DE19725360C2 - Mixtures with 1,1,1,3,3-pentafluorobutane - Google Patents

Description

The present invention relates to mixtures with 1,1,1,3,3- Pentafluorobutane (HFC-365mfc) and its use in manufacturing position of foamed plastics.

It is already known to use partially fluorinated hydrocarbons as propellants for the production of foamed plastics to use. The international patent application WO 92/00345 discloses the use of partially fluorinated alkanes with 4 or 5 carbon atoms, which has a "tertiary structure" exhibit, as a blowing agent for the production of polyurethane and polyisocyanurate foams.

DD-PS 298 419 discloses that polyfluoroalkanes with three up to seven carbon atoms and at least two fluorine atoms as propellants for plastic foams, for example Polyurethane foams are useful. 1,1,1,3,3-pentafluor Butane is mentioned as an example of such a propellant.

The German patent application DE 44 22 714 A1 discloses Compositions containing 1,1,2-trifluoroethane and the Use of such compositions as blowing agents for Manufacture of foamed plastics. The international patent application WO 96/14354 discloses the production of foamed Plastics, being a liquid blowing agent composition is used, the carbon dioxide liquefied under pressure contains. The blowing agent composition can also Chlorofluorocarbons and fluorocarbons ent hold, for example, 1,1,1,3,3-pentafluorobutane (HFC-365mfc). The German patent application 195 41 013 discloses u. a. Blowing agent compositions for the production of poly urethane flexible foams. The blowing agent compositions comprise 50 to 95 parts by weight of 1,1,1,2-tetrafluoroethane and 5 up to 50 parts by weight of 1,1-difluoroethane and / or volatile organic compounds. The international patent application WO 96/30439 discloses azeotropic compositions comprising  u. a. 1,1,1,4,4,4-hexafluorobutane or perfluorohexane and be agreed C5 or C6 hydrocarbons. These compositions can be used as blowing agents for the production of polyurethane Rigid foams can be used.

The object of the present invention is a method to indicate which of simpler processing the manufacturer development of advantageous, foamed plastics, in particular Polyurethane foams, to be specified. Task of the present Er It is also the invention to specify mixtures without a flash point, with which, for example, foamed polymer plastics with qualitatively advantageous properties in a simpler way let generate.

This object is achieved by the present invention.

According to the invention, as a propellant gas for the production ge foamed plastics usable, mixtures consist of 50 up to 99% by weight 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and 1 up to 50 wt .-% of at least one fluorocarbon chooses from the group consisting of 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3,3-hexafluoropropane and 1,1,1,2,3,3,3-heptafluoropropane.

1,1,1,3,3-pentafluorobutane lies on the border with Ent flammability. The mixtures according to the invention are notable for for example from the fact that they are not flammable liquids display at 20 ° C. They are particularly suitable for use Use as a propellant for the production of foamed art fabrics, but can also be used for other purposes such as can be used as refrigerants, solvents or cleaning agents.

Preferred mixtures consist of 80 to 99% by weight 1,1,1,3,3-pentafluorobutane and 1 to 20% by weight of 1,1,1,2-tetra fluoroethane, 1,1,1,3,3,3-hexafluoropropane and / or 1,1,1,2,3,3,3- Heptafluoropropane, especially mixtures consisting of 80 to  99% by weight HFC-365mfc and 1 to 20% by weight HFC-134a and / or HFC- 227ea exist.

Particularly preferred mixtures with HFC-134a consist of 91 to 95% by weight 1,1,1,3,3-pentafluorobutane and 5 to 9% by weight 1,1,1,2-tetrafluoroethane; from the specified compounds in existing mixtures have a boiling point point of 20 ° C.

Particularly preferred mixtures with HFC-227ea are those which consists of 80 to 99% by weight 365mfc and 1 to 20% by weight HFC 227ea, in particular 85 to 89% by weight of 1,1,1,3,3-pentafluorobutane and 11 to 15% by weight of 1,1,1,2,3,3,3-heptafluoropropane; from the specified connections in the last specified Amounts of existing mixtures have a boiling point in the range from approx. 23 ° C.

Mixtures with HFC-245fa are also excellent 50% by weight 1,1,13,3-pentafluorobutane and 50% by weight 1,1,1,3,3- Pentafluoropropane have a boiling point in the range of 22 ° C. These mixtures give particularly good results when used Insulation values.

The mixtures according to the invention are under standard conditions conditions in liquid form. The preferred mixtures are e.g. B. at ambient pressure (approx. 1 atm) and 20 ° C liquid. In the ser form they are used appropriately if they are in ver foaming plastics or their premixes incorporated should be. They are particularly suitable as a propellant for the production of foamed plastics, for example even after the extrusion process. In this procedure the thermoplastic plastics containing the blowing agent directly extruded into foamed sheets, foils or profiles. The Plastic mass foams immediately after leaving the nozzle on. For example, XPS and XPE foams (Polystyrene or polyethylene based foams) len.  

The mixtures according to the invention are particularly suitable for the production of foams based on isocyanates. They are particularly suitable for the production of Hard but also soft foams based on isocyanate. The Her Position of foams based on isocyanate is known. Their manufacture and the basic materials that can be used for them are, for example, in the European patent application EP-A-0 381 986; in "Ullmanns Encyclopedia of Industrial Chemistry ", 5th edition, volume A 21, pages 665 to 680; den international patent applications WO 92/00345, 96/30439, 96/14354 and the German patent application DE 44 22 714 A1 disclosed.

Aliphatic, cycloali phatic, araliphatic, aromatic and heterocyclic Polyisocyanates, for example with 2 to 4 isocyanate groups be used. They have an aliphatic hydrocarbon material residue with up to 18 carbon atoms, a cycloaliphatic Koh Hydrogen hydrogen residue with up to 15 carbon atoms, an aromatic Hydrocarbon residue with 6 to 15 carbon atoms or an arali phatic hydrocarbon residue with 8 to 15 carbon atoms. Technically particularly preferred starting components are at for example 2,4- and 2,6-tolylene diisocyanate, diphenylmethane di isocyanate, polymethylene polyphenyl isocyanate and mixtures thereof So-called "modified polyisocyanates" can also be used. which carbodiimide groups, urethane groups, Allophanate groups, isocyanurate groups, urea groups or Biuret groups included.

Other starting components are connections with min at least 2 hydrogenato reactive towards isocyanates men. These are in particular connections with a Molecular weight of 400 to 10,000, which are preferably 2 to Have 8 hydroxyl groups and also amino groups, thiol may have groups or carboxyl groups. Particularly good polyethers, polyesters, polycarbonates and poly are suitable ester amides which have 2 to 8 hydroxyl groups.  

If necessary, connections can also be used as an output component are used as chain extenders or crosslinking agents and preferably 2 to 8 against have hydrogen atoms which are reactive via isocyanates. Such agents usually have a molecular weight of 32 to 400. Instead of or in addition to hydroxyl groups amino groups, thiol groups or carboxyl groups are also present his.

If necessary, additional aids and additives can be used be used. For example, you can also use chemical Propellants such as water or other volatile organic Use substances as physical blowing agents. Can be used are also catalysts such as tertiary amines such as Dimethylcyclohexylamine, and / or organic metal compounds such as tin salts of carboxylic acids. It can surface-active additives such as emulsifiers or foam stabilizers catalysts, for example siloxane polyether copolymers reaction retarders, cell regulators such as paraffins, fatty alcohols alcohols or dimethylpolysiloxanes, pigments, dyes, flames protective agents such as phosphate esters or phosphonate esters, such as for example trischloroisopropyl phosphate. Can also be used towards stabilizers against aging and weather influences, Plasticizers, fillers, dyes, antistatic agents, nucleation agents medium, pore regulator substances or biocidally active substances.

Suitable catalysts are for example in the in called international patent application WO 96/14354. These include organic amines, amino alcohols and amino ethers such as morpholine compounds, for example dimethylcyclohexylamine, diethanol amine, 2-dimethylaminoethyl-3-dimethylaminopropyl ether, 2-di methylaminoethyl ether, 2,2-dimorpholinodiethyl ether, N, N-Di methylaminoethylmorpholine, N-dimethylmorpholine. Also metal organic compounds such as tin, cobalt or Iron compounds are useful as a catalyst. Can be used is for example tin dioctoate, cobalt naphthenate, dibutyl tin dilaurate and iron acetonylacetate.  

Another object of the invention are blowing agents for Production of foamed plastics that are used on a ver effective foam content of the mixture according to the invention as Propellant gas based. The blowing agents from the invent mixture according to the invention. In addition to the Mixtures according to the invention contain auxiliaries and additives such as water, one or more catalysts, flame retardant tel, emulsifiers, foam stabilizers, binders, crosslinking agents agents, UV stabilizers, nucleating agents and additives if necessary, further propellants.

Another object of the invention are in use plastic foams obtained from the mixtures according to the invention, especially those that fiction, in closed cells moderate mixture. Corresponding inventions are preferred rigid polyurethane foams according to the invention. They can be made from ver produce foamable mixtures which contain 1 to 50% by weight of the Mixture according to the invention as a propellant gas, based on polyol component included.

Flexible polyurethane foams can also be used mixtures according to the invention are produced as propellants. They can be made from known raw material mixtures testify which 1 to 35 wt .-% of the mixture according to the invention as a propellant gas, based on the polyol used as 100% by weight component included.

The mixtures according to the invention have the advantage that they are not flammable liquids. On the other hand, there is pure 1,1,1,3,3-pentafluorobutane on the threshold between flammable and non-flammable substances. It also has one for you che applications to high boiling point. The Ge according to the invention Mixtures have the further advantage that they act as blowing agents advantages for polyurethane foams and easier processing can bring with it. The are particularly favorable given mixtures of HFC-365mfc with HFC-134a in weight ratio  Ratio 93: 7 with a boiling point of approx. 20 ° C as well as mixtures of HFC-365mfc and HFC-227ea in the ratio 87: 13 with one apparent boiling point of approx. 23 ° C. Such mixtures ent speak in their boiling point to the CFC-11 previously used. The Incombustibility of the mixtures according to the invention means for the application has the status of a safety propellant like him was previously awarded for CFC-11. By adjusting the effec tive boiling point of the propellant gases to the recipe Quality of the foams obtained with regard to the insulation behavior be improved, especially when used for deep Temperatures. This is how condensation occurs at low temperatures reduced or avoided. Accordingly, the Foams, especially the polyurethane foams that produced using a propellant according to the invention have been particularly good for insulation purposes in construction and living rich, especially because the closed in Cells contain high levels of thermal insulation bring.

The following examples are intended to illustrate the invention refine without restricting their scope.

Examples Example 1: Preparation of a mixture of 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and 1,1,1,2-tetrafluoroethane (HFC-134a)

465 g of HFC-365mfc was placed in a pressure vessel and 35 g of HFC-134a added. The result is a liquid mixture with a boiling point of around 20 ° C.  

Example 2: Preparation of a mixture of 1,1,1,3,3-pentafluorobutane and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea)

435 g of HFC-365mfc was placed in a pressure vessel and 65 g of HFC-227ea added. The result is a liquid mixture with a boiling point of around 23 ° C.

Example 3: Production of a rigid polyurethane foam with HFC-365mfc / HFC- 134a as a propellant Approach:

• 1. 1.) mixture of
  100 g polyol mixture of polyether polyols and an aromatic brominated polyether polyol, hydroxyl number 450
  20 g tris-chloropropyl phosphate (as flame retardant)
  2 g dimethylcyclohexylamine (as a catalyst)
  1.5 g siloxane polyether copolymer (as foam stabilizer)
  1 g water
  29 g of the mixture prepared according to Example 1 (93 parts of HFC-365mfc and 7 parts of HFC-134a)
• 2. 2.) 131 g of 4,4'-diisocyanatodiphenylmethane

The substances mentioned under 1.) were mixed and obtained The mixture was mixed with the diisocyanate and made into a PUR rigid foam foamed.

The foam has a density of 35 kg / m ³ .

Example 4: Production of a rigid PUR foam with HFC-365mfc / HFC-227ea as Propellant

Example 3 was repeated. 30 g of the propellant according to Example 2 prepared mixture used.

The density of the foam obtained corresponded accordingly Example 3 foam obtained.

Example 5: Production of a rigid PUR foam with HFC-365mfc / HFC-134a as Propellant using glycerin as a polyol Approach:

• 1. Mixture of
  100 g polyol component from a mixture of poly ether polyols and an aromatic brominated polyether polyol, hydroxyl number 450
  11 g of dimethyl methyl phosphonate
  1.8 g of a catalyst mixture
  2 g siloxane polyether copolymer
  1 g water
  32 g of the mixture of HFC-365mfc / HFC-134a prepared according to Example 1
• 2. 2.) 170 g of 4,4'-diisocyanatodiphenylmethane

The mixture obtained by mixing the components mentioned under 1. was foamed with the diisocyanate compound. During the foaming process, a hard PUR foam with a bulk density of 33 kg / m ^{3 was created} .

Example 6: Rigid PUR foam with HFC-365mfc / HFC-227ea

Example 5 was repeated. However, this time 37 g of the in Example 2 produced mixture as a physical propellant used. The density of the foam was 30 g / l.

Example 7: Production of a soft foam Approach:

• 1. Mixture of
  100 g of a polyether polyol with hydroxyl number 56
  0.05 g of dibuthyltin dilaurate as a catalyst
  2 g siloxane polyether copolymer
  10 g of the mixture of HFC-365mfc / HFC-134a mixture prepared according to Example 1
• 2. 2.) 42 g of tolylene diisocyanate

The raw materials were mixed and foamed.

The resulting PUR soft foam had a bulk density of 22 kg / m ³ .

Example 8: Production of a soft PUR foam

Example 7 was repeated, but using 12 g of the mixture according to Example 2.

The bulk density of the foam was 22 kg / m ³ .

Claims (10)

1. Mixture consisting of 50 to 99% by weight 1,1,1,3,3- Pentafluorobutane and 1 to 50 wt .-% of at least one fluorine hydrocarbon selected from the group consisting of 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3,3-hexafluoropropane and 1,1,1,2,3,3,3-heptafluoropropane. 2. Mixture according to claim 1, consisting of 80 to 99 wt .-% 1,1,1,3,3-pentafluorobutane and 1 to 20% by weight of 1,1,1,2-tetra fluoroethane, 1,1,1,3,3,3-hexafluoropropane and / or 1,1,1,2,3,3,3- Heptafluoropropane. 3. Mixture according to claim 2, consisting of 91 to 95 wt .-% 1,1,1,3,3-pentafluorobutane and 5 to 9% by weight 1,1,1,2-tetra fluoroethane with a boiling point in the range of 20 ° C. 4. Mixture according to claim 2, consisting of 85 to 89 wt .-% 1,1,1,3,3-pentafluorobutane and 11 to 15% by weight 1,1,1,2,3,3,3- Heptafluoropropane with a boiling point in the range of 23 ° C. 5. Mixture of 50 wt .-% 1,1,1,3,3-pentafluorobutane and 50% by weight 1,1,1,3,3-pentafluoropropane with a boiling point of 22 ° C. 6. Mixture according to one of the preceding claims, since characterized in that it flows under standard conditions in rivers form. 7. Use of mixtures of claims 1 to 6 as Propellant gas for the production of foamed plastics preferably polyurethane foams and XPS / XPE foams. 8. Use according to claim 7, characterized by the Application for the production of rigid polyurethane foams.   9. Process for the production of foamed plastics using a physical blowing agent based of polyfluoroalkane propellants, characterized in that a physical blowing agent with a propellant gas based on the Mixtures of claims 1 to 6 is used. 10. blowing agent for the production of foamed plastics, based on an effective level of foaming of a Mixture of claims 1 to 6 as a propellant.