DE202009013510U1 - Pressure vessel for dispensing a foam consisting of at least two components - Google Patents

Abstract

Pressure vessel (1) for delivering a foam consisting of at least 2 components by internal gas pressure, wherein the interior of the pressure vessel (1) is divided into at least two mutually sealed chambers (2a, 3a) and each chamber (2a, 3a) with at least one active component (WK1, WK2) and at least one propellant gas is filled,
characterized in that
one chamber (2a) at least one first active component (WK1) selected from the group consisting of urethanes, isocyanates, isocyanurates, alcohols, amines, silicones, silicates, epoxides, acrylates, acids, bases, salts, hydroxides, chlorides, carbonates, sulfates , Nitrates, oxides, carbides, ammonium, esters, nitriles, phenols, ketones, peroxides, water or combinations thereof having at least one propellant having a GWP of less than 150 selected from the group consisting of C ₁ -C ₁₀ saturated or unsaturated or halogenated hydrocarbons, C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons, ethers, noble gases, nitrogen and its oxides, carbon oxides, amines, chlorides and mercaptans, or combinations thereof,
and that the other ...

Description

The The invention relates to a pressure vessel for delivering a from at least two components foam according to the preamble of claim 1.

Polyurethane (PU) -Ortsschaum is filled into so-called aerosol cans. Through the in the can taken propellant and possibly by a chemical Reaction results when discharging a foam. There are one-component (1K) and two-component (2K) foams. For 1K foams a so-called prepolymer resulting from the reaction of isocyanate, mostly diphenylmethane-4,4'-diisocyanate and polyol has arisen, filled in the can. In addition there are Flame retardants, auxiliaries and liquefied propellants such as 1,1,1,2-tetrafluoroethane (R134a) and dimethyl ether (DME) in the Formulation. If you spray the contents of the can, will the prepolymer is foamed by the abruptly evaporating propellant gas. The hardening takes place with air humidity, thereby arises also carbon dioxide, which further inflates the foam. 1K foam it takes a long time to harden and depending on the humidity is not dimensionally stable. It can be long after curing still shrinking or simmering. This is for example when foaming Door frames a considerable disadvantage, because the frame bends on swelling of the foam and thereby blocks the door can be. That's why such applications usually work 2K foam used, which does not have these disadvantages.

For 2K foams will be different aerosol packaging systems used. Common is the inside mixing aerosol can, at the in a commercial can an inner container is installed. In the main box is essentially the same formulation as a 1K foam. In the inner container there is a catalyst formulation for curing of the prepolymer. Before you spray the can you have to they activate by the inner container from the outside is opened. Usually a wire is pulled on the or a button to press. After opening of the inner container, the catalyst formulation pours into the prepolymer in the main can. By vigorous shaking mix the two components in the can. The sprayed out Mass is not dependent on humidity for curing, the curing of the prepolymer z. B. by trimerization of NCO groups of the isocyanate initiated by the catalyst. The finished foam is harder and more dimensionally stable than 1K foam.

One The major disadvantage of these systems is that you have to activate them must consume the whole can at once in a short time. exceeds the user the so-called pot life, the mixture is in the can hard and must be disposed of. In addition, there is a risk of bursting if you exceed the pot life on warm days. By The chemical reaction in the can creates heat, the increases the pressure of the liquefied propellant gas. Some manufacturers therefore stipulate that the can above a Temperature of 25 ° C must not be activated.

To solve this problem is in the EP 0 111 089 describes a 2-component aerosol can, which allows to mix outside and which does not have the disadvantages described above. The box is provided with two independent compartments filled with different components. The first chamber is formed by the actual main can, in which the first component is received in preferably liquid form. The second chamber is formed by an inner container in which the second, the curing of the discharged foam accelerating component is filled. This second component is preferably also liquid. Each chamber of the aerosol can is connected to a closable outflow channel leading to the outside.

Until now, propellant gases which are relatively harmful to the environment are used in particular for 2-component cans for generating the internal gas pressure. As an example, the widespread propellant R134a is mentioned, which has a so-called GWP value of 1300. GWP stands for "Global Warming Potential". This GWP value describes the global warming potential of a gas compared to carbon dioxide (CO ₂ ). Global warming potential is calculated as the warming potential of one kilogram of a gas over a period of 100 years against the corresponding one kilogram of CO ₂ .

The high GWP value of R134a is critical. In the Regulation (EC) No 842/2006 of 17 May 2006 the use of R134a for 1K cans or 1K foams is prohibited. For 2K foams the above regulation does not apply, nevertheless it would be desirable to find replacement for these polluting propellants.

However, in the search for a replacement for the hitherto used to the main propellants has shown that the replacement of a common propellant gas such as R134a is not readily possible by a more environmentally friendly propellant gas. For example, if a gas other than R134a is mixed with a catalyst based on potassium acetate and / or potassium octoate, crystallization takes place during storage in the inner container. When spraying the contents of the can thereby blocked the discharge channel. Important for pressure vessels for holding such Products, however, that the products can be stored long-term stable in it. It should be ensured that the products can be included in the pressure vessel during a period of several months to a few years, without the risk that changes the contents, the pressure is reduced or the components under the influence of humidity and / or react chemically with oxygen.

outgoing from the described prior art, the object of the Invention thus, a, according to the preamble of Claim 1 trained pressure vessel in such a way that the released during discharge of the contents of the container propellants are less harmful to the environment, with the respective propellant gas the absorbed in the same chamber drug component or drug components should not adversely affect and being used Gas should be economically applicable.

These Task is solved with a pressure vessel, the with the features cited in the characterizing part of claim 1 is provided.

at looking for suitable, d. H. more environmentally friendly propellants it has been shown that it may be necessary not only to change the propellant, but also the chemical Formulation of at least one active ingredient component, in particular the hardener or catalyst. For that reason, that needs Propellant gas or propellants on the active substance component (s) to be contained in the same chamber be matched.

preferred Further developments of the pressure vessel are in the dependent Claims 2 to 17 defined.

The The invention will be described in greater detail below with reference to a drawing explained, with the single figure a pressure vessel shows, in a particularly preferred manner for receiving the suitable for forming a foam components.

The trained in the form of an aerosol can pressure vessel 1 is with two independent, mutually sealed chambers 2a . 3a Mistake. The first chamber 2a is through the actual main socket 2 formed while the second chamber 3a through an inner container 3 is formed. Both chambers 2a . 3a serve to accommodate one or more active components together with one or more propellant gases.

To form a 2K foam such as a PU foam is in the one, larger chamber 2a usually the actual main component, for example, a liquefied prepolymer taken together with two liquefied propellants, while in the other, smaller chamber 3a a hardening agent or catalyst accelerating the hardening of the main component is taken up together with a liquefied propellant gas, wherein the hardener or catalyst is preferably also present in liquefied form.

On the top of the pressure vessel 1 is a spray head 4 Arranged with a discharge nozzle 5 is provided. Both chambers 2a . 3a of the pressure vessel 1 are each with one through the spray head 4 outward leading outflow channel 6 . 7 connected. The respective outflow channel 6 . 7 is by means of a valve body 8th . 9 closable.

The inner container 3 is on a valve disk 10 bolted to the bottom of the spray head 4 is arranged. At this valve plate 10 are the two valve bodies 8th . 9 arranged such that these when pressing down the spray head 4 open together and preferably simultaneously, leaving the contents of both chambers 2a . 3a over the respective outflow channel 6 . 7 in the discharge nozzle 5 can flow where the components are merged. At the discharge nozzle 5 of the spray head 4 a prolonged discharge pipe (not shown) can be fastened, which is optionally provided with mixing baffles, which is a mixing of the two chambers 2a . 3a feed active ingredients or active ingredient components. Such a container 1 has the advantage of being in both chambers 2a . 3a recorded active components WK1, WK2 only outside the pressure vessel 1 be brought together and therefore the chemical-physical reaction takes place outside the container. As a result, the container is preferably suitable for multiple use.

The inner container 3 is rigid in the present example, so that it can be acted upon in the uninstalled state with LPG. Depending on the application, the inner container 3 also made of flexible material. To fill the inner container 3 first the chamber 3a with active ingredient such as. B. hardener filled. Then the valve is screwed on and the container through the valve body 8th fumigated through. Then the chamber 2a filled with the other active ingredient, the inner container with valve inserted and clinched. The chamber 2a is through the valve body 9 fumigated through. Finally, the whole tin is shaken.

The pressure vessel 1 to produce a local foam according to the invention is filled with the following active components and propellants:

main chamber 2a :

A first active ingredient component WK1 is selected from the group consisting of urethanes, isocyanates, isocyanurates, alcohols, amines, silicones, silicates, epoxides, acrylates, acids, bases, salts, hydroxides, chlorides, carbonates, sulfates, nitrates, oxides, carbides, ammonium , Esters, nitriles, phenols, ketones, peroxides, water or a combination thereof, and at least one propellant selected from the group consisting of C ₁ -C ₁₀ saturated or unsaturated or halogenated hydrocarbons, C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons , Ethers, noble gases, nitrogen and its oxides, carbon oxides, amines, chlorides and mercaptans or their combination.

inner chamber 3a :

Another active ingredient component WK2 is selected from the group consisting of urethanes, isocyanates, isocyanurates, alcohols, amines, silicones, silicates, epoxides, acrylates, acids, bases, salts, hydroxides, chlorides, carbonates, sulfates, nitrates, oxides, carbides, ammonium , Esters, nitriles, phenols, ketones, peroxides, water or a combination thereof, and at least one propellant selected from the group consisting of C ₁ -C ₁₀ saturated or unsaturated or halogenated hydrocarbons, C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons , Ethers, noble gases, nitrogen and its oxides, carbon oxides, amines, chlorides and mercaptans or their combination.

It goes without saying that, in addition to the active substance components mentioned, other components also enter the respective chamber 2a . 3a can be introduced. The same applies to the propellant gases, which can also be enriched with additional gases.

Preferably, the main chamber contains 2a at least one first active ingredient component WK1 selected from the group consisting of urethanes, isocyanates, alcohols, amines, silicones, silicates, epoxides, acids, salts, peroxides, water or a combination thereof with at least one propellant selected from the group consisting of C ₁ - C _{10 is} saturated or unsaturated or halogenated hydrocarbons, C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons, ethers, nitrogen and its oxides, carbon oxides mixed singly or in combination. The other chamber 3a preferably contains at least one further active ingredient component WK2 selected from the group consisting of urethanes, isocyanates, alcohols, amines, silicones, silicates, epoxides, acids, salts, peroxides, water or a combination thereof with at least one propellant selected from the group consisting of C C ₁ -C ₁₀ saturated or unsaturated or halogenated hydrocarbons, C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons, ethers, nitrogen and its oxides, carbon oxides or combinations thereof.

In any case, propellants with a GWP value below 150 are used in particular. Preferably, this is in the respective chamber 2a . 3a absorbed propellant under an overpressure between 2.5 and 10 bar at 20 ° C. Preferably, at least the propellant gas received in the one chamber is liquefied, in particular that in both chambers 2a . 3a absorbed propellant is liquefied. The propellant gas is preferably designed in such a way that it causes a physical foaming of said active substance component during the spraying with the active substance component accommodated in the chamber. Optionally, in the chemical reaction of the two discharged active ingredient components, gas can be formed which promotes foaming.

additionally can flame retardants, stabilizers and possibly further auxiliaries are taken up in the respective chamber.

The following is an example of a recipe for the filling of the main chamber 2a as well as the inner chamber 3a without the use of the gas R134a indicated.

Filling the main chamber 2a :

• 100-300 grams of diphenylmethane-4,4'-diisocyanate
• 50-100 grams of polyol
• 50-100 grams of flame retardant
• 1-5 grams of foam stabilizer
• 0.1-2 grams of catalyst to form the prepolymer
• 10-50 grams of propane-butane 4.2
• 10-50 grams of DME

Filling of the inner chamber 3a :

• 5-30 grams of polyol
• 5-30 grams of trimerization amine catalyst
• 5-30 grams of trimerization co-catalyst
• 0.1-1 grams of dye
• 2-10 grams of difluoroethane (R152a)

The End product is PU mounting foam, which is preferably for foaming of door frames is suitable.

The number behind "propane-butane" stands for an overpressure of 4.2 bar in relation to the surrounding area operating pressure at 20 ° C. For example, propane-butane 4.2 is under an overpressure of 4.2 bar in relation to the ambient pressure. The term "propane-butane" stands for a technical mixture of the gases propane, isobutane and n-butane. Depending on the mixture, an overpressure between approx. One and approx. 9 bar can be generated (at 20 ° C). In the above recipe example you do not need to take propane-butane 4.2, there are also other pressure ranges such. For example, propane-butane 5.7.

The proposed propellant R152a has a GWP value of 120 and is therefore much more environmentally friendly than R134a. The amine-based catalyst formulation does not crystallize in contact with R152a. The catalyst also initiates trimerization so that the discharged foam is hard and dimensionally stable. In the inner container 3 one should preferably not use the propellant propane-butane or DME, since their diffusion through the sealing materials is very high. This may cause it in the inner container 3 during storage come to a large loss of gas, whereby the pressure drops accordingly and the can after prolonged storage may no longer work properly.

Below is an example of another recipe for the filling of the main chamber 2a as well as the inner chamber 3a without the use of the gas R134a indicated. In this case the discharged product represents a fire protection foam:

Filling the main chamber 2a :

• 460 g silicone rubber [from Wacker-Chemie]
• 57 g propane-butane 6.7

Filling of the inner chamber 3a :

• 50 g hardener [from Wacker-Chemie]
• 6 g of propane-butane 6.7

The Figure behind propane-butane stands again for the overpressure, in the concrete example, therefore, for an overpressure of 6.7 bar in relation to the ambient pressure. Usually One can use a propane-butane gas mixture with 4.2 bar overpressure to use. For the above foam, this mixture does not work because propane-butane dissolves very well in silicone and thereby greatly reduces the pressure. The Aussprührate is then very low and not accepted by the user. An advantage of the good Solubility is that diffusion through the sealing materials decreases and thus the loss of gas during storage becomes so low that use is possible.

Of the sprayed silicone foam has interesting technical Features such as easy processing; Permanent elasticity; lack of delivery of harmful or odor-intensive substances during vulcanization; excellent thermal durability up to 200 ° C; slight change in mechanical properties in a wide temperature range of -45 to + 180 ° C; flammability; excellent dielectric properties over a wide range Temperature and frequency range remain almost constant; good weather, Ozone and radiation resistance, as well as low moisture absorption. The foam is due to the heavy combustibility in the structural fire protection used. In case of fire, hardly any toxic decomposition products are produced.

Below is an example of another recipe for the filling of the main chamber 2a as well as the inner chamber 3a without the use of the gas R134a indicated. In this case, the discharged product represents a fire protection foam with large foam volume. It is particularly suitable for foaming the frame of fire doors:

Filling the main chamber 2a :

• 100-300 grams of diphenylmethane-4,4'-diisocyanate
• 50-100 grams of halogenated polyol
• 50-100 grams of tris (2-chloroisopropyl) phosphate
• 1-5 grams of foam stabilizer
• 10-50 grams of difluoroethane (R152a)
• 10-50 grams of DME

Filling of the inner chamber 3a :

• 5-30 grams of polyol
• 5-30 grams of trimerization amine catalyst
• 5-30 grams of trimerization co-catalyst
• 0.1-1 grams of dye
• 2-10 grams of difluoroethane (R152a)

• – Das Treibgas darf die verwendeten Werkstoffe nicht angreifen.
• – Das Treibgas darf nicht mit dem Füllgut [Wirkstoffkomponente(n)] reagieren.
• – Das Treibgas darf das Füllgut nicht verändern, wie z. B. Kristallisation erzeugen.
• – Das Treibgas muss sich im Füllgut lösen.
• – Die Diffusion des Treibgases durch die Dichtelemente soll sehr gering (möglichst nahe Null) sein.
• – Das Treibgas muss bei Raumtemperatur genügend Druck aufbauen, um eine akzeptable Aussprührate zu erzeugen.
• – Das Treibgas darf bei 50°C nicht zuviel Druck aufbauen. Ansonsten darf das Produkt nicht in den Verkehr gebracht werden.
• – Das Treibgas darf keine zu große verdünnende Wirkung auf das Füllgut haben.

Incidentally, the requirements for the mixture propellant gas / product are high and also the interactions of propellant gas and filling material with the materials of the box are to be observed. The general rule:

• - The propellant must not attack the materials used.
• - The propellant gas must not react with the contents [active substance component (s)].
• - The propellant may not change the contents, such. B. generate crystallization.
• - The propellant gas must dissolve in the product.
• - The diffusion of the propellant gas through the sealing elements should be very low (as close to zero).
• - The propellant must generate enough pressure at room temperature to produce an acceptable discharge rate.
• - The propellant must not build up too much pressure at 50 ° C. Otherwise, the product may not be placed on the market.
• - The propellant must not have too great a diluting effect on the contents.

In summary It can be stated that there are several possibilities to replace the polluting propellant R134a in local foam formulations gives. In practice, the liquefied propellants have Propane-butane, DME and R152a especially proven. Especially the interactions of the gases with the contents and / or The cans are each critical and require a precise Poll.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 0111089 [0005]

Cited non-patent literature

• - Regulation (EC) No 842/2006 of 17 May 2006 [0007]

Claims (16)

Pressure vessel ( 1 ) for delivering a foam consisting of at least 2 components by internal gas pressure, wherein the interior of the pressure vessel ( 1 ) in at least two mutually sealed chambers ( 2a . 3a ) and each chamber ( 2a . 3a ) is filled with at least one active substance component (WK1, WK2) and at least one propellant gas, characterized in that the one chamber ( 2a ) at least one first active ingredient component (WK1) selected from the group consisting of urethanes, isocyanates, isocyanurates, alcohols, amines, silicones, silicates, epoxides, acrylates, acids, bases, salts, hydroxides, chlorides, carbonates, sulfates, nitrates, oxides, Carbides, ammonium, esters, nitriles, phenols, ketones, peroxides, water or a combination thereof containing at least one having a GWP value of less than 150 propellant selected from the group consisting of C ₁ -C ₁₀ saturated or unsaturated or halogenated hydrocarbons , C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons, ethers, noble gases, nitrogen and its oxides, carbon oxides, amines, chlorides and mercaptans or combinations thereof, and in that the other chamber ( 3a ) at least one further active ingredient component (WK 2) selected from the group consisting of urethanes, isocyanates, isocyanurates, alcohols, amines, silicones, silicates, epoxides, acrylates, acids, bases, salts, hydroxides, chlorides, carbonates, sulfates, nitrates, oxides, Carbides, ammonium, esters, nitriles, phenols, ketones, peroxides, water or a combination thereof containing at least one having a GWP value of less than 150 propellant selected from the group consisting of C ₁ -C ₁₀ saturated or unsaturated or halogenated hydrocarbons , C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons, ethers, noble gases, nitrogen and its oxides, carbon oxides, amines, chlorides and mercaptans, or combinations thereof. Pressure vessel ( 1 ) according to claim 1, characterized in that the one chamber ( 2a ) contains at least one first active ingredient component (WK1) selected from the group consisting of urethanes, isocyanates, alcohols, amines, silicones, silicates, epoxides, acids, salts, peroxides, water or a combination thereof having at least one GWP value of less than or equal to 150 comprising propellant gas selected from the group consisting of C ₁ -C ₁₀ saturated or unsaturated or halogenated hydrocarbons, C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons, ethers, nitrogen and its oxides, carbon oxides or their combination is mixed, and that the other chamber ( 3a ) contains at least one further active ingredient component (WK2) selected from the group consisting of urethanes, isocyanates, alcohols, amines, silicones, silicates, epoxides, acids, salts, peroxides, water or a combination thereof having at least one GWP value of below 150 propellant gas selected from the group consisting of C ₁ -C ₁₀ saturated or unsaturated or halogenated hydrocarbons, C ₃ -C ₁₀ saturated or unsaturated or halogenated cyclic hydrocarbons, ethers, nitrogen and its oxides, carbon oxides or combinations thereof is mixed. Pressure vessel ( 1 ) according to claim 1 or 2, characterized in that the propellant gas of the first chamber ( 2a ) equal or different from the propellant gas of the second chamber ( 3a ). Pressure vessel ( 1 ) according to one of the preceding claims, characterized in that in the one chamber (3a) an active component (WK2) is received, which is the curing of the in the other chamber ( 2a ) is intended to effect the absorbed active ingredient component (WK1). Pressure vessel ( 1 ) according to claim 4, characterized in that the hardening of an active ingredient component (WK1) causing further active ingredient component (WK2) is an amine-based catalyst formulation. Pressure vessel ( 1 ) according to one of the preceding claims, characterized in that in the respective chamber ( 2a , 3a) recorded propellant gas is under an overpressure between 1 and 10 bar. Pressure vessel ( 1 ) according to one of the preceding claims, characterized in that at least that in the one chamber ( 2a . 3a ) liquefied propellant is liquefied. Pressure vessel ( 1 ) according to claim 7, characterized in that at least in one chamber ( 2a . 3a ) is added as propellant propane-butane, dimethyl ether or difluoroethane. Pressure vessel ( 1 ) according to one of the preceding claims, characterized in that in one chamber ( 2a ) as active ingredient component (WK1) is a liquefied PU and in the other chamber ( 3a ) an amine-based active component (WK2) is taken together with a propellant acting, liquefied difluoroethane (R152a). Pressure vessel (1) according to one of the preceding claims, characterized in that in the one chamber ( 2a ) as the active ingredient component (WK1) a liquefied silicone is taken together with liquefied propane-butane as a propellant gas. Pressure vessel ( 1 ) according to one of the preceding claims, characterized in that the one chamber ( 2a ) is filled with the following components: 100-300 grams of diphenylmethane-4,4'-diisocyanate 50-100 grams of polyol 50-100 grams of flame retardant 1-5 grams of foam stabilizer 0.1-2 grams of catalyst to form the prepolymer 10-50 grams of propane -Butan 10-50 grams of DME and that the other chamber ( 3a ) is filled with the following components: 5-30 grams of polyol 5-30 grams of trimerization amine catalyst 5-30 grams of trimerization co-catalyst 0.1-1 grams of dye 2-10 grams of difluoroethane (R152a) Pressure vessel ( 1 ) according to one of the preceding claims, characterized in that the one chamber ( 2a ) is filled with the following components: 300-600 grams of liquefied silicone rubber 30-100 grams of propane-butane and that the other chamber ( 3a ) is filled with the following components: 30-100 grams of hydrogen and CH ₃ group-containing silicone polymer as crosslinker 3-10 grams of propane-butane Pressure vessel ( 1 ) according to one of the preceding claims, characterized in that the propellant gas is preferably designed such that it causes a physical foaming of said active component during spraying with the absorbed in the chamber active ingredient component. Pressure vessel ( 1 ) according to one of the preceding claims, characterized in that the inner container ( 2 ) is rigid and can be applied in the uninstalled state with LPG. Pressure vessel according to one of the preceding claims, characterized in that the inner container ( 2 ) is made of flexible material. Pressure vessel according to one of the preceding claims, characterized in that the volume of the chamber containing a first active substance component (WK1) ( 2a ) is many times greater than the volume of the further active ingredient component (WK2) containing chamber ( 3a ).