EP1599531A1 - Noncombustible premix - Google Patents

Noncombustible premix

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Publication number
EP1599531A1
EP1599531A1 EP04709140A EP04709140A EP1599531A1 EP 1599531 A1 EP1599531 A1 EP 1599531A1 EP 04709140 A EP04709140 A EP 04709140A EP 04709140 A EP04709140 A EP 04709140A EP 1599531 A1 EP1599531 A1 EP 1599531A1
Authority
EP
European Patent Office
Prior art keywords
hfc
blowing agent
agent mixture
premix
combustible
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04709140A
Other languages
German (de)
French (fr)
Inventor
Lothar Zipfel
Karsten BÖRNER
Dierk-Ingolf Recke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Fluor GmbH
Original Assignee
Solvay Fluor GmbH
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Filing date
Publication date
Application filed by Solvay Fluor GmbH filed Critical Solvay Fluor GmbH
Publication of EP1599531A1 publication Critical patent/EP1599531A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to non-combustible polyester polyol and / or polyether polyol premixes for the production of foams, in particular polyurethane foam products.
  • Polyurethane foams are produced by reacting isocyanates with a polyol or a polyol mixture in the presence of blowing agents, preferably hydrofluoric acids.
  • 1, 1, 1, 3,3-pentafluorobutane (HFC 365mfc) as a blowing agent for the production of polyurethane foams is known. Since 1, 1,1, 3,3-pentafluorobutane has a flash point below -27 ° C, it is considered an easily flammable liquid and there are limits to its use as a blowing agent. Therefore, 1, 1, 1, 3,3-pentafluorobutane is usually used in a mixture with other fluorocarbons.
  • blowing agent mixtures contain in addition to HFC 365mfc e.g. 1, 1, 1, 2-tetrafluoroethane (HFC 134a) or 1, 1, 1, 2,3,3,3-heptafluoropropane (HFC 227ea) or 1, 1,1, 3,3-pentafluoropropane (HFC 245fa). These blowing agent mixtures have no flash point and are suitable for the production of foamed plastics.
  • WO 02/099006 describes a non-combustible composition of 1, 1, 1, 3,3-pentafluorobutane, 1,1, 1, 3,3-pentafluoropropane and 1, 2-dichloroethylene.
  • WO 00/56833 describes ternary and quaternary mixtures which, in addition to 1, 1,1,3,3-pentafluorobutane, can also contain N-propyl bromide. It is also known and customary to first produce so-called premixes from the various starting materials for foam production, which are then reacted with the isocyanate. To prepare the premix, polyols or polyethers, blowing agents, catalysts and, if appropriate, further additives are mixed with one another in the required amounts. The foams are then produced by contacting the premix with the isocyanate or isocyanates.
  • the object of the invention is to provide a non-combustible, stable premix for the production of foams which has no flash point.
  • the non-combustible premix for the production of foam products from polyols preferably polyether polyol and / or polyester polyol, additives such as catalyst, stabilizer, additives and blowing agents or blowing agent mixture is characterized in that this premix contains halogenated alkanes.
  • Premixes according to the invention preferably contain
  • polyol preferably polyether polyols or polyester polyols are used;
  • blowing agent mixture in addition to HFC-365mfc at least 5 wt .-%, preferably 7 to 50 wt .-% of another hydrofluorocarbon, preferably HFC 134a Contains HFC 227ea or HFC 245fa;
  • halogenated alkanes preferably means substitution with chlorine or bromine.
  • Compounds from group 1, 2-dichloroethane, 2-chloropropane, 1-bromopropane can be used as halogenated alkanes.
  • phosphorus compounds as flame retardants is unnecessary - preferably no phosphorus compounds are used.
  • known phosphorus-based flame retardants could also be used.
  • additives such as e.g. Catalyst, stabilizer and other additives added.
  • the premix according to the invention is brought into contact with the isocyanate or isocyanates and foamed in a known manner.
  • Polyisocyanates for example with 2 to 4 isocyanate groups, are usually used to produce the polyurethane foams. Their manufacture and the basic chemicals that can be used for them are known.
  • isocyanates have an aliphatic hydrocarbon residue with up to 18 carbon atoms, a cycloaliphatic hydrocarbon residue with up to 15 carbon atoms, an aromatic hydrocarbon residue with 6 to 15 carbon atoms or an araliphatic hydrocarbon residue with 8 to 15 carbon atoms on.
  • Technically particularly preferred starting components are, for example, 2,4- and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate and mixtures thereof.
  • So-called modified polyisocyanates can also be used, which contain carbodiimide groups, urethane groups, alophnate groups, isocyanorate groups, urea groups or urethral groups.
  • Other starting components are compounds with at least 2 hydrogen atoms which are reactive toward isocyanates.
  • they are compounds with a molecular weight of 300 to 10,000, which preferably have 2 to 8 hydroxyl groups and can also have amino groups, thio groups or carboxyl groups.
  • Chemical blowing agents such as water can also be used as additional aids and additives in the system to be foamed.
  • Catalysts such as, for example, tertiary amines, such as dimethylcyclohexylamine, and / or organic metals can also be used. metal compounds.
  • Surface-active additives such as emulsifiers or foam stabilizers, for example siloxane-polyether copolymers, reaction retarders, cell regulators such as paraffins, fatty alcohols or dimethylpolysiloxanes, pigments and dyes can be used. Stabilizers against aging and weather influences, fillers, dyes, antistatic agents, nucleating agents, pore regulator substances or biocide-active substances can also be used.
  • Suitable catalysts are mentioned, for example, in international patent application WO 96/14354. These include organic amines, amino alcohols and amino ethers such as morphoine compounds, for example dimethylcyclohexylamine, diethanolamine, 2-dimethylaminoethyl-3-dimethylaminopropyl ether, 2-dimethylaminoethyl ether, 2,2-dimorpholinodiethyl ether, N, N-dimethylaminoethylmorpholine, N-dimethylmorpholine.
  • Organometallic compounds such as tin, cobalt or iron compounds are also useful as catalysts. For example, tin dioctate, cobalt naphthenate, dibutyltin dilaurate and iron acetone acetate can be used.
  • the advantage of the premix according to the invention is that the addition behavior of halogenated alkanes obviously modifies the dissolving behavior of the components, so that the flash point increases and the "combustible" classification is omitted. This makes it easy to store and transport the premix.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention relates to noncombustible polyether polyol and/or polyester polyol mixtures for producing foam products, particularly PU foam materials. According to the invention, the premix contains polyol, more that 4 % by weight of an expanding agent mixture consisting of HFC 365mfc and of at least one additional fluorohydrocarbon, and contains halogenated alkanes.

Description

Nichtbrennbare Vormischung Non-flammable premix
Beschreibungdescription
Die vorliegende Erfindung betrifft nichtbrennbare Polyesterpolyol- und/oder Poly- etherpolyolvormischungen zur Herstellung von Schaumstoffen, insbesondere von Polyurethanschaumprodukten.The present invention relates to non-combustible polyester polyol and / or polyether polyol premixes for the production of foams, in particular polyurethane foam products.
Polyurethanschäume werden durch Umsetzung von Isocyanaten mit einem Polyol oder einer Polyolmischung in Gegenwart von Treibmittel, vorzugsweise Hydrofluoraikanen hergestellt.Polyurethane foams are produced by reacting isocyanates with a polyol or a polyol mixture in the presence of blowing agents, preferably hydrofluoric acids.
Die Verwendung von 1 ,1 ,1 ,3,3-Pentafluorbutan (HFC 365mfc) als Treibmittel zur Herstellung von Polyurethanschaumstoffen ist bekannt. Da 1 ,1,1 ,3,3-Pentafluorbutan einen Flammpunkt unter -27 °C besitzt, gilt es als leicht entzündliche Flüssigkeit und seiner Verwendung als Treibmittel sind Grenzen gesetzt. Üblicherweise wird daher 1 ,1 ,1 ,3,3- Pentafluorbutan im Gemisch mit anderen Fluorkohlenwasserstoffen eingesetzt.The use of 1, 1, 1, 3,3-pentafluorobutane (HFC 365mfc) as a blowing agent for the production of polyurethane foams is known. Since 1, 1,1, 3,3-pentafluorobutane has a flash point below -27 ° C, it is considered an easily flammable liquid and there are limits to its use as a blowing agent. Therefore, 1, 1, 1, 3,3-pentafluorobutane is usually used in a mixture with other fluorocarbons.
Bekannte Treibmittelmischungen enthalten neben HFC 365mfc z.B. 1 ,1 ,1 ,2- Tetrafluorethan (HFC 134a) oder 1 ,1 ,1 , 2,3,3,3-Heptafluorpropan (HFC 227ea) oder 1 ,1,1 ,3,3-Pentafluorpropan (HFC 245fa). Diese Treibmittelgemische haben keinen Flammpunkt und eignen sich zur Herstellung von geschäumten Kunststoffen.Known blowing agent mixtures contain in addition to HFC 365mfc e.g. 1, 1, 1, 2-tetrafluoroethane (HFC 134a) or 1, 1, 1, 2,3,3,3-heptafluoropropane (HFC 227ea) or 1, 1,1, 3,3-pentafluoropropane (HFC 245fa). These blowing agent mixtures have no flash point and are suitable for the production of foamed plastics.
WO 02/099006 beschreibt eine nichtbrennbare Zusammensetzung aus 1 ,1 ,1 ,3,3- Pentafluorbutan, 1,1 ,1 ,3,3-Pentafluorpropan und 1 ,2-Dichlorethylen.WO 02/099006 describes a non-combustible composition of 1, 1, 1, 3,3-pentafluorobutane, 1,1, 1, 3,3-pentafluoropropane and 1, 2-dichloroethylene.
US 2002/019822273 A 1 beschreibt eine Treibmittelmischung, die keinen Flammpunkt aufweist. Diese Treibmittelmischung enthält neben bekannten fluorhaltigen Treibmitteln 2-Chlorpropan.US 2002/019822273 A1 describes a blowing agent mixture which has no flash point. In addition to known fluorine-containing blowing agents, this blowing agent mixture contains 2-chloropropane.
WO 00/56833 beschreibt ternäre und quaternäre Gemische, die neben 1 ,1,1,3,3- Pentafluorbutan auch N-Propylbromid enthalten können. Es ist ebenfalls bekannt und üblich, zur Schaumherstellung zunächst aus den verschiedenen Einsatzstoffen so genannte Vormischungen herzustellen, die dann mit dem Isocyanat zur Reaktion gebracht werden. Zur Herstellung der Vormischung werden Polyole oder Polyether, Treibmittel, Katalysatoren und gegebenenfalls weitere Additive in den benötigten Mengen miteinander vermischt. Die Schäume werden dann durch Inkon- taktbringen der Vormischung mit dem Isocyanat bzw. Isocyanaten hergestellt.WO 00/56833 describes ternary and quaternary mixtures which, in addition to 1, 1,1,3,3-pentafluorobutane, can also contain N-propyl bromide. It is also known and customary to first produce so-called premixes from the various starting materials for foam production, which are then reacted with the isocyanate. To prepare the premix, polyols or polyethers, blowing agents, catalysts and, if appropriate, further additives are mixed with one another in the required amounts. The foams are then produced by contacting the premix with the isocyanate or isocyanates.
Werden Vormischungen unter Verwendung von den genannten Treibmittelmischungen hergestellt, kann es bei Überschreitung einer kritischen Treibmittelmenge überraschenderweise dazu kommen, dass das gesamte System aufgrund des niedrigen Flammpunktes als brennbar einzustufen ist, obwohl Treibmittelmischung und Polyol- system für sich nicht brennbar sind.If premixes are produced using the blowing agent mixtures mentioned, if a critical amount of blowing agent is exceeded, it can surprisingly occur that the entire system is to be classified as combustible due to the low flash point, although the blowing agent mixture and polyol system are not combustible in themselves.
Die Aufgabe der Erfindung besteht darin, eine nichtbrennbare, stabile Vormischung zur Herstellung von Schaumstoffen bereitzustellen, die keinen Flammpunkt aufweist.The object of the invention is to provide a non-combustible, stable premix for the production of foams which has no flash point.
Gemäß der Erfindung ist die nichtbrennbare Vormischung zur Herstellung von Schaumprodukten aus Polyolen, vorzugsweise Polyetherpolyol und/oder Polyesterpolyol, Zusatzstoffen wie Katalysator, Stabilisator, Additiven und Treibmittel oder Treibmittelmischung dadurch gekennzeichnet, dass diese Vormischung halogenierte Alkane enthält.According to the invention, the non-combustible premix for the production of foam products from polyols, preferably polyether polyol and / or polyester polyol, additives such as catalyst, stabilizer, additives and blowing agents or blowing agent mixture is characterized in that this premix contains halogenated alkanes.
Erfindungsgemäße Vormischungen enthalten bevorzugtPremixes according to the invention preferably contain
a) Polyol, vorzugsweise werden Polyetherpolyole oder Polyesterpolyole eingesetzt;a) polyol, preferably polyether polyols or polyester polyols are used;
b) '4 bis 35 Gew.-%, vorzugsweise 10 bis 15 Gew.-% Treibmittelmischung, wobei die Treibmittelmischung neben HFC 365mfc mindestens 5 Gew.-%, vorzugsweise 7 bis 50 Gew.-% eines weiteren Fluorkohlenwasserstoffes, vorzugsweise HFC 134a, HFC 227ea oder HFC 245fa enthält;b) '4 to 35 wt .-%, preferably 10 to 15 wt .-% blowing agent mixture wherein the blowing agent mixture in addition to HFC-365mfc at least 5 wt .-%, preferably 7 to 50 wt .-% of another hydrofluorocarbon, preferably HFC 134a Contains HFC 227ea or HFC 245fa;
und sind gekennzeichnet durch einen Zusatz von halogenierten Alkanen. In Bezug auf die "halogenierten Alkane" bedeutet "halogeniert" bevorzugt die Substitution durch Chlor oder Brom. Als halogenierte Alkane können Verbindungen aus der Gruppe 1 ,2-Dichlorethan, 2-Chlorpropan, 1 -Brompropan eingesetzt werden.and are characterized by the addition of halogenated alkanes. With respect to the "halogenated alkanes", "halogenated" preferably means substitution with chlorine or bromine. Compounds from group 1, 2-dichloroethane, 2-chloropropane, 1-bromopropane can be used as halogenated alkanes.
Zusatz von Phosphorverbindungen als Flammschutzmittel ist unnötig - bevorzugt werden keine Phosphorverbindungen eingesetzt. Es könnten aber zusätzlich bekannte Flammschutzmittel auf Phosphorbasis eingesetzt werden.The addition of phosphorus compounds as flame retardants is unnecessary - preferably no phosphorus compounds are used. However, known phosphorus-based flame retardants could also be used.
Der Vormischung werden in bekannter Art und Weise weitere Zusatzstoffe wie z.B. Katalysator, Stabilisator und weitere Additive zugemischt.In the known manner, further additives such as e.g. Catalyst, stabilizer and other additives added.
Die erfindungsgemäße Vormischung wird in bekannter Art und Weise mit dem Isocyanat bzw. Isocyanaten in Kontakt gebracht und verschäumt.The premix according to the invention is brought into contact with the isocyanate or isocyanates and foamed in a known manner.
Zur Herstellung der Polyurethanschäume werden üblicherweise Polyisocyanate beispielsweise mit 2 bis 4 Isocyanatgruppen eingesetzt. Ihre Herstellung und die dafür verwendbaren Grundchemikalien sind bekannt.Polyisocyanates, for example with 2 to 4 isocyanate groups, are usually used to produce the polyurethane foams. Their manufacture and the basic chemicals that can be used for them are known.
Diese Isocyanate weisen einen aliphatischen Kohlenwasserstoff rest mit bis zu 18 C- Atomen, einen cycloaliphatischen Kohlenwasserstoff rest mit bis zu 15 C-Atomen, einen aromatischen Kohlenwasserstoff rest mit 6 bis 15 C-Atomen oder einen araliphatischen Kohlenwasserstoff rest mit 8 bis 15 C-Atomen auf. Technisch besonders bevorzugte Ausgangskomponenten sind beispielsweise 2,4- und 2,6-Toluylendiisocyanat, Diphenyl- methandiisocyanat, Polymethylenpolyphenylisocyanat und deren Mischungen. Es können such so genannte modifizierte Polyisocyanate eingesetzt werden, welche Carbodiimidgrup- pen, Urethangruppen, Alophnatgruppen, Isocyanoratgruppen, Harnstoffgruppen oder Biu- retgruppen enthalten.These isocyanates have an aliphatic hydrocarbon residue with up to 18 carbon atoms, a cycloaliphatic hydrocarbon residue with up to 15 carbon atoms, an aromatic hydrocarbon residue with 6 to 15 carbon atoms or an araliphatic hydrocarbon residue with 8 to 15 carbon atoms on. Technically particularly preferred starting components are, for example, 2,4- and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate and mixtures thereof. So-called modified polyisocyanates can also be used, which contain carbodiimide groups, urethane groups, alophnate groups, isocyanorate groups, urea groups or urethral groups.
Weitere Ausgangskomponenten sind Verbindungen mit mindestens 2 gegenüber Isocyanaten reaktionsfähigen Wasserstoffatomen. Es handelt sich insbesondere umNer- bindungen mit einem Molekulargewicht von 300 bis 10.000, welche vorzugsweise 2 bis 8 Hydroxylgruppen aufweisen und außerdem Aminogruppen, Thiogruppen oder Carboxyl- gruppen aufweisen können.Other starting components are compounds with at least 2 hydrogen atoms which are reactive toward isocyanates. In particular, they are compounds with a molecular weight of 300 to 10,000, which preferably have 2 to 8 hydroxyl groups and can also have amino groups, thio groups or carboxyl groups.
Als weitere Hilfs- und Zusatzmittel kann man dem zu verschäumenden System zusätzlich chemische Treibmittel wie Wasser einsetzen. Einsetzbar sind auch Katalysatoren wie beispielsweise tertiäre Amine, wie Dimethylcyclohexylamin, und/oder organische Me- tallverbindungen. Es können oberflächenaktive Zusatzstoffe wie Emulgatoren oder Schaumstabilisatoren, beispielsweise Siloxanpolyetherkopolymere eingesetzt werden, Reaktionsverzögerer, Zellregler wie Paraffine, Fettalkohole oder Dimethylpolysiloxane, Pigmente und Farbstoffe. Einsetzbar sind weiterhin Stabilisatoren gegen Alterungs- und Witterungseinflüsse, Füllstoffe, Farbstoffe, Antistatika, Nukleisierungsmittei, Porenregler- substanzen oder Biocid-wirksame Wirkstoffe.Chemical blowing agents such as water can also be used as additional aids and additives in the system to be foamed. Catalysts such as, for example, tertiary amines, such as dimethylcyclohexylamine, and / or organic metals can also be used. metal compounds. Surface-active additives such as emulsifiers or foam stabilizers, for example siloxane-polyether copolymers, reaction retarders, cell regulators such as paraffins, fatty alcohols or dimethylpolysiloxanes, pigments and dyes can be used. Stabilizers against aging and weather influences, fillers, dyes, antistatic agents, nucleating agents, pore regulator substances or biocide-active substances can also be used.
Gut geeignete Katalysatoren sind beispielsweise in der internationalen Patentanmeldung WO 96/14354 genannt. Dazu zählen organische Amine, Aminoalkohole und Aminoether wie Morphoiinverbindungen, beispielsweise Dimethylcyclohexylamin, Di- ethanolamin, 2-Dimethylaminoethyl-3-dimethylaminopropylether, 2-Dimethylamino- ethylether, 2,2-Dimorpholinodiethylether, N,N-Dimethylaminoethylmorpholin, N-Dimethyl- morpholin. Auch metallorganische Verbindungen wie beispielsweise Zinn-, Kobalt- oder Eisenverbindungen sind brauchbar als Katalysator. Einsetzbar ist beispielsweise Zinn- dioctat, Kobaltnaphthenat, Dibutylzinndilaurat und Eisenacetonylacetat.Suitable catalysts are mentioned, for example, in international patent application WO 96/14354. These include organic amines, amino alcohols and amino ethers such as morphoine compounds, for example dimethylcyclohexylamine, diethanolamine, 2-dimethylaminoethyl-3-dimethylaminopropyl ether, 2-dimethylaminoethyl ether, 2,2-dimorpholinodiethyl ether, N, N-dimethylaminoethylmorpholine, N-dimethylmorpholine. Organometallic compounds such as tin, cobalt or iron compounds are also useful as catalysts. For example, tin dioctate, cobalt naphthenate, dibutyltin dilaurate and iron acetone acetate can be used.
Der Vorteil der erfindungsgemäßen Vormischung besteht darin, dass durch die Zugabe von halogenierten Alkanen offensichtlich das Löseverhalten der Komponenten modifiziert wird, so dass der Flammpunkt sich erhöht und die Einstufung "brennbar" entfällt. Somit ist eine einfache Lagerung und Transport der Vormischung möglich. The advantage of the premix according to the invention is that the addition behavior of halogenated alkanes obviously modifies the dissolving behavior of the components, so that the flash point increases and the "combustible" classification is omitted. This makes it easy to store and transport the premix.

Claims

Patentansprüche claims
1. Nichtbrennbare Vormischung zur Herstellung von Schaumprodukten aus Polyetherpolyol und/oder Polyesterpolyol, Zusatzstoffen wie Katalysator, Stabilisator, Additiven und Treibmittel oder Treibmittelmischung gekennzeichnet dadurch, dass diese Vormischung halogenierte Alkane enthält.1. Non-combustible premix for the production of foam products from polyether polyol and / or polyester polyol, additives such as catalyst, stabilizer, additives and blowing agents or blowing agent mixture, characterized in that this premix contains halogenated alkanes.
2. Nichtbrennbare Vormischung nach Anspruch 1 , dadurch gekennzeichnet, dass als halogenierte Alkane 1.2. Dichlorethan, 2-Chlorpropan, 1-Brompropan enthalten sind.2. Non-combustible premix according to claim 1, characterized in that as halogenated alkanes 1.2. Dichloroethane, 2-chloropropane, 1-bromopropane are included.
3. Nichtbrennbare Vormischung nach Anspruch 1 , dadurch gekennzeichnet, dass eine Treibmittelmischung eingesetzt wird, die 1 ,1 ,1 ,3,3-Pentafluorbutan (HFC-365mfc) und mindestens einen weiteren Fluorkohlenwasserstoff enthält.3. Non-combustible premix according to claim 1, characterized in that a blowing agent mixture is used which contains 1, 1, 1, 3,3-pentafluorobutane (HFC-365mfc) and at least one further fluorocarbon.
4. Nichtbrennbare Vormischung nach Anspruch 3, dadurch gekennzeichnet, dass der oder die weiteren Fluorkohlenwasserstoffe ausgewählt werden aus der Gruppe bestehend aus 1 ,1 ,1 ,2-Tetrafluorethan (HFC-134a), 1 ,1,1 ,2,3,3,3-Heptafluorpropan (HFC- 227ea) und 1 ,1 ,1, 3,3-Pentafluorpropan (HFC-245fa).4. Non-combustible premix according to claim 3, characterized in that the one or more fluorohydrocarbons are selected from the group consisting of 1, 1, 1, 2-tetrafluoroethane (HFC-134a), 1, 1,1, 2,3,3 , 3-heptafluoropropane (HFC-227ea) and 1, 1, 1, 3,3-pentafluoropropane (HFC-245fa).
5. . Nichtbrennbare Vormischung nach Anspruch 3, dadurch gekennzeichnet, dass der oder die weiteren Fluorkohlenwasserstoffe in einer Menge von mindestens 5 Gew.-% in der Treibmittelmischung enthalten sind, wobei die Summe der Treibmittel (die Treibmittelmischung) als 100 Gew.-% gesetzt ist.5.. Non-combustible premix according to claim 3, characterized in that the further fluorocarbon or hydrocarbons are contained in an amount of at least 5% by weight in the blowing agent mixture, the sum of the blowing agents (the blowing agent mixture) being set as 100% by weight.
6. Nichtbrennbare Vormischung nach Anspruch 4, dadurch gekennzeichnet, dass der oder die weiteren Fluorkohlenwasserstoffe in einer Menge von 7 bis 50 Gew.-% in der Treibmittelmischung enthalten sind, wobei die Summe der Treibmittel (die Treibmittelmischung als 100 Gew.-% gesetzt ist.6. Non-combustible premix according to claim 4, characterized in that the further fluorocarbon or hydrocarbons are contained in an amount of 7 to 50% by weight in the blowing agent mixture, the sum of the blowing agents (the blowing agent mixture being set as 100% by weight) ,
7. Nichtbrennbare Vormischung nach Anspruch 4, dadurch gekennzeichnet, dass die Treibmittelmischung aus HFC-365mfc sowie mindestens einem weiteren Treibmittel aus der Gruppe bestehend aus 1 ,1 ,1 ,2-Tetrafluorethan (HFC-134a), 1 ,1 ,1 ,2,3,3,3- Heptafluorpropan (HFC-227ea) und 1 ,1 ,1 ,3,3-Pentafluorpropan (HFC-245fa) besteht. 7. Non-combustible premix according to claim 4, characterized in that the blowing agent mixture of HFC-365mfc and at least one further blowing agent from the group consisting of 1, 1, 1, 2-tetrafluoroethane (HFC-134a), 1, 1, 1, 2 , 3,3,3-heptafluoropropane (HFC-227ea) and 1, 1, 1, 3,3-pentafluoropropane (HFC-245fa).
EP04709140A 2003-02-22 2004-02-07 Noncombustible premix Withdrawn EP1599531A1 (en)

Applications Claiming Priority (3)

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DE10307572A DE10307572A1 (en) 2003-02-22 2003-02-22 Non-flammable premix
DE10307572 2003-02-22
PCT/EP2004/001134 WO2004074358A1 (en) 2003-02-22 2004-02-07 Noncombustible premix

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FR2868428B1 (en) * 2004-04-06 2006-06-23 Arkema Sa NON-FLAMMABLE COMPOSITION USEFUL AS SWELLING AGENT
MX2013010824A (en) * 2011-03-23 2013-10-17 Dow Global Technologies Llc Phosphorous-containing flame retardants for polyurethane foams.

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WO1998027145A1 (en) * 1996-12-17 1998-06-25 Solvay Fluor Und Derivate Gmbh Mixtures containing 1,1,1,3,3 pentafluorobutane
ATE302812T1 (en) * 1998-05-22 2005-09-15 Solvay Fluor Gmbh BLOWING AGENT COMPOSITION FOR PRODUCING FOAMED THERMOPLASTICS
DE10024590A1 (en) * 2000-05-19 2001-11-29 Solvay Fluor & Derivate Non-combustible polyether and/or polyol pre-mixes, useful for production of foams in apparatus without explosion protection, contain 1,1,1,3,3-pentafluorobutane
JP2002047323A (en) * 2000-05-26 2002-02-12 Bridgestone Corp Rigid polyurethane foam and its production method
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CN1753940A (en) 2006-03-29
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KR20050104380A (en) 2005-11-02
RU2005129294A (en) 2006-06-27
US20060033079A1 (en) 2006-02-16
JP2006518401A (en) 2006-08-10
DE10307572A1 (en) 2004-09-02
WO2004074358A1 (en) 2004-09-02

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