WO2004081092A1 - Hydrofluorocarbon compositions - Google Patents

Hydrofluorocarbon compositions Download PDF

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Publication number
WO2004081092A1
WO2004081092A1 PCT/EP2004/002656 EP2004002656W WO2004081092A1 WO 2004081092 A1 WO2004081092 A1 WO 2004081092A1 EP 2004002656 W EP2004002656 W EP 2004002656W WO 2004081092 A1 WO2004081092 A1 WO 2004081092A1
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WO
WIPO (PCT)
Prior art keywords
hfc
365mfc
polyurethane
composition according
polyol
Prior art date
Application number
PCT/EP2004/002656
Other languages
French (fr)
Inventor
Lothar Zipfel
Werner Kruecke
Karsten Boerner
Pierre Dournel
Dierk-Ingolf Recke
Original Assignee
Solvay (Société Anonyme)
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to ES04720003T priority Critical patent/ES2393920T3/en
Application filed by Solvay (Société Anonyme) filed Critical Solvay (Société Anonyme)
Priority to KR1020137013427A priority patent/KR20130087539A/en
Priority to JP2006504688A priority patent/JP2007524716A/en
Priority to MXPA05009797A priority patent/MXPA05009797A/en
Priority to CA2518050A priority patent/CA2518050C/en
Priority to BRPI0408294-0A priority patent/BRPI0408294A/en
Priority to AU2004220348A priority patent/AU2004220348B2/en
Priority to EP04720003A priority patent/EP1606340B1/en
Priority to US10/548,895 priority patent/US20060160910A1/en
Publication of WO2004081092A1 publication Critical patent/WO2004081092A1/en
Priority to IL170449A priority patent/IL170449A/en
Priority to US12/400,345 priority patent/US20090286898A1/en
Priority to US14/712,175 priority patent/US9963539B2/en

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Classifications

    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • 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
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • 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 compositions of 1,1,1,3,3-pentafluoro- butane (HFC-365mfc) and 1,1,1,3,3-pentafh ⁇ oropropane (HFC-245fa), which are useful as blowing agents for polymer foams.
  • HFC-365mfc and HFC-245fa are suitable in particular for the manufacture of polyurethane foams and modified polyurethane foams such as polyisocyanurate foams.
  • US patent 6,080,799 discloses inter alia a blowing agent mixture of HFC-365mfc/HFC-245fa.
  • blowing agent composition which does not display a flash point when used in fully formulated systems and which allows for manufacture of foams which display good insulation properties over a wide temperature range.
  • the invention concerns a composition which comprises 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) in a weight ratio HFC-365mfc/HFC-245fa of from 60:40 to 75:25.
  • HFC-365mfc 1,1,1,3,3-pentafluorobutane
  • HFC-245fa 1,1,1,3,3-pentafluoropropane
  • the compositions according to the invention allow for safe manufacture of (modified) polyurethane foams with fully formulated systems having no flash point whereas obtained closed-cell foams are particularly suitable for thermal insulation at low temperatures, as condensation of the cell gas can be substantially avoided.
  • Polyurethane is understood to mean the polymers resulting essentially from the reaction of polyols and of isocyanates.
  • Modified polyurethane is understood to mean the polymers resulting from the reaction of polyols and of isocyanates which contain, in addition to urethane functional groups, other types of functional groups, in particular triisocyanuric rings formed by trimerization of isocyanates. These modified polyurethanes are normally known as polyisocyanurates. These polymers are typically obtained from formulations exhibiting an isocyanate number from 180 to 550. In the composition according to the invention, the weight ratio HFC-365mfc/HFC-245fa is greater than or equal to 60:40.
  • the weight ratio HFC-365mfc HFC-245fa is greater than or equal to 65:35.
  • the weight ratio HFC-365mfc HFC-245fa is greater than or equal to 67:33.
  • a weight ratio HFC-365mfc/HFC-245fa of about 70:30 is particularly preferred.
  • the weight ratio HFC-365mfc/HFC-245fa is lower than or equal to 75:25. Often the weight ratio HFC-365mfc/HFC-245fa is lower than or equal to 73:27. Preferably, the weight ratio ITFC-365rnfc/HFC-245fa is lower than or equal to 72:28.
  • the compositions according to the invention which consist essentially of
  • HFC-365mfc and HFC-245fa are particularly preferred.
  • the invention concerns also a premix intended for the preparation of polyurethane or modified polyurethane foams comprising a) at least one polyol b) a catalyst for the reaction of isocyanates with polyols c) a composition according to the invention
  • premix is understood to mean any composition comprising at least one polyol, at least one blowing agent and at least one catalyst.
  • the compositions according to the invention are chemically stable in the premix. Consequently, the latter can optionally be formulated without a stabilizer against the potential degradation of the composition according to the invention.
  • polyol is understood to mean any compound containing at least two functional groups which react with isocyanates. These functional groups contain at least one active hydrogen atom, such as defined by the Zerewittinof reaction.
  • the active hydrogen atom is generally a hydrogen atom bonded to an oxygen, nitrogen or sulphur atom.
  • Any polyol conventionally used to prepare polyurethane foams can be used in the premixes according to the invention. Mention may in particular be made of polyether polyols and polyester polyols.
  • the catalyst of the premixes according to the invention comprises a compound with catalyses the formation of the -NH-CO-O- urethane bond by reaction between a polyol and an isocyanate or which activates the reaction between an isocyanate and water, such as tertiary amines and organic tin, iron, mercury or lead compounds.
  • Mention may in particular by made, as tertiary amines, of triethylamine, N,N-dimethylcyclohexylamine DMCHA), N-methylmorpholine (NMM), N-ethylmorpholine, dimethylethanolamine, diaza[2.2.2]bicyclooctane (triethylenediamine) and substituted benzylamines, such as N,N-dimethylbenzylamine DB). Mention may in particular be made, as organic tin or lead compounds, of dibutyltin dilaurate, stannous octanoate and lead octanoate.
  • the catalyst of the premixes according to the invention can, in particular when the latter are intended for the manufacture of modified polyurethane (polyisocyanurate) foams, comprise a compound which catalyses the trimerization of isocyanates to triisocyanurates.
  • Compounds which catalyse the trimerization of isocyanates which can be used in the premixes according to the invention are in particular triazines.
  • the premixes according to the invention can additionally contain various additives commonly used to prepare polyurethane or modified polyurethane foams, such as, in particular, water, surface-active agents, antioxidizing agents, fiame-retardant agents and/or pigments.
  • various additives commonly used to prepare polyurethane or modified polyurethane foams such as, in particular, water, surface-active agents, antioxidizing agents, fiame-retardant agents and/or pigments.
  • the more particularly preferred premixes according to the invention are essentially composed of at least one polyol, the composition according to the invention, at least one catalyst which promotes the polyol/isocyanate reaction and at least one of the usual additives mentioned above.
  • proportions of polyol, catalyst, the composition according to the invention and optional additives in the premixes according to the invention vary, in particular according to the application, the type of foam prepared, the nature of the polyol and the nature of the catalyst.
  • the amount of catalyst used generally varies from approximately 0.05 to 10 parts by weight per 100 parts by weight of polyol.
  • the amount of the composition according to the invention is from 1 to 80 parts by weight per 100 parts by weight of polyol. It is preferably from 10 to 60 parts by weight per 100 parts by weight of polyol.
  • the amounts of water, surface-active agents, plasticizing agents and/or flame-retardant agents are those conventionally used to prepare polyurethane or modified polyurethane foams.
  • the invention also relates to a process for the manufacture of polyurethane or modified polyurethane foams, in which at least one isocyanate is reacted with at least one polyol in the presence of the composition according to the invention, of at least one catalyst and, optionally, of other usual additives.
  • Any isocyanate conventionally used to manufacture such foams can be used in the process according to the invention. Mention may be made, by way of example, of aliphatic isocyanates, such as hexamethylene diisocyanate, and aromatic isocyanates, such as tolylene diisocyanate or diphenylmethane diisocyanate.
  • the process according to the invention is carried out in the presence of water.
  • the amount of water used is preferably equal to or greater than 1 part by weight per 100 parts of polyol. More preferably, the amount of water used equal to or greater than 1.5 parts by weight per 100 parts of polyol.
  • the amount of water used is preferably equal to or less than 2.5 parts by weight per 100 parts of polyol. More preferably, the amount of water used equal to or less than 2 parts by weight per 100 parts of polyol.
  • the composition according to the invention can be supplied to the reaction in the form of the premix according to the invention.
  • the composition according to the invention can also be supplied to the reaction in the form of a mixture of the composition with the isocyanate.
  • the invention concerns also a polyurethane or modified polyurethane foam which is obtainable according to the process according to the invention.
  • the polyurethane or modified polyurethane foam according to the invention is preferably a rigid closed-cell foam.
  • the polyurethane or modified polyurethane foam can also be selected from a flexible or semi-flexible foam, an integral skin foam and a monocomponent foam.
  • the invention concerns also a thermal insulation material, which comprises a polyurethane or modified polyurethane foam according to the invention.
  • thermal insulation material according to the invention include insulation panels, tubes for pipe insulation, sandwich panels, laminates and block foams.
  • the thermal insulation material according to the invention generally substantially keeps its insulating properties when used in contact with an atmosphere having a temperature of 10°C or lower. Often the temperature of use can be 5°C or lower. The temperature can even be 0°C or lower without substantial condensation.
  • the thermal insulation material according to the invention is particularly suitable when used in contact with an atmosphere having a temperature of - 10°C or higher.
  • the examples here after are intended to illustrate the invention in a non- limitative manner.
  • Example 1 PUR manufacture with a 70:30 composition of HFC-365mfc and HFC-245 fa A preparation of HFC-365mfc/HFC-2 5fa in a ratio 70:30 starts boiling at
  • Example 2 PUR manufacture with a 75:25 composition of HFC-365mfc/ HFC-245fa
  • Example 1 was repeated with 20g of HFC-365mfc/HFC-245fa in a ratio 75:25 having a boiling start of 28°C.
  • the density was the same as in Example 1.
  • Example 1 was repeated, adding the blowing agent composition separately, at first 14g HFC-365mfc and then 6 g of HFC-245fa, using a dip tube. A rigid foam was obtained with a density of 35 kg/m 3 .
  • compositions do not present any flash point when used in a premix with polyols.

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

Abstract

A composition which comprises 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) in a weight ratio HFC-365mfc/HFC-245fa of from 60:40 to 75:25.

Description

Hydrofluorocarbon compositions
The present invention relates to compositions of 1,1,1,3,3-pentafluoro- butane (HFC-365mfc) and 1,1,1,3,3-pentafhιoropropane (HFC-245fa), which are useful as blowing agents for polymer foams. Mixtures HFC-365mfc and HFC-245fa are suitable in particular for the manufacture of polyurethane foams and modified polyurethane foams such as polyisocyanurate foams. US patent 6,080,799 discloses inter alia a blowing agent mixture of HFC-365mfc/HFC-245fa.
It has been discovered that in certain formulated systems for polyurethanes containing polyols and mixtures of HFC-365mfc and HFC-245fa, a flash point may be observed in spite of the nonflammable nature of the polyols and of the mixtures of HFC-365mfc and HFC-245fa respectively.
It was desirable to find a blowing agent composition which does not display a flash point when used in fully formulated systems and which allows for manufacture of foams which display good insulation properties over a wide temperature range.
Consequently, the invention concerns a composition which comprises 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) in a weight ratio HFC-365mfc/HFC-245fa of from 60:40 to 75:25. It has been found, surprisingly, that the compositions according to the invention allow for safe manufacture of (modified) polyurethane foams with fully formulated systems having no flash point whereas obtained closed-cell foams are particularly suitable for thermal insulation at low temperatures, as condensation of the cell gas can be substantially avoided. Polyurethane is understood to mean the polymers resulting essentially from the reaction of polyols and of isocyanates. These polymers are typically obtained from formulations exhibiting an isocyanate number from 100 to 180. Modified polyurethane is understood to mean the polymers resulting from the reaction of polyols and of isocyanates which contain, in addition to urethane functional groups, other types of functional groups, in particular triisocyanuric rings formed by trimerization of isocyanates. These modified polyurethanes are normally known as polyisocyanurates. These polymers are typically obtained from formulations exhibiting an isocyanate number from 180 to 550. In the composition according to the invention, the weight ratio HFC-365mfc/HFC-245fa is greater than or equal to 60:40. Often the weight ratio HFC-365mfc HFC-245fa is greater than or equal to 65:35. Preferably, the weight ratio HFC-365mfc HFC-245fa is greater than or equal to 67:33. A weight ratio HFC-365mfc/HFC-245fa of about 70:30 is particularly preferred.
In the composition according to the invention, the weight ratio HFC-365mfc/HFC-245fa is lower than or equal to 75:25. Often the weight ratio HFC-365mfc/HFC-245fa is lower than or equal to 73:27. Preferably, the weight ratio ITFC-365rnfc/HFC-245fa is lower than or equal to 72:28. The compositions according to the invention, which consist essentially of
HFC-365mfc and HFC-245fa are particularly preferred.
The invention concerns also a premix intended for the preparation of polyurethane or modified polyurethane foams comprising a) at least one polyol b) a catalyst for the reaction of isocyanates with polyols c) a composition according to the invention
For the purposes of the present invention, premix is understood to mean any composition comprising at least one polyol, at least one blowing agent and at least one catalyst. Surprisingly, the compositions according to the invention are chemically stable in the premix. Consequently, the latter can optionally be formulated without a stabilizer against the potential degradation of the composition according to the invention.
For the purposes of the present invention, polyol is understood to mean any compound containing at least two functional groups which react with isocyanates. These functional groups contain at least one active hydrogen atom, such as defined by the Zerewittinof reaction. The active hydrogen atom is generally a hydrogen atom bonded to an oxygen, nitrogen or sulphur atom. Any polyol conventionally used to prepare polyurethane foams can be used in the premixes according to the invention. Mention may in particular be made of polyether polyols and polyester polyols.
The catalyst of the premixes according to the invention comprises a compound with catalyses the formation of the -NH-CO-O- urethane bond by reaction between a polyol and an isocyanate or which activates the reaction between an isocyanate and water, such as tertiary amines and organic tin, iron, mercury or lead compounds. Mention may in particular by made, as tertiary amines, of triethylamine, N,N-dimethylcyclohexylamine DMCHA), N-methylmorpholine (NMM), N-ethylmorpholine, dimethylethanolamine, diaza[2.2.2]bicyclooctane (triethylenediamine) and substituted benzylamines, such as N,N-dimethylbenzylamine DB). Mention may in particular be made, as organic tin or lead compounds, of dibutyltin dilaurate, stannous octanoate and lead octanoate.
The catalyst of the premixes according to the invention can, in particular when the latter are intended for the manufacture of modified polyurethane (polyisocyanurate) foams, comprise a compound which catalyses the trimerization of isocyanates to triisocyanurates. Compounds which catalyse the trimerization of isocyanates which can be used in the premixes according to the invention are in particular triazines.
In addition to the polyol, the composition according to the invention and the catalyst, the premixes according to the invention can additionally contain various additives commonly used to prepare polyurethane or modified polyurethane foams, such as, in particular, water, surface-active agents, antioxidizing agents, fiame-retardant agents and/or pigments. The more particularly preferred premixes according to the invention are essentially composed of at least one polyol, the composition according to the invention, at least one catalyst which promotes the polyol/isocyanate reaction and at least one of the usual additives mentioned above.
The proportions of polyol, catalyst, the composition according to the invention and optional additives in the premixes according to the invention vary, in particular according to the application, the type of foam prepared, the nature of the polyol and the nature of the catalyst.
In practice, the amount of catalyst used generally varies from approximately 0.05 to 10 parts by weight per 100 parts by weight of polyol. In general, the amount of the composition according to the invention is from 1 to 80 parts by weight per 100 parts by weight of polyol. It is preferably from 10 to 60 parts by weight per 100 parts by weight of polyol. The amounts of water, surface-active agents, plasticizing agents and/or flame-retardant agents are those conventionally used to prepare polyurethane or modified polyurethane foams.
The invention also relates to a process for the manufacture of polyurethane or modified polyurethane foams, in which at least one isocyanate is reacted with at least one polyol in the presence of the composition according to the invention, of at least one catalyst and, optionally, of other usual additives. Any isocyanate conventionally used to manufacture such foams can be used in the process according to the invention. Mention may be made, by way of example, of aliphatic isocyanates, such as hexamethylene diisocyanate, and aromatic isocyanates, such as tolylene diisocyanate or diphenylmethane diisocyanate.
Generally, the process according to the invention is carried out in the presence of water. In this case the amount of water used is preferably equal to or greater than 1 part by weight per 100 parts of polyol. More preferably, the amount of water used equal to or greater than 1.5 parts by weight per 100 parts of polyol.
In this case the amount of water used is preferably equal to or less than 2.5 parts by weight per 100 parts of polyol. More preferably, the amount of water used equal to or less than 2 parts by weight per 100 parts of polyol.
In the process according to the invention, the composition according to the invention can be supplied to the reaction in the form of the premix according to the invention. The composition according to the invention can also be supplied to the reaction in the form of a mixture of the composition with the isocyanate.
The invention concerns also a polyurethane or modified polyurethane foam which is obtainable according to the process according to the invention. The polyurethane or modified polyurethane foam according to the invention is preferably a rigid closed-cell foam. The polyurethane or modified polyurethane foam can also be selected from a flexible or semi-flexible foam, an integral skin foam and a monocomponent foam.
The invention concerns also a thermal insulation material, which comprises a polyurethane or modified polyurethane foam according to the invention.
Specific examples of thermal insulation material according to the invention include insulation panels, tubes for pipe insulation, sandwich panels, laminates and block foams.
The thermal insulation material according to the invention generally substantially keeps its insulating properties when used in contact with an atmosphere having a temperature of 10°C or lower. Often the temperature of use can be 5°C or lower. The temperature can even be 0°C or lower without substantial condensation. The thermal insulation material according to the invention is particularly suitable when used in contact with an atmosphere having a temperature of - 10°C or higher. The examples here after are intended to illustrate the invention in a non- limitative manner.
Example 1 : PUR manufacture with a 70:30 composition of HFC-365mfc and HFC-245 fa A preparation of HFC-365mfc/HFC-2 5fa in a ratio 70:30 starts boiling at
27°C. lOOg Polyol-composition of an aromatic Polyesterpolyol and an aromatic Polyetherolyol with an OH number of 450 and 15 g Tris-Chloroiso- propylphosphate as a flame retardant, 2g Mimethylcyclohexylamine as a catalyst and l,5g of a Siloxanepolyalkeneoxide-Copolymer as a stabilizer, 2g of water and 20g of HFC-365mfc HFC-245fa in a ratio 70:30 were blended and then mixed with 130 g of 4,4-Diisocyanatediphenylmethane. A rigid foam was obtained with a density of 35 kg/m3.
Example 2 : PUR manufacture with a 75:25 composition of HFC-365mfc/ HFC-245fa Example 1 was repeated with 20g of HFC-365mfc/HFC-245fa in a ratio 75:25 having a boiling start of 28°C. The density was the same as in Example 1.
Example 3
Example 1 was repeated, adding the blowing agent composition separately, at first 14g HFC-365mfc and then 6 g of HFC-245fa, using a dip tube. A rigid foam was obtained with a density of 35 kg/m3.
The compositions do not present any flash point when used in a premix with polyols.

Claims

C L AIM S
1 - A composition which comprises 1,1, 1,3,3-pentaf orobutane (HFC-365mfe) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) in a weight ratio HFC-365mfc HFC-245fa of from 60:40 to 75:25.
2 - The composition according to claim 1, wherein the weight ratio
HFC-365mfc/HFC-245fa is from 65:35 to 73:27.
3 - The composition according to claim 1, wherein the weight ratio HFC-365mfc/HFC-245fa is from 67:33 to 72:28.
4 - The composition according to claim 1, wherein the weight ratio HFC-365mfc/HFC-245fa is about 70:30.
5 - The composition according to any one of claims 1 to 4, which consists essentially of HFC-365mfc and HFC-245fa.
6 - A premix intended for the preparation of polyurethane or modified polyurethane foams comprising a) at least one polyol b) a catalyst for the reaction of isocyanates with polyols c) a composition according to any one of claims 1 to 5.
7 - A process for the manufacture of polyurethane or modified polyurethane foams in which at least one isocyanate is reacted with at least one polyol in the presence of at least one catalyst and in the presence of the composition according to any one of claims 1 to 5.
8 - A polyurethane or modified polyurethane foam which is obtainable according to the process of claim 7.
9 - The polyurethane or modified polyurethane foam according to claim 8, which is a rigid closed cell foam.
10 - A thermal insulation material, which comprises a polyurethane or modified polyurethane foam according to claim 8 or 9.
PCT/EP2004/002656 2003-03-13 2004-03-12 Hydrofluorocarbon compositions WO2004081092A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
BRPI0408294-0A BRPI0408294A (en) 2003-03-13 2004-03-12 composition, premix intended for the preparation and process for the manufacture of polyurethane or modified polyurethane foams, polyurethane or modified polyurethane foam, and thermal insulation material
KR1020137013427A KR20130087539A (en) 2003-03-13 2004-03-12 Hydrofluorocarbon compositions
JP2006504688A JP2007524716A (en) 2003-03-13 2004-03-12 Hydrofluorocarbon composition
MXPA05009797A MXPA05009797A (en) 2003-03-13 2004-03-12 Hydrofluorocarbon compositions.
CA2518050A CA2518050C (en) 2003-03-13 2004-03-12 Hydrofluorocarbon compositions consisting of hfc-365mfc and hfc-245fa
ES04720003T ES2393920T3 (en) 2003-03-13 2004-03-12 Hydrofluorocarbon Compositions
AU2004220348A AU2004220348B2 (en) 2003-03-13 2004-03-12 Hydrofluorocarbon compositions
EP04720003A EP1606340B1 (en) 2003-03-13 2004-03-12 Hydrofluorocarbon compositions
US10/548,895 US20060160910A1 (en) 2003-03-13 2004-03-12 Hydrofluorocarbon compositions
IL170449A IL170449A (en) 2003-03-13 2005-08-23 Hydrofluorocarbon compositions
US12/400,345 US20090286898A1 (en) 2003-03-13 2009-03-09 Hydrofluorocarbon compositions
US14/712,175 US9963539B2 (en) 2003-03-13 2015-05-14 Hydrofluorocarbon compositions

Applications Claiming Priority (4)

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EP03100641.4 2003-03-13
EP03100641A EP1475404A1 (en) 2003-03-13 2003-03-13 Hydrofluorocarbon compositions
US46597903P 2003-04-28 2003-04-28
US60/465,979 2003-04-28

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US10548895 A-371-Of-International 2004-03-12
US12/400,345 Continuation US20090286898A1 (en) 2003-03-13 2009-03-09 Hydrofluorocarbon compositions

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RU2395539C2 (en) 2010-07-27
US20150246997A1 (en) 2015-09-03
EP1606340A1 (en) 2005-12-21
CN1756793A (en) 2006-04-05
KR20130087539A (en) 2013-08-06
AU2004220348A1 (en) 2004-09-23
KR20050109554A (en) 2005-11-21
BRPI0408294A (en) 2006-03-07
JP2007524716A (en) 2007-08-30
US20060160910A1 (en) 2006-07-20
KR20110135424A (en) 2011-12-16
AU2004220348B2 (en) 2009-10-29
EP1475404A1 (en) 2004-11-10
US20090286898A1 (en) 2009-11-19
ZA200506880B (en) 2007-04-25
CA2518050A1 (en) 2004-09-21
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MXPA05009797A (en) 2005-10-26

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