas containers are significantly lighter than type I or type II compressed gas containers, but are much more expensive to purchase due to their structural form.

A type IV compressed gas container, such as a type III compressed gas container, includes a liner that is completely coated with a composite material. However, in contrast to the type III compressed gas containers, the inner liner is made of a thermoplastic material, for example polyethylene or polyamide, which is very gas-tight in terms of its properties. In type IV pressure vessels, the composite material is almost completely loaded with the stresses generated by the internal pressure of the conveyed gas. Type IV compressed gas containers are by far the lightest, but because of their structural form, are also the most expensive of the compressed gas containers described herein.

In addition to the type I to type IV compressed gas containers, which are permitted by the governing authority under these names, there are additional V-shaped compressed gas containers. Such compressed gas containers include a novel container structure made of composite materials having different compositions in sub-layers.

Compressed gas containers of type I, II, III or IV have been widely used and are the subject of the patent literature. Reference is made here, by way of example, to the following documents: DE 10156377A 1, DE 102015016699A 1, EP 2857428A 1, WO 2013/083172A 1. Furthermore, international patent applications WO 2013/083152 a1 and WO 2016/06639 a1 describe methods for manufacturing V-shaped compressed gas containers.

At present, it is increasingly desirable to manufacture compressed gas containers of types III and IV with particularly large volumes, and to enable the manufacture of such compressed gas containers in a continuous process. These requirements place particular demands on the manufacturing technology of the compressed gas container. In particular, more time is required for applying the composite layer to the liner. Furthermore, a greater layer thickness of the composite material is required in order to absorb the pressure generated by the liquid gas on the container. Both the increased production time and the required layer thickness place high demands on the polymer matrix to be used. Furthermore, there is thus also a need to provide a suitable production method.

Disclosure of Invention

The object of the present invention is therefore to provide a method for producing compressed gas containers, which can be used widely and which can be used to produce compressed gas containers that meet the high requirements with regard to mechanical safety. Furthermore, a method should be provided which is suitable for the production of large compressed gas containers, in particular of types II, III and IV.

According to the invention, these objects are solved by a method according to claim 1. The subject of the invention is therefore a method for producing a compressed gas container having a storage volume for a gas under pressure and an envelope enclosing the storage volume, wherein the envelope comprises a liner in contact with the storage volume and at least partially at least one second layer applied to the liner, comprising the method steps of:

a) providing:

i) the inner lining is arranged on the outer side of the inner lining,

ii) a curable epoxy resin matrix, and

iii) a reinforcing fiber, wherein the reinforcing fiber is a fiber,

b) applying a curable epoxy resin matrix to the reinforcing fibers, wherein the curable epoxy resin matrix has a temperature in the range of 15 to 50 ℃,

c) winding, laying or applying reinforcing fibres onto the liner, for forming a second layer,

d) curing the second layer at a temperature in the range of 70 to 140 ℃;

wherein the curable epoxy resin matrix has a viscosity of 200 to 1000mPa · s at a temperature of 40 to 50 ℃ over a period of at least 48 hours.

Preferred is a process for manufacturing a compressed gas cylinder, in which process a curable epoxy resin matrix has a viscosity in the range of 300 to 1000 mPa-s, in particular in the range of 400 to 1000 mPa-s, further preferred in the range of 300 to 900 mPa-s, further preferred in the range of 400 to 900 mPa-s, at a temperature in the range of 40 to 50 ℃ over a period of at least 48 hours.

The compressed gas container according to the invention is provided in particular for storing a gas under pressure. Here, gas is understood to be a material which is gaseous under normal conditions, in particular at a normal temperature of 0 ℃ and a normal pressure of 1.0 bar. In the compressed gas container itself, the gas can also be present in the liquid state, for example as a result of a high pressure or a low temperature.

The gas is especially hydrogen, natural gas or liquefied gas, especially propane, propylene, butane, butene, isobutane or isobutene or mixtures thereof. Particularly preferably, the gas is hydrogen or natural gas.

The storage volume of the compressed gas container produced according to the invention is in particular from 30 to 9000 litres, preferably from 30 to 900 litres and more preferably from 30 to 400 litres.

The layer thickness of the cured second layer is preferably from 8 to 100mm, in particular from 8 to 80mm, and in particular from 8 to 70 mm.

In particular, the subject of the invention is a method for continuously producing compressed gas cylinders each having a storage volume for a gas under pressure and an envelope surrounding the storage volume, wherein the envelope comprises a liner in contact with the storage volume and at least partially at least one second layer applied to the liner, wherein the method comprises the above-mentioned method steps a) to d) and the curable epoxy resin matrix has a viscosity in the range of 200 to 1000mPa · s at a temperature in the range of 40 to 50 ℃ for a period of at least 48 hours.

Preference is given here to a continuous process which, in addition to process steps a) to d), comprises additional process steps. In this additional method step, the curable epoxy resin matrix is preferably refilled, in particular continuously refilled, in an amount corresponding to the amount extracted during the application of the reinforcing fibers.

In the sense of the present invention, the term "curable epoxy resin" includes, in particular, the use, as epoxy resin, of an epoxy resin which is thermally curable, that is to say polymerizable, crosslinkable and/or crosslinkable transversely on account of its functional groups, i.e. epoxy groups, and polymerizable, crosslinkable and/or crosslinkable transversely, in particular by heat. In this case, polymerization, crosslinking and/or transverse crosslinking occur as a result of polyaddition initiated by the curing agent.

According to the invention, the curable epoxy resin matrix comprises at least one epoxy resin. Preferably, the epoxy resin is a polyether having at least one, preferably at least two epoxy groups. In a further preferred embodiment, the curable epoxy resin matrix comprises a curable epoxy resin and additionally a curing agent. Preference is given to using bisphenol-based epoxy resins, in particular bisphenol A diglycidyl ether or bisphenol F diglycidyl ether, novolak epoxy resins, in particular epoxy phenol novolak or aliphatic epoxy resins. As the curing agent, a cyanamide-containing curing agent is particularly used.

Particularly good results are obtained according to the invention by using bisphenol a diglycidyl ether or bisphenol F diglycidyl ether as epoxy resin and/or by using cyanamide as curing agent.

The epoxy equivalent (EEW, epoxy equivalent, hereinafter also referred to as equivalent) of the epoxy resin or the epoxy component according to the present invention is determined as a material property of each epoxy resin, and represents having 1 equivalent [ val ]]Of the epoxy functional group of [ g ]]Is the amount of epoxy resin in units. It is prepared by mixing the components in the amount of [ g/mol ]]Molar mass in units divided by [ Val/mol ]]Calculated as the functionality f of the unit. EEW is expressed as [ g/eq ]]Or [ g/Val]Average value in units

EEW[g/val]＝M[g/mol]/f[val/mol]

When using different reactive components for the formulation of the resin, a mixture of i epoxy components or an impregnating resin comprising i epoxy components: (EEW_{Mixture of}[g/Val]) The equivalent weight of (c) is calculated as follows:

EEW_{mixture of}[g/val]＝m_ges/(∑m_i/EEW_i)

m_ges＝∑m_iWherein, in the step (A),

m_imass of the individual components of the mixture

EEW_iOf component iEpoxy equivalent.

Viscosity describes the viscosity of the liquid and is measured by means of an antopa MCR302 with CTD 450 viscometer. Here, the curable epoxy resin matrix is subjected to an isothermal viscosity measurement, wherein the temperature of the curable epoxy resin matrix in the impregnation bath is selected as the measurement temperature and thus is in the range between 40 ℃ and 50 ℃. The respective measuring plate of the rheometer is heated to a determined measuring temperature and a curable epoxy matrix sample is applied when this temperature is reached. The viscosity of the curable epoxy resin matrix was measured at temperatures of 40 ℃ and 50 ℃ respectively, with a measurement gap of 0.052mm and a rotational shear rate of 51/s, until a viscosity of 1000 mPa-s was reached. The viscosity of the curable epoxy resin matrix at which the viscosity reaches 1000mPa · s is used as a measurement limit, and the time at which the measurement limit is reached is a comparison between the curable epoxy resin matrix belonging to the method according to the invention and the conventional ammonia-based and anhydride-based epoxy resin matrix of the method for manufacturing compressed gas cylinders.

An important point in the sense of the method according to the invention for producing compressed gas containers with the aid of a curable epoxy resin matrix, which brings about advantages in particular in the case of compressed gas cylinders having a large volume, is that, due to its properties over a period of at least 48 hours, the curable epoxy resin matrix is liquid and has a viscosity in the range from 200 to 1000mPa · s. These compressed gas cylinders may require more processing time, wherein the curable matrix causes a constant wetting of the reinforcing fibers by maintaining a constant viscosity over a long period of time.

The subject of the invention is therefore also a method for producing a compressed gas container, in particular a continuous method for producing a compressed gas container, having a storage volume for a gas under pressure and an envelope enclosing the storage volume, wherein the envelope comprises a liner which is in contact with the storage volume and at least partially comprises at least one second layer applied to the liner, the method comprising method steps a) to d),

wherein the curable epoxy resin matrix has a viscosity in the range of 200 to 1000mPa · s over a period of at least 48 hours at a temperature in the range of 40 to 50 ℃ and a deviation in viscosity of at most +/-15%, in particular at most +/-10%, in particular at most +/-8% over a period of at least 48 hours at a temperature in the range of 40 to 50 ℃.

Furthermore, due to the long time delay, continuous production can be achieved. Thus, the first winding with the manufactured epoxy resin matrix can be performed for at least 48 hours. Because the epoxy matrix is continuously consumed during the winding process due to the impregnation of the reinforcing fibers, the curable epoxy matrix must be refilled for a continuous process. By refilling with fresh curable epoxy resin matrix, the old matrix in the impregnation bath is diluted and the time delay of the matrix is thereby additionally extended, i.e. more than 48 hours. With the epoxy resin matrices which are currently generally used and contain curing agents from the group of amines or anhydrides, refilling or refilling is only possible to a limited extent. The winding process using this epoxy matrix must be stopped after 4 to 8 hours in order to be able to clean the equipment completely.

The subject of the invention is therefore also a continuous method for producing a compressed gas container having a storage volume for a gas under pressure and an envelope enclosing the storage volume, respectively, wherein the envelope comprises a liner in contact with the storage volume and at least partially at least one second layer applied to the liner, the method comprising the following method steps:

a) providing:

i) the inner lining is arranged on the outer side of the inner lining,

ii) a curable epoxy resin matrix, and

iii) a reinforcing fiber, wherein the reinforcing fiber is a fiber,

b) applying a curable epoxy resin matrix onto the reinforcing fibers, wherein the curable epoxy resin matrix has a temperature in the range of 15 to 50 ℃,

c) winding, laying or applying the reinforcing fibers onto the liner to form a second layer,

d) the curable epoxy resin matrix is refilled, in particular continuously refilled, in an amount corresponding to the amount extracted during the application of the reinforcing fibers,

e) curing the second layer at a temperature in the range of 70 to 140 ℃;

wherein the curable epoxy resin matrix has a viscosity in the range of 200 to 1000mPa · s at a temperature of 40 to 50 ℃ over a period of at least 48 hours.

Preference is given to a continuous process in which process step d) is carried out in such a way that the refill amount is from 2 to 8kg of epoxy resin matrix per hour, in particular from 2 to 6kg of epoxy resin matrix per hour.

By tempering the impregnation bath and thus the curable epoxy resin matrix to a temperature between 40 and 50 ℃, the matrix is not affected by the external temperature prevailing in the production room. Thus, always maintaining the same temperature of the matrix results in maintaining a constant, temperature controlled, immersion viscosity. Due to the constant viscosity and thus constant impregnation, a constant mass can be obtained when manufacturing a rolled compressed gas container.

Furthermore, the long time delay of the curable epoxy resin matrix also provides the possibility of manufacturing 1K batches (1 component batches) within one or more production days. Thus, for a determined production period, a larger amount of curable epoxy resin matrix can be pre-mixed, stored at room temperature and removed when needed. Due to the large batch production, the quality is likewise improved compared with several freshly mixed matrices, since the same mixture is always used.

Due to the high time delay, the possibility of continuous production and the production of large quantities of curable epoxy resin matrix as batches for production, a reduction of wasted curable epoxy resin matrix can thereby be achieved. For this purpose, cleaning of the dip tank can be considered, wherein a cleaning agent, for example acetone, must also be consumed and removed in addition to the curable epoxy resin residues in each cleaning process. If all aspects are considered, less waste can be generated, more cleaning and disposal costs are saved, and a more environmentally friendly product is produced.

According to the invention, the method is carried out such that the reinforcing fibers are loaded with a curable epoxy resin matrix at a temperature in the range of 15 to 50 ℃. Preferably, the process can be carried out such that the curable epoxy resin matrix in process step b) has a temperature in the range from 20 to 50 ℃, preferably in the range from 25 to 50 ℃, preferably in the range from 30 to 50 ℃, particularly preferably in the range from 40 to 50 ℃.

The impregnation viscosity of the substrate in the impregnation bath is thus set by setting the temperature of the curable epoxy resin substrate up to a temperature of 50 ℃. The impregnation viscosity can be set here to 200 to 1000 mPas, in particular 300 to 900 mPas. Furthermore, the preferred temperature of the epoxy resin matrix in the range of 40 to 50 ℃ is higher than the ambient temperature in the production plant, so that the temperature or viscosity of the curable epoxy resin matrix remains unaffected and thus a constant loading of the reinforcing fibers of a quality can be achieved by maintaining a constant impregnation viscosity over a longer production period.

Thus, for the method according to the invention for producing a compressed gas container, an epoxy resin matrix is required which can be easily applied to the reinforcing fibers by impregnation due to the filament winding method. A relevant parameter for the optimum loading of the epoxy resin matrix on the reinforcing fibers is the impregnation viscosity. Here, the impregnation viscosity must be set such that the weight ratio of reinforcing fibers to epoxy resin matrix is in the range of 50: 50 to 80: 20, or more. As is known to the user, this range of weight ratios is advantageous because with a low loading of the epoxy resin matrix a high weight proportion of the reinforcing fibers is produced and faulty bonding can occur due to the controlled maximum packing density of the reinforcing fibers on the process side. Too high a loading of the epoxy matrix may reduce the packing density of the reinforcing fibers. In both cases this leads to a reduction in the mechanical properties of the cured composite component, such as the modulus of elasticity or the tensile strength.

Thus, according to a further concept, the subject of the invention is also a method in which the reinforcing fibres are loaded with a curable epoxy resin matrix so that the second layer has a thickness of between 50: 50 to 80: 20, preferably in the range of 60: 40 to 80: a weight ratio of reinforcing fibers to epoxy resin matrix in the range of 20.

In order to ensure that the reinforcing fibers are optimally loaded with the epoxy resin matrix for the method according to the invention and that the second layer therefore also has a weight ratio of reinforcing fibers to epoxy resin matrix in the range from 50 to 80 to 20, it is necessary that the epoxy resin matrix developed for the method according to the invention has an average EEW value in the range from 100 to 250g/eq before curing, so that the epoxy resin matrix has a lower molecular weight and is therefore also present with a low viscosity. In addition to these properties which are important for the loading of the epoxy resin matrix, it also appears that the curable epoxy resin matrix has an impregnation viscosity of 300 to 900mPa · s, in particular 400 to 800mPa · s, in particular 400 to 700mPa · s, at 40 to 50 ℃, since the epoxy resin matrix is sufficiently low-viscous at the temperatures used for impregnating the reinforcing fibers and the temperatures are not influenced by the external temperatures prevailing in the production chamber at 40 to 50 ℃. It is therefore possible to carry out an optimized impregnation of the reinforcing fibers with the epoxy resin matrix used according to the method according to the invention, which impregnation leads to high mechanical properties of the cured compressed gas container.

According to the invention, the method is carried out such that the epoxy resin matrix has a viscosity of 200 to 1000 mPas at a temperature in the range of 40 to 50 ℃. It is preferred here that the epoxy resin matrix has a viscosity of 300 to 900mPa · s, in particular 400 to 800mPa · s, in particular 400 to 700mPa · s, at a temperature in the range from 40 to 50 ℃.

The curing of the second layer may be carried out at a temperature in the range of 70 to 110 ℃. The subject of the invention is therefore also a process in which the curing of the second layer is carried out at a constant temperature in the range from 70 to 110 ℃.

According to the invention, the process can advantageously be carried out when the curable epoxy resin matrix comprises the following components i) to iii), i.e. components

i) At least one epoxy resin having at least one epoxy group,

ii) at least one reactive diluent from the group of glycidyl ethers,

iii) at least one curing agent, in particular a liquid curing agent, in particular from the group of cyanamide-containing curing agents.

The curable epoxy resin matrix is in particular configured such that, in addition to providing the properties for a fiber-reinforced compressed gas container, the requirements of the method according to the invention for producing a compressed gas container are also met. Preference is given here to difunctional epoxy resins and/or epoxy resins having an average EEW value of from 150 to 200 g/eq. The cross-linking properties here enhance the mechanical properties of the compressed gas container by the bifunctionality of the epoxy resin, but at the same time are low-viscosity for optimum loading of the reinforcing fibers.

The same applies to the reactive diluent which additionally dilutes the epoxy resin matrix further. Here, too, the difunctional glycidyl ethers are selected in order to meet the performance characteristics of the compressed gas containers.

Liquid cyanamide-containing curing agents belong to the group of latent liquid curing agents and enable long processing times of the resins used in the process according to the invention in curable epoxy resin matrices.

The curing characteristics of the formulations according to the invention can be modified by the addition of other commercially available additives, such as those known to the person skilled in the art for the treatment and curing of epoxy resin matrices in this process.

Additives for improving the processability of the uncured epoxy resin composition or for adapting the thermomechanical properties of the thermoset product produced therefrom to the required characteristics include, for example, fillers, rheological additives such as thixotropic or dispersing additives, defoamers, dyes, pigments, toughness modifiers, impact modifiers or fire-retardant additives.

With regard to the epoxy resins to be used, all commercial products are conceivable, which generally have more than one 1,2 epoxy group (ethylene oxide) and can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic here. In addition, the epoxy resin may have a substituent such as a halogen, a phosphorus group, and a hydroxyl group. Particularly preferred are epoxy resins based on glycidyl polyethers of 2,2 bis (4 hydroxyphenyl) propane (bisphenol a) and bromine-substituted derivatives (tetrabromobisphenol a), epoxy resins based on glycidyl polyethers of 2,2 bis (4 hydroxyphenyl) methyl ether (bisphenol F), and epoxy resins based on glycidyl polyethers of novolacs, and epoxy resins based on aniline or substituted anilines, such as p-aminophenol or 4,4' diaminodiphenylmethane. Very particular preference is given to epoxy resins based on glycidyl polyethers of 2,2 bis (4 hydroxyphenyl) propane (bisphenol A) and epoxy resins based on glycidyl polyethers of 2,2 bis (4 hydroxyphenyl) methane (bisphenol F). Such epoxy resins can be cured particularly well by using the curing agent compositions preferred herein. With regard to the process according to the invention, it is preferred that one or a combination of the listed resins in combination with the reactive diluent and the curing agent should form an epoxy resin matrix having an average EEW value in the range of 100 to 250 g/eq.

Very particular preference is given according to the invention to the use of epoxy resins which may be referred to as "low-tack modified bisphenol A". These epoxy resins have a dynamic viscosity of 4000 to 6000 mPas at room temperature (25 ℃). Therefore, it is further preferable that an epoxy resin based on glycidyl polyether of 2,2 bis (4 hydroxyphenyl) propane (bisphenol a) and an epoxy resin based on glycidyl polyether of 2,2 bis (4 hydroxyphenyl) methane (bisphenol F) having a dynamic viscosity of 4000 to 6000mPa · s at room temperature (25 ℃) can be used.

Very particular preference is given to using epoxy resins based on glycidyl polyethers of 2,2 bis (4 hydroxyphenyl) propane (bisphenol A) and epoxy resins based on glycidyl polyethers of 2,2 bis (4 hydroxyphenyl) methane (bisphenol F), which have a dynamic viscosity of 4000 to 6000mPa · s at room temperature (25 ℃) and which have an average EEW value in the range from 100 to 250g/eq, in particular in the range from 100 to 210g/eq, in particular in the range from 100 to 190 g/eq.

Therefore, in the process according to the invention, it is particularly preferred to use a curable epoxy resin matrix having an average EEW value in the range of 100 to 250g/eq before curing.

Furthermore, in the process according to the invention, it may be particularly preferred to use a curable epoxy resin matrix comprising an epoxy resin from the group of difunctional epoxy resins and/or an epoxy resin having an average EEW value of from 150 to 200g/eq, in particular a difunctional epoxy resin.

Furthermore, in the process according to the invention, it may be particularly preferred to use a curable epoxy resin matrix comprising a reactive diluent selected from the group of difunctional glycidyl ethers and/or comprising glycidyl ethers, in particular difunctional glycidyl ethers having an average EEW value of from 100 to 200 g/eq.

According to a particularly preferred embodiment of the process, the epoxy resin matrix comprises a curing agent, in particular a liquid curing agent, which contains cyanamide (CAS 420-04-2; NC-NH) in its composition₂). The mode of action of these curing agents, especially liquid curing agents, in epoxy resins is comparable to the curing properties of dicyandiamide promoted with imidazole. However, it is retained for a delay of several days at room temperature, as compared with an epoxy resin composition containing a typical amine curing agent. Further, it is possible to provide a polymer resin cured with a cyanamide-based liquid curing agent, which has a high glass transition temperature as compared with a polymer resin cured with an amine curing agent.

In general, it is thus possible to provide curing agents or curing agent compositions, in particular liquid curing agents, which are particularly suitable for the method according to the invention for producing a compression cylinder by filament winding, due to the high time delay in the polymer resin composition and the high reactivity in the polymer resin composition at the curing temperature.

In the process according to the invention or in the epoxy resin matrix, glycidyl ethers can be used in particular as reactive diluents. Here, monofunctional, difunctional and polyfunctional glycidyl ethers can be further preferably used. In particular, mention should be made here of glycidyl ethers, diglycidyl ethers, triglycidyl ethers, polyglycidyl ethers and combinations thereof. Particularly preferably, glycidyl ethers from the group comprising: 1, 4-butanediol diglycidyl ether, trimethylolpropane trisacetalGlycidyl ether, 1, 6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, C₈-C₁₀Alcohol glycidyl ethers, C₁₂-C₁₄Alcohol diglycidyl ether, cresol glycidyl ether, poly (tetramethylene oxide) diglycidyl ether, 2-ethylhexyl glycidyl ether, polyoxypropylene glycol triglycidyl ether, neopentyl glycol diglycidyl ether, p-tert-butylphenol glycidyl ether, polyglycerol polyglycidyl ether, and combinations thereof.

Very particularly preferred glycidyl ethers are 1, 4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether and combinations thereof. These reactive diluents can be used to set the viscosity of the epoxy resin. Here, monofunctional glycidyl ethers can be reacted with epoxy resins without forming transverse cross-links. Thus, for the process according to the invention, at least one difunctional glycidyl ether, one diglycidyl ether, is used for setting the impregnation viscosity. This helps to make the curable epoxy resin matrix cross-linkable in the transverse direction in order to obtain good mechanical properties of the compressed gas container. Furthermore, the diglycidyl ethers preferably have an average EEW value of 100 to 200g/eq and therefore a smaller molecular weight, with the result that they have a lower viscosity than diglycidyl ethers having a higher EEW.

With regard to the selection of the reinforcing fibers used, reinforcing fibers selected from the group consisting of carbon fibers, glass fibers, aramid fibers and basalt fibers may be used, among others, in the method described herein.

These reinforcing fibers may further preferably be provided or used in the form of filaments, threads, yarns, woven fabrics, knits or knits.

The reinforcing fibers may also be selected from silicon carbide, alumina, graphite, tungsten carbide, boron. Furthermore, the reinforcing fibers may also be selected from the group of natural fibers, such as seed fibers (e.g. kapok, cotton), bast fibers (e.g. bamboo, hemp, kenaf, flax), leaf fibers (e.g. agave, manila hemp). Combinations of fibers can also be used in the method according to the invention.

Among the reinforcing fibers mentioned, preference is given above all to glass fibers and carbon fibers, in particular in the form of filaments, threads or yarns. These reinforcing fibers have particularly good mechanical properties, in particular a high tensile strength.

As mentioned at the outset, the choice of the inner liner depends on the type of compressed gas container to be produced. Thus, in the method according to the invention, thermoplastic inner liners, in particular made of HD polyethylene or polyamide, as well as metallic inner liners, in particular made of aluminum or steel, may be used. The liner may also be considered as a first layer onto which a second layer comprising an epoxy resin matrix and reinforcing fibers is applied according to the invention.

Drawings

The invention is explained in more detail below with the aid of the figures and the examples associated therewith. Here, there are shown:

fig. 1 shows a simple schematic view of a filament winding process for producing a compressed gas container according to the invention.

Detailed Description

Fig. 1 schematically shows a winding plant for producing compressed gas containers. Starting from the coil former system (1), the reinforcing fibers (2) are pulled via a reinforcing fiber guide (3) into a heatable impregnation bath (4) having an impregnation roller, a resin scraper and a reinforcing fiber guide. The rotation of the clamping device with the inner lining (6) on which the reinforcing fiber bundles are fixed at the beginning of the process produces a pulling of the reinforcing fibers through the impregnation tank (4). By this pulling, the reinforcing fibres on the impregnation roller are wetted by the curable epoxy resin matrix, excess resin is scraped off by means of a resin scraper and the reinforcing fibre guide is pulled in the direction of the outlet head (5). The outlet head (5) controls the placement of the reinforcing fibers on the liner (6).

The following examples of the method are carried out with equipment corresponding to this principle arrangement.

Examples of the invention

1) Curable compositionEpoxy resin matrix

a) The raw materials used

Product name of component (a):RF2100(AlzChem Trostberg GmbH)

modified bifunctional bisphenol A epoxy resin

(EEW 170 to 190g/eq) (viscosity at 25 ℃ 4000 to 6000 mPa. multidot.s)

Product name of component (B):Fluid 212(AlzChem Trostberg GmbH)

liquid cyanamide-based curing agents (viscosity at 25 ═ 80 to 160mPa · s)

Product name of component (C): EPON RESIN 828(Hexion Inc.)

Unmodified bisphenol A epoxy resins (EEW 185 to 192g/eq)

(viscosity at 25 ℃ C. is 11 to 16 Pa. s)

Product name of component (D):(Huntsman Cooperation)

amine-based liquid curing agent (viscosity at 25 ℃ C. of 72 mPas)

Product name of component (E):1564SP(Huntsman Cooperation)

formulated bisphenol A based epoxy resins

(epoxy content: 5.8 to 6.05eq/kg) (viscosity at 25 ℃ 1200 to 1400 mPa. multidot.s)

Product name of component (F):(Huntsman Cooperation)

liquid curing agents of the anhydride type (viscosity at 25 ═ 50 to 100mPa · s)

Product name of component (G): DMP-30^TM(Sigma-Aldrich Chemie GmbH)

Accelerator (b): 2,4, 6-tris (dimethylaminomethyl) phenol

Product name of component (H):1556SP(Huntsman Cooperation)

bisphenol A based epoxy resins

(epoxy content: 5.30 to 5.45eq/kg) (viscosity at 25 ℃: 10 to 12 pas)

Product name of component (I): 1-methylimidazole (Carl Roth GmbH & Co KG)

Accelerator

b) Manufacture of substrates

To the corresponding epoxy resin (component A, C, E, H) was added the corresponding liquid curing agent (component B, D, F) and to the anhydride-based liquid curing agent (component F) was added the corresponding accelerator (component G or I) and stirred until homogeneous. Then, for the gel time measurement, 100g of the formulation was taken out each time. At the same time, the isothermal viscosity was measured on a viscometer. For the measurement on the DSC, a small portion of the mixture is extracted. For the winding process, the separately manufactured, curable epoxy resin matrix was heated to 40 ℃ and placed in a tempered dipping bath. At constant temperature, the filament winding process begins.

TABLE 1: composition of curable epoxy resin matrix 1 according to the invention and comparative matrices 2, 3 and 4

Composition of	Base body 1	Base body 2	Base body 3	Base 4
					Component A	100	--	--	--
Component B	10	--	--	--
					Component C	--	100	--	--
Component D	--	43	--	--
					Component E	--	--	100	--
Component F	--	--	98	90
					Component G	--	--	3	--
Component H	--	--	--	100
					Component I				1

c) Test specification for testing material properties

DSC：

Mettler Toledo DSC 1

Dynamic DSC:

a sample of the formulation was heated from 30 ℃ to 250 ℃ at a heating rate of 10K/min. The peak of the exothermic reaction was evaluated by determining the onset temperature (T)_Onset) Temperature of peak maximum (T)_Max) And as a measure of the heat of reaction released (Δ)_RH) Is performed according to the peak area of (a).

Isothermal DSC:

samples of the formulation were held constant at the indicated temperature for the indicated time (isothermal solidification of the formulation). The evaluation was carried out by determining the time of peak maximum of the exothermic reaction peak (as a measure of the beginning of the solidification process) and the 90% conversion (as a measure of the end of the solidification process).

A rheometer:

antopa MCR302 with CTD 450

Isothermal viscosity:

the isothermal viscosity curves of the samples at 40 ℃ and 50 ℃ were determined on an andopa viscometer MCR302 with a measurement system D-PP25(1 ℃ measurement cone) with a measurement gap of 0.052 mm. When a predetermined temperature is reached in the measurement chamber of the viscometer, the measurement sample is applied to the measurement plate. The preset values for the measurement point recording are set to continuously record 1 or 0.5 measurement points per minute, respectively.

The measurement was rotated at a shear rate of 51/s. The measuring cone enters a preset measuring gap height of 0.052mm and the measurement is started. After the end of the measurement, the measurement curve is evaluated with the aid of the data record in the software Rheoplus version 3.62, and the time until a viscosity of 1000 mPas is reached is thus obtained from the data record.

Gel time test:

exactly 100g of the corresponding formulation were prepared and immediately afterwards placed in a drying cabinet at 40 ℃ and 50 ℃. Stir every hour and check the formulation. If the mixture is no longer stirred homogeneously, the time is recorded as gel time and the sample is classified as no longer liquid.

Example 1 (according to the invention):

to 100 parts by weight of component (a), 10 parts by weight of component (B) was added and stirred until uniform. Then, for the gel time measurement, 100g of the formulation was taken out each time. At the same time, the isothermal viscosity was measured on a viscometer. For the measurement on the DSC, a small portion of the mixture is extracted.

Table 2:the epoxy resin composition includes the test results (material parameters)

Pot life measurements by rheometer; until a viscosity of 1000 mPas was reached.

As can be seen from table 2, the initial viscosity was determined from isothermal viscosity measurements and from the isothermal series of measurements of the matrices 1-4, said matrix 1 achieving high pot life values both at 40 ℃ and 50 ℃, 59 hours at 40 ℃ and 95 hours at 50 ℃ and thus having a viscosity range of 200 to 1000mPa · s over 48 hours. Manual gel time testing of substrates 1-4 also demonstrated that substrate 1 was liquid at both temperatures well over 48 hours and thus cured from 144 hours at 50 ℃ and over 240 hours at 40 ℃.

Thus, these comparisons show a higher pot life and thus also a higher time delay for substrate 1 compared to comparative substrates 2-4.

This means that the matrix system 1 is advantageous for meeting the requirements for compressed gas cylinders, in particular with a large volume, due to the high time delay. Longer treatment times with reduced cleaning stops and treatment residues are possible, and a low viscosity that remains constant during the winding time may result in a constant wetting of the reinforcement fibers.

2) Examples of liner manufacturer evidence

For this experiment, an HDPE (PE-HD; high density polyethylene) liner with a capacity of 51 litres, with a total length of 882mm, a diameter of 314.5mm and a weight of 8.9kg (including the boss portion) was used.

3) Examples of reinforcing fiber manufacturer evidence

Carbon fiber: mitsubishi Rayon MRC _37_800WD _30K

The manufacturer: mitsubishi chemical carbon fiber and composite Material Ltd

4) Examples of methods for manufacturing compressed gas containers

a) General method rules-perhaps with reference to the accompanying drawings

The winding structure of the carbon fibers, designed to a theoretical rupture pressure of 460 bar, was calculated with the aid of software composite. Our experimental series is based on a cylinder designed for 200 bar. For this type of pressure vessel, the standard requires a safety factor of 2.3 of the working pressure, so the minimum burst pressure is 460 bar. The HDPE liner was initially secured at both ends on a winder in a clamp, cleaned with acetone, and activated with a small flame on the outside with a bunsen burner. For the formulation, 100 parts of component a and 10 parts of component B were stirred until homogeneous and heated to 40 ℃. The formulation is then added to the tempered dipping tank.

To set the optimum impregnation viscosity, the impregnation cell was heated to 40 ℃. The external temperature during winding was 15.9 ℃. The doctor blade was set to a gap of 0.6 mm. The reinforcing fibers from the 8 coils were pulled through the bath toward the liner and gathered into strips about 2.7cm wide on the member. The winding process was 35 minutes. Winding is effected both axially and radially around the liner, according to calculations and settings in the program. To fix the reinforcing fiber ends, they are laid as ferrules under the penultimate winding and the protruding fibers are cut. Curing was carried out at 95 ℃ for 8 hours. The cylinder is suspended horizontally in the furnace and rotated during curing.

b) Test provisions

Fracture test according to ISO 11439

Pressure Change test according to ISO 11439 and NGV02

c) Test results

The cured cylinder had a weight of 17.70 kg. The diameter is 330 mm. For the winding, 5.494kg of carbon fibers were used in total. Thus, the amount of formulation was 3.306 kg.

And (3) fracture test: maximator analog pressure gauge 0 to 2500 bar (Serial No. 247298001), GS 4200USB pressure sensor (Serial No. 510305)

Table 3:the resulting fracture and fiber stresses and the properties calculated therefrom

Burst pressure [ bar ]]	519
		Achieved fibre stress [ MPa]	3000
Performance of container	1495.4
		Laminate Properties	3007.8

And (3) testing pressure change: galiso analog pressure gauge 0 to 11.000PSI (Serial number 508130013)

Table 4:results obtained from pressure change testing at room temperature.

Number of cycles (cycle)	61432
		Effective number of cycles (cycles)	61372
Maximum temperature [ deg.C ]]	39.4
		Average circulation rate (cycles/minute)	9.1
Average minimum pressure [ bar ]]	2.7

After the test, the cylinder was inspected and no appearance defects were found. When cut in half, small cracks were identified only in the HDPE liner after 61432 cycles. The laminate remains intact.