EP2010596A2 - Blowing agent composition - Google Patents

Blowing agent composition

Info

Publication number
EP2010596A2
EP2010596A2 EP07731822A EP07731822A EP2010596A2 EP 2010596 A2 EP2010596 A2 EP 2010596A2 EP 07731822 A EP07731822 A EP 07731822A EP 07731822 A EP07731822 A EP 07731822A EP 2010596 A2 EP2010596 A2 EP 2010596A2
Authority
EP
European Patent Office
Prior art keywords
weight
hydro
blowing agent
compound
composition according
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Withdrawn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
EP07731822A
Other languages
German (de)
French (fr)
Inventor
Vincent Enaux
Laurent Latil
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.)
Arkema France SA
Original Assignee
Arkema France SA
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
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2010596A2 publication Critical patent/EP2010596A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • 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
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/146—Saturated hydrocarbons containing oxygen and halogen atoms, e.g. F3C-O-CH2-CH3
    • 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 an expanding agent composition suitable for use in the manufacture of thermoplastic and thermosetting foams.
  • HFC as blowing agent in the manufacture of isocyanate-based foams
  • WO 02/099006 discloses an azeotropic composition of HFC and trans 1,2-dichloroethylene as an expanding agent in the manufacture of foams.
  • the object of the present invention is to provide an expanding agent composition that meets both negligible ODP and low GWP criteria.
  • the present invention has, as a first object, an expansion agent composition comprising an organic solvent of boiling point, at atmospheric pressure, greater than 0 ° C and having a low GWP, preferably less than 100, or better still less than 20, and at least one compound (C) chosen from haloketones, fluoroacids, fluoroesters, fluoroamines, (hydro) fluoroethers, (hydro) fluorothioethers, (hydro) fluoroolefins, cyclic (hydro) fluorocarbons and iodofluoro (hydro) carbides.
  • C compound chosen from haloketones, fluoroacids, fluoroesters, fluoroamines, (hydro) fluoroethers, (hydro) fluorothioethers, (hydro) fluoroolefins, cyclic (hydro) fluorocarbons and iodofluoro (hydro) carbides.
  • the blowing agent composition essentially contains an organic solvent with a boiling point, at atmospheric pressure, greater than 0 ° C. and having a low GWP, preferably less than 100, or better still less than 20, and at least a compound (C) chosen from haloketones, fluoroacids, fluoroesters, fluoroamines, (hydro) fluoroethers, (hydro) fluorothioethers, (hydro) fluoroolefins, cyclic (hydro) fluorocarbons and iodofluoro (hydro) carbides .
  • the blowing agent composition according to the present invention has not only negligible ODP but also a low GWP, preferably less than 100.
  • This blowing agent composition preferably comprises 1 to 99% by weight of solvent and 99 to 1% by weight of compound (s) C.
  • it comprises 50 to 99% by weight of solvent and 1 to 50% by weight of compound (s) C.
  • the advantageously preferred composition comprises 70 to 99% by weight of solvent and 1 to 30% by weight of compound (s) C.
  • the (hydro) fluoroethers are preferably chosen as compound C.
  • (Hydro) fluoroethers denote compounds containing carbon, fluorine, at least one ether function and optionally hydrogen.
  • hydro fluoroethers mention may be made in particular of those of general formula (Rh - O) x - Rf in which x is equal to 1 or 2; R n represents an optionally fluorinated alkyl group having from 1 to 4 carbon atoms and Rf represents a (per) fluorinated aliphatic group having at least 2 carbon atoms, preferably between 2 and 9 carbon atoms. R may also include heteroatoms such as oxygen, nitrogen and sulfur.
  • the preferred hydrofluoroethers are those for which the value of x is equal to 1.
  • the compounds of the following formula may also be suitable as hydrofluoroethers: C 8 F 17 OCH 3 , C 5 F 11 OC 2 H 5 , C 3 F 7 OCH 3 , or 1,1-dimethoxyperfluorocyclohexane.
  • nC 4 F 9 OCH 3 , CF 3 CF (CF 3 ) CF 2 OCH 3 and (CF 3 ) 3 COCH 3 and 1 ethoxy nonafluorobutane, nC 4 F 9 OC 2 H 5 , CF 3 CF ( CF 3 ) CF 2 OC 2 H 5 and (CF 3 ) 3 COC 2 H 5 are advantageously chosen as hydrofluoroethers.
  • organic solvent there may be mentioned in particular 1, 1-dichloroethane, dioxolane, dimethylcarbonate, propylene carbonate, nonafluoro-tert-butanol, acetone, tert-butylmethyl ether, diisopropyl ether, diethyl ether , dipropyl ether, ethyltertiobutyl ether, 1,2-dimethoxyethane, dimethoxymethane, 1,1-dimethoxyethane, methanol, ethanol, n-propanol, isopropanol, n, s, t- butanol, ethyl propionate, ethyl acetate, ethyl formate, methyl acetate, methyl formate, propyl acetate, isopropyl acetate, isopentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2,3-dimethylp
  • the dioxolane and the dimethylcarbonate are advantageously chosen as organic solvent.
  • Fluoroamines denote compounds containing carbon, fluorine, at least one amine function, and optionally hydrogen and chlorine.
  • N- (difluoromethyl) -N, N-dimethylamine may be mentioned,
  • (Hydro) fluorothioethers are compounds containing carbon, fluorine, at least one thio ether function and optionally hydrogen and chlorine.
  • 1, 1, 1, 2,2-pentafluoro-2 - [(pentafluoroethyl) thio] ethane can be mentioned.
  • An example of a cyclic (hydro) fluorocarbon is heptafluorocyclopentane.
  • Fluoroacids denote compounds containing carbon, fluorine, at least one acid function, and optionally hydrogen and chlorine.
  • Fluoroesters denote compounds containing carbon, fluorine, at least one ester function, and optionally hydrogen and chlorine.
  • iodofluoro (hydro) carbides there may be mentioned in particular iodotrifluoromethane (CF 3 I), iodopentafluoroethane (C 2 F 5 I), 1-iodoheptafluoropropane (CF 3 CF 2 CF 2 I), 2-iodoheptafluoropropane (CF 3 CFICF 3 ), iodo-1, 1, 2,2-tetrafluoroethane (CHF 2 CF 2 I), 2-iodo-1, 1, 1-trifluoroethane (CF 3 CH 2 I), iodotrifluoroethylene (C 2 F 3 I), 1-iodo-1, 1, 2,3,3,3-hexafluoropropane (CF 3 CHFCF 2 I), 2-iodononafluoro-tert-butane ((CF 3 ) 3 CI).
  • Haloketones denote compounds containing carbon, fluorine, at least one ketone function, and optionally hydrogen, chlorine and bromine.
  • the haloketones may be represented by the general formula RiCOR 2 , wherein R 1 , R 2, which may be identical or different, are independently selected from the group consisting of aliphatic or alicyclic fluorinated carbon radicals optionally containing hydrogen, bromine or chlorine.
  • the chain of carbon radicals can be linear or branched, saturated or unsaturated.
  • R 1 and R 2 may optionally form a ring.
  • the haloketones may contain from 3 to 10 carbon atoms, preferably from 4 to 8 carbon atoms.
  • haloketones may further contain other heteroatoms such as oxygen to form an additional ketone function or an ether, aldehyde or ester group.
  • haloketones there may be mentioned in particular 1, 1, 1, 2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone, 1, 1, 1, 2,4,5 5,5-octafluoro-2,4-bis (trifluoromethyl) -3-pentanone, 1,1,2,4,4,5,5-octafluoro-2-
  • 1,1,1,2,2,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone is preferred.
  • haloketones mention may also be made of bromofluoro ketones, for example monobromoperfluoro ketones, monohydromonobromoperfluoro ketones, (perfluoroalkoxy) monobromoperfluoro ketones, (fluoroalkoxy) monobromoperfluoro ketones and monochloromonobromoperfluoro ketones.
  • 1,1,1,3,3-Pentafluoropropene HFO-1225zc
  • cis and trans isomer of 1,1,1,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,2-tetrafluoropropene (HFO-1234yf) are particularly preferred.
  • the particularly preferred blowing agent composition comprises 1,3 dioxolane and at least one hydrofluoroether.
  • An expansion agent composition comprising 1,3 dioxolane and 1 methoxy nonafluorobutane has given very interesting results.
  • a composition comprising 1,3 dioxolane and 1 ethoxy nonafluorobutane.
  • blowing agent composition there may be mentioned in particular that comprising dimethylcarbonate and at least one hydrofluoroether, such as 1-methoxy-nonafluorobutane and 1-ethoxy-nonafluorobutane.
  • the blowing agent composition according to the present invention advantageously leads to thermoplastic and thermosetting foams having a good dimensional stability. It is particularly suitable for the manufacture of polyurethane foams and advantageously to the manufacture of rigid polyurethane foams.
  • polyurethane foam components are premixes. More generally, the formulation of the foams is premixed into two components.
  • the first component better known under the name “component A” comprises the isocyanate or polyisocyanate composition.
  • component B comprises the polyol or polyol mixture, the surfactant, the catalyst (s), and the blowing agent (s).
  • the subject of the present invention is therefore a composition comprising a polyol or mixture of polyols and the blowing agent of the first object.
  • the composition according to the second object is preferably in emulsion form.
  • the blowing agent is preferably from 1 to 60 parts by weight per 100 parts by weight of polyol or mixture of polyols in the composition of the second article.
  • it represents between 5 and 35 parts by weight per 100 parts by weight of polyol or mixture of polyols.
  • polyols there may be mentioned glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, polyether polyols, for example those obtained by condensation of an alkylene oxide or a mixture of alkylene oxides with the glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, polyesterspolyols, for example those obtained from polycarboxylic acids, in particular oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, , fumaric acid, isophthalic acid, terephthalic acid, with glycerol, ethylene glycol, trimethylolpropane, pentaerythritol.
  • polyether polyols for example those obtained by condensation of an alkylene oxide or a mixture of alkylene oxides with the glycerol, ethylene glycol, trimethylolpropane, pentaerythritol
  • polyether polyols obtained by the addition of alkylene oxides, in particular ethylene oxide and / or propylene oxide, to the aromatic amines, in particular the mixture of 2,4 and 2,6 toluene diamine, are also suitable.
  • alkylene oxides in particular ethylene oxide and / or propylene oxide
  • polyols that may be mentioned include hydroxyl-terminated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes.
  • the present invention also relates to a process for manufacturing polyurethane foams.
  • This process comprises reacting an organic polyisocyanate (including diisocyanate) with the composition according to the second object.
  • This reaction can be activated using an amine and / or other catalysts and surfactants.
  • the process for producing polyurethane foams can be carried out in the presence of a chemical blowing agent such as water.
  • polyisocyanate there may be mentioned in particular aliphatic polyisocyanates with a hydrocarbon group of up to 18 carbon atoms, cycloaliphatic polyisocyanates with a hydrocarbon group of up to 15 carbon atoms, aromatic polyisocyanates with an aromatic hydrocarbon group having from 6 to 15 carbon atoms and arylaliphatic polyisocyanates with an arylaliphatic hydrocarbon group having 8 to 15 carbon atoms.
  • the preferred polyisocyanates are 2,4-diisocyanato and 2,6-toluyl, diphenylmethane diisocyanate, polymethylenepolyphenyl isocyanate and mixtures thereof.
  • Modified polyisocyanates such as those containing carbodiimide groups, urethane groups, isocyanurate groups, urea groups or biurea groups may also be suitable.
  • Procedure for producing a rigid polyurethane foam 100 parts by weight of polyol Stepanpol PS2412 (polyester type), 1.5 parts by weight of surfactant Tegostab B8465, 3 parts by weight of water and 10 parts by weight of the composition of the composition are introduced into a beaker. expansion agent according to the invention. Then, we shake for a minute, using a vertical mechanical stirrer at a medium speed of 2000 rpm, the resulting mixture.
  • Desmodur 44V70L isocyanate
  • the catalyst consisting of 2.82 parts by weight of Dabco K15 (mixture of potassium salt 2-ethyl hexanoic acid and diethylene glycol) is injected with a plastic syringe and 0 18 parts by weight of Polycat 5 (Pentamethyldiethylenetriamine).
  • the mixture is poured into a rectangular mold covered with paper. It is then waited 5 minutes before demolding the foam and after 24 hours, the foam is cut with a band saw. The volume of the cut foam is measured before passing to the oven and after 72 hours at 70 ° C. in an oven. The difference between the volume of the foam after and before the oven gives an indication of the dimensional stability and the data are reported in the table below.
  • volume difference (%) (Final volume - Initial volume) / Initial volume.
  • blowing agent used for the examples are as follows:
  • Example 1 (according to the invention): 75% by weight of dimethyl carbonate (DMC) and 25% by weight of 1-methoxy-nonafluorobutane
  • Example 2 (according to the invention): 75% by weight of 1,3-dioxolane and 25% by weight of 1-methoxy-nonafluorobutane.

Landscapes

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

Abstract

The invention concerns a blowing agent composition comprising an organic solvent having a boiling point, at atmospheric temperature, higher than 0°C and having a low GWP and at least one compound (C) selected among haloketones, fluoroacids, fluoroesters, fluoroamines, (hydro)fluoroethers, (hydro)fluorothioethers, (hydro)fluoroolefins, cyclic (hydro)fluorocarbides and iodofluoro(hydro)carbides.

Description

COMPOSITION D'AGENT D'EXPANSION EXPANSION AGENT COMPOSITION
La présente invention concerne une composition d'agent d'expansion, apte à être utilisée dans la fabrication des mousses thermoplastiques et thermodurcissables.The present invention relates to an expanding agent composition suitable for use in the manufacture of thermoplastic and thermosetting foams.
Dans le domaine des mousses thermoplastiques et thermodurcissables comme dans d'autres applications, le protocole de Montréal visant à limiter la dégradation de la couche d'ozone a imposé des règles strictes concernant l'utilisation de produits fluorés. Ces derniers sont caractérisés par leur ODP (Ozone Depletion Potential). Les CFC (chlorofluorocarbure) étaient la première génération de produits, les HCFC (hydrochlorofluorocarbure) la seconde, tous deux n'ont pas un ODP nul ou négligeable. C'est le cas de la troisième génération de produits, à savoir les HFC (hydrofluorocarbure). Ces produits sont d'ailleurs largement utilisés à ce jour dans le domaine des mousses. La ratification du protocole de KYOTO sur la maîtrise des émissions de gaz à effet de serre génère une contrainte supplémentaire sur ces produits fluorés, à savoir un abaissement de leur GWP (Global Warming Potential).In the field of thermoplastic and thermosetting foams as in other applications, the Montreal Protocol to limit the degradation of the ozone layer has imposed strict rules regarding the use of fluorinated products. These are characterized by their ODP (Ozone Depletion Potential). CFCs (chlorofluorocarbons) were the first generation of products, HCFCs (hydrochlorofluorocarbons) the second, both do not have zero or negligible ODPs. This is the case of the third generation of products, namely HFCs (hydrofluorocarbon). These products are also widely used to date in the field of foams. The ratification of the KYOTO protocol on the control of greenhouse gas emissions generates an additional constraint on these fluorinated products, namely a lowering of their GWP (Global Warming Potential).
Ainsi, l'utilisation d'au moins un HFC comme agent d'expansion dans la fabrication des mousses à base d'isocyanates a été décrite dans le brevet EP 381986. Devant les contraintes environnementales de plus en plus sévères, le remplacement partiel de HFC dans la composition d'agent d'expansion a été suggéré. Le document WO 02/099006 divulgue une composition azéotropique de HFC et de trans 1 ,2-dichloroéthylène comme agent d'expansion dans la fabrication des mousses. L'objet de la présente invention vise à fournir une composition d'agent d'expansion qui répond à la fois aux critères d'ODP négligeable et de bas GWP.Thus, the use of at least one HFC as blowing agent in the manufacture of isocyanate-based foams has been described in patent EP 381986. In the face of increasingly severe environmental constraints, the partial replacement of HFCs in the blowing agent composition has been suggested. WO 02/099006 discloses an azeotropic composition of HFC and trans 1,2-dichloroethylene as an expanding agent in the manufacture of foams. The object of the present invention is to provide an expanding agent composition that meets both negligible ODP and low GWP criteria.
La présente invention a, pour premier objet, une composition d'agent d'expansion comprenant un solvant organique de point d'ébullition, à pression atmosphérique, supérieur à 0° C et ayant un bas GWP, de préférence inférieur à 100, ou mieux encore inférieur à 20, et au moins un composé (C) choisi parmi les halocétones, les fluoroacides, les fluoroesters, les fluoroamines, les (hydro)fluoroéthers, les (hydro)fluorothioéthers, les (hydro)fluorooléfines, les (hydro)fluorocarbures cycliques et les iodofluoro(hydro)carbures.The present invention has, as a first object, an expansion agent composition comprising an organic solvent of boiling point, at atmospheric pressure, greater than 0 ° C and having a low GWP, preferably less than 100, or better still less than 20, and at least one compound (C) chosen from haloketones, fluoroacids, fluoroesters, fluoroamines, (hydro) fluoroethers, (hydro) fluorothioethers, (hydro) fluoroolefins, cyclic (hydro) fluorocarbons and iodofluoro (hydro) carbides.
Avantageusement, la composition d'agent d'expansion contient essentiellement un solvant organique de point d'ébullition, à pression atmosphérique, supérieur à 0° C et ayant un bas GWP, de préférence inférieur à 100 ou mieux encore inférieur à 20 et au moins un composé (C) choisi parmi les halocétones, les fluoroacides, les fluoroesters, les fluoroamines, les (hydro)fluoroéthers, les (hydro)fluorothioéthers, les (hydro)fluorooléfines, les (hydro)fluorocarbures cycliques et les iodofluoro(hydro)carbures. La composition d'agent d'expansion selon la présente invention a non seulement un ODP négligeable mais aussi un bas GWP, de préférence inférieur à 100.Advantageously, the blowing agent composition essentially contains an organic solvent with a boiling point, at atmospheric pressure, greater than 0 ° C. and having a low GWP, preferably less than 100, or better still less than 20, and at least a compound (C) chosen from haloketones, fluoroacids, fluoroesters, fluoroamines, (hydro) fluoroethers, (hydro) fluorothioethers, (hydro) fluoroolefins, cyclic (hydro) fluorocarbons and iodofluoro (hydro) carbides . The blowing agent composition according to the present invention has not only negligible ODP but also a low GWP, preferably less than 100.
Cette composition d'agent d'expansion comprend de préférence 1 à 99 % en poids de solvant et 99 à 1 % en poids de composé(s) C. Avantageusement, elle comprend 50 à 99 % en poids de solvant et 1 à 50 % en poids de composé(s) C. La composition avantageusement préférée comprend 70 à 99 % en poids de solvant et 1 à 30 % en poids de composé(s) C.This blowing agent composition preferably comprises 1 to 99% by weight of solvent and 99 to 1% by weight of compound (s) C. Advantageously, it comprises 50 to 99% by weight of solvent and 1 to 50% by weight of compound (s) C. The advantageously preferred composition comprises 70 to 99% by weight of solvent and 1 to 30% by weight of compound (s) C.
Les (hydro)fluoroéthers sont de préférence choisis comme composé C. Les (hydro)fluoroéthers désignent des composés contenant du carbone, du fluor, d'au moins une fonction éther et éventuellement de l'hydrogène.The (hydro) fluoroethers are preferably chosen as compound C. (Hydro) fluoroethers denote compounds containing carbon, fluorine, at least one ether function and optionally hydrogen.
Comme (hydro)fluoroéthers, on peut citer notamment ceux de formule générale (Rh - O)x - Rf dans laquelle x est égale à 1 ou 2 ; Rn représente un groupe alkyle, éventuellement fluoré, ayant de 1 à 4 atomes de carbone et Rf représente un groupement aliphatique (per)fluoré ayant au moins 2 atomes de carbone, de préférence entre 2 et 9 atomes de carbone. R peut également comprendre des hétéroatomes tels que l'oxygène, l'azote et le soufre. Les hydrofluoroéthers préférés sont ceux pour lesquels la valeur de x est égale à 1. On peut citer notamment le 1 methoxy nonafluorobutane, IT-C4F9OCH3 CF3CF(CF3)CF2OCH3 et (CF3)3COCH3, le 1 éthoxy nonafluorobutane, n- C4F9OC2H5, CF3CF(CF3)CF2OC2H5 et (CF3)3COC2H5 . Les composés de formule suivante peuvent également convenir comme hydrofluoroéthers : C8F17OCH3, C5F11OC2H5, C3F7OCH3, ou le 1 ,1 - dimethoxyperfluorocyclohexane.As (hydro) fluoroethers, mention may be made in particular of those of general formula (Rh - O) x - Rf in which x is equal to 1 or 2; R n represents an optionally fluorinated alkyl group having from 1 to 4 carbon atoms and Rf represents a (per) fluorinated aliphatic group having at least 2 carbon atoms, preferably between 2 and 9 carbon atoms. R may also include heteroatoms such as oxygen, nitrogen and sulfur. The preferred hydrofluoroethers are those for which the value of x is equal to 1. Mention may in particular be made of 1 methoxy nonafluorobutane, IT-C 4 F 9 OCH 3 CF 3 CF (CF 3 ) CF 2 OCH 3 and (CF 3 ) 3 COCH 3 , 1 ethoxy nonafluorobutane, n-C 4 F 9 OC 2 H 5 , CF 3 CF (CF 3 ) CF 2 OC 2 H 5 and (CF 3 ) 3 COC 2 H 5 . The compounds of the following formula may also be suitable as hydrofluoroethers: C 8 F 17 OCH 3 , C 5 F 11 OC 2 H 5 , C 3 F 7 OCH 3 , or 1,1-dimethoxyperfluorocyclohexane.
Le 1 methoxy nonafluorobutane, n-C4F9OCH3, CF3CF(CF3)CF2OCH3 et (CF3)3COCH3 et le 1 éthoxy nonafluorobutane, n-C4F9OC2H5, CF3CF(CF3)CF2OC2H5 et (CF3)3COC2H5 sont avantageusement choisis comme hydrofluoroéthers.1 methoxy nonafluorobutane, nC 4 F 9 OCH 3 , CF 3 CF (CF 3 ) CF 2 OCH 3 and (CF 3 ) 3 COCH 3 and 1 ethoxy nonafluorobutane, nC 4 F 9 OC 2 H 5 , CF 3 CF ( CF 3 ) CF 2 OC 2 H 5 and (CF 3 ) 3 COC 2 H 5 are advantageously chosen as hydrofluoroethers.
Comme solvant organique, on peut citer notamment le 1 ,1 - dichloroéthane, le dioxolane, le diméthylcarbonate, le carbonate de propylène, le nonafluoro-ter-butanol, l'acétone, le ter-butylmethyl éther, le diisopropyl éther, le diéthyl éther, le dipropyl éther, l'éthyltertiobutyl éther, le 1 ,2-diméthoxyéthane, le diméthoxyméthane , le 1 ,1 -diméthoxyéthane, le méthanol, l'éthanol, le n- propanol, l'isopropanol, le n, s, t-butanol, le propionate d'éthyle, l'acétate d'éthyle, le formiate d'éthyle, l'acétate de méthyle, le formiate de méthyle, l'acétate de propyle, l'acétate d'isopropyle, l'isopentane, le 2,2-diméthylbutane, le 2,3- diméthylbutane, le 2,3-diméthylpentane, le 2-méthylhexane, le 3- méthylhexane, le 2-méthylpentane, le 3-éthylpentane, le 3-méthylpentane, le cyclohexane, le cyclopentane, le n-heptane, le méthylcyclopentane, le n- pentane, le n-hexane, le méthylal, le 2-chloropropane, le chlorure de méthylène, le chlorure d'éthylène, le trichloroéthane, le (méthyl)tetrahyfrofuranne et le diméthylacétalformol.As organic solvent, there may be mentioned in particular 1, 1-dichloroethane, dioxolane, dimethylcarbonate, propylene carbonate, nonafluoro-tert-butanol, acetone, tert-butylmethyl ether, diisopropyl ether, diethyl ether , dipropyl ether, ethyltertiobutyl ether, 1,2-dimethoxyethane, dimethoxymethane, 1,1-dimethoxyethane, methanol, ethanol, n-propanol, isopropanol, n, s, t- butanol, ethyl propionate, ethyl acetate, ethyl formate, methyl acetate, methyl formate, propyl acetate, isopropyl acetate, isopentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2,3-dimethylpentane, 2-methylhexane, 3-methylhexane, 2-methylpentane, 3-ethylpentane, 3-methylpentane, cyclohexane, cyclopentane , n-heptane, methylcyclopentane, n-pentane, n-hexane, methylal, 2-chloropropane, methylene chloride, ethylene chloride, trichloroethane, (methyl) tetrahyfrofuran and dimethylacetalformol.
Le dioxolane et le diméthylcarbonate sont avantageusement choisis comme solvant organique. Les fluoroamines désignent des composés contenant du carbone, du fluor, d'au moins une fonction aminé, et éventuellement de l'hydrogène et du chlore. On peut citer notamment la N-(difluorométhyl)-N,N-diméthylamine,The dioxolane and the dimethylcarbonate are advantageously chosen as organic solvent. Fluoroamines denote compounds containing carbon, fluorine, at least one amine function, and optionally hydrogen and chlorine. In particular N- (difluoromethyl) -N, N-dimethylamine may be mentioned,
Les (hydro)fluorothioéthers désignent des composés contenant du carbone, du fluor, d'au moins une fonction thio éther et éventuellement de l'hydrogène et du chlore. On peut citer notamment le 1 ,1 ,1 ,2,2-pentafluoro-2- [(pentafluoroéthyl)thio]éthane. Un exemple d'(hydro)fluorocarbures cyclique est l'heptafluorocyclopentane.(Hydro) fluorothioethers are compounds containing carbon, fluorine, at least one thio ether function and optionally hydrogen and chlorine. In particular, 1, 1, 1, 2,2-pentafluoro-2 - [(pentafluoroethyl) thio] ethane can be mentioned. An example of a cyclic (hydro) fluorocarbon is heptafluorocyclopentane.
Les fluoroacides désignent des composés contenant du carbone, du fluor, d'au moins une fonction acide, et éventuellement de l'hydrogène et du chlore.Fluoroacids denote compounds containing carbon, fluorine, at least one acid function, and optionally hydrogen and chlorine.
Les fluoroesters désignent des composés contenant du carbone, du fluor, d'au moins une fonction ester, et éventuellement de l'hydrogène et du chlore.Fluoroesters denote compounds containing carbon, fluorine, at least one ester function, and optionally hydrogen and chlorine.
Comme iodofluoro(hydro)carbures, on peut citer notamment le iodotrifluorométhane (CF3I), le iodopentafluoroéthane (C2F5I), le 1 - iodoheptafluoropropane (CF3CF2CF2I), le 2-iodoheptafluoropropane (CF3CFICF3), le iodo-1 ,1 ,2,2-tetrafluoroéthane (CHF2CF2I ), le 2-iodo-1 ,1 ,1 - trifluoroéthane (CF3CH2I ), le iodotrifluoroéthylène (C2F3I ), le 1 -iodo-1 , 1 ,2,3,3,3 - hexafluoropropane (CF3CHFCF2I), le 2-iodononafluoro-ter-butane ( (CF3)3CI ). Le iodotrifluorométhane et le iodopentafluoroéthane sont préférés.As iodofluoro (hydro) carbides, there may be mentioned in particular iodotrifluoromethane (CF 3 I), iodopentafluoroethane (C 2 F 5 I), 1-iodoheptafluoropropane (CF 3 CF 2 CF 2 I), 2-iodoheptafluoropropane (CF 3 CFICF 3 ), iodo-1, 1, 2,2-tetrafluoroethane (CHF 2 CF 2 I), 2-iodo-1, 1, 1-trifluoroethane (CF 3 CH 2 I), iodotrifluoroethylene (C 2 F 3 I), 1-iodo-1, 1, 2,3,3,3-hexafluoropropane (CF 3 CHFCF 2 I), 2-iodononafluoro-tert-butane ((CF 3 ) 3 CI). Iodotrifluoromethane and iodopentafluoroethane are preferred.
Les halocétones désignent des composés contenant du carbone, du fluor, d'au moins une fonction cétone, et éventuellement de l'hydrogène, du chlore et du brome. Les halocétones peuvent être représentés par la formule générale RiCOR2, dans laquelle R1, R2 identiques ou différents sont sélectionnés indépendamment dans le groupe consistant en radicaux carbonés fluorés aliphatiques ou alicycliques contenant éventuellement de l'hydrogène, du brome ou du chlore. La chaîne des radicaux carbonés pouvant être linéaire ou ramifiée, saturée ou insaturée. R1 et R2 peuvent éventuellement former un cycle. Les halocétones peuvent contenir de 3 à 10 atomes de carbone, de préférence de 4 à 8 atomes de carbone. Les halocétones peuvent en outre contenir d'autres hétéroatomes tels que l'oxygène pour former une fonction cétone supplémentaire ou un groupement éther, aldéhyde ou ester. Comme halocétones, on peut citer notamment le 1 ,1 , 1 ,2,2,4, 5,5,5-nonafluoro-4- (trifluorométhyl)-3-pentanone, le 1 ,1 ,1 ,2,4,5, 5,5-octafluoro-2,4- bis(trifluorométhyl)-3-pentanone, le 1 ,1 , 1 ,2,4,4, 5,5-octafluoro-2-Haloketones denote compounds containing carbon, fluorine, at least one ketone function, and optionally hydrogen, chlorine and bromine. The haloketones may be represented by the general formula RiCOR 2 , wherein R 1 , R 2, which may be identical or different, are independently selected from the group consisting of aliphatic or alicyclic fluorinated carbon radicals optionally containing hydrogen, bromine or chlorine. The chain of carbon radicals can be linear or branched, saturated or unsaturated. R 1 and R 2 may optionally form a ring. The haloketones may contain from 3 to 10 carbon atoms, preferably from 4 to 8 carbon atoms. The haloketones may further contain other heteroatoms such as oxygen to form an additional ketone function or an ether, aldehyde or ester group. As haloketones, there may be mentioned in particular 1, 1, 1, 2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone, 1, 1, 1, 2,4,5 5,5-octafluoro-2,4-bis (trifluoromethyl) -3-pentanone, 1,1,2,4,4,5,5-octafluoro-2-
(trifluorométhyl)-3-pentanone, le 1 ,1 ,1 ,2,4,4, 5,5, 6,6, 6-undecafluoro-2- (trifluorométhyl)-3-hexanone, le 1 ,1 ,2,2,4, 5,5,5-octafluoro-1 -(trifluorométhoxy)- 4- (trifluorométhyl)-3-pentanone, le 1 ,1 ,1 ,3,4,4,4-heptafluoro-3-(trifluorométhyl)- 2-butanone, le 1 ,1 ,1 ,2,2,5,5,5-octafluoro-4-(trifluorométhyl)-3-pentanone, le 2- chloro-1 ,1 ,1 ,4,4,5, 5,5-octafluoro-2-(trifluorométhyl)-3-pentanone. Le(1-trifluoromethyl) -3-pentanone, 1,1,2,4,4,5,6,6,6-undecafluoro-2- (trifluoromethyl) -3-hexanone, 1, 1, 2, 2,4,5,5-octafluoro-1- (trifluoromethoxy) - 4- (trifluoromethyl) -3-pentanone, 1,1,1,4,4,4-heptafluoro-3- (trifluoromethyl) -2-butanone, 1,1,1,2,2,5, 5,5-octafluoro-4- (trifluoromethyl) -3-pentanone, 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl) -3-pentanone. The
1 ,1 ,1 ,2,2,4,5,5,5-nonafluoro-4-(trifluorométhyl)-3-pentanone est préféré. Comme halocétones, on peut également citer les bromofluorocétones, par exemple les monobromoperfluorocétones, les monohydromonobromoperfluorocétones, les (perfluoroalkoxy) monobromoperfluorocétones, les (fluoroalkoxy) monobromoperfluorocétones et les monochloromonobromoperfluorocétones. Peuvent convenir comme (hydro)fluorooléfines, le 3,3,4,4,5,5,6,6,6- nonafluoro-1 -hexène, les fluoropropènes de formule générale CF3CY=CXnHp dans laquelle X et Y représentent indépendamment un atome d'hydrogène ou d'halogène choisi parmi le fluoré, le chlore, le brome et l'iode et n et p sont des nombres entiers ayant pour valeur 0, 1 ou 2 et tel que (n+p) est égale à 2. On peut citer par exemple CF3CH=CF2, CF3CH=CFH, CF3CBr=CF2, CF3CH=CH2, CF3CF=CF2, CF3CCI=CF2, CF3CH=CHCI, CF3CCI=CHF, CF3CH=CCI2 et CF3CF=CCI2.1,1,1,2,2,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone is preferred. As haloketones, mention may also be made of bromofluoro ketones, for example monobromoperfluoro ketones, monohydromonobromoperfluoro ketones, (perfluoroalkoxy) monobromoperfluoro ketones, (fluoroalkoxy) monobromoperfluoro ketones and monochloromonobromoperfluoro ketones. May be suitable as (hydro) fluoroolefins, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, fluoropropenes of general formula CF 3 CY = CX n Hp wherein X and Y independently represent a hydrogen or halogen atom selected from fluorine, chlorine, bromine and iodine and n and p are integers having the value 0, 1 or 2 and such that (n + p) is equals 2. For example CF 3 CH = CF 2 , CF 3 CH = CFH, CF 3 CBr = CF 2 , CF 3 CH = CH 2 , CF 3 CF = CF 2 , CF 3 CCI = CF 2 , CF 3 CH = CHCl 3 , CF 3 CCI = CHF, CF 3 CH = CCI 2 and CF 3 CF = CCI 2 .
Le 1 ,1 ,1 ,3,3-pentafluoropropène (HFO-1225zc), l'isomère cis et trans de 1 ,1 ,1 ,3-tetrafluoropropène (HFO- 1234ze) et le 1 ,1 ,1 ,2-tetrafluoropropène (HFO-1234yf) sont particulièrement préférés.1,1,1,3,3-Pentafluoropropene (HFO-1225zc), cis and trans isomer of 1,1,1,3-tetrafluoropropene (HFO-1234ze) and 1,1,1,2-tetrafluoropropene (HFO-1234yf) are particularly preferred.
La composition d'agent d'expansion particulièrement préférée comprend le 1 ,3 dioxolane et au moins un hydrofluoroéther. Une composition d'agent d'expansion comprenant le 1 ,3 dioxolane et le 1 méthoxy nonafluorobutane a donné des résultats très intéressants. De même pour une composition comprenant le 1 ,3 dioxolane et le 1 éthoxy nonafluorobutane.The particularly preferred blowing agent composition comprises 1,3 dioxolane and at least one hydrofluoroether. An expansion agent composition comprising 1,3 dioxolane and 1 methoxy nonafluorobutane has given very interesting results. Likewise for a composition comprising 1,3 dioxolane and 1 ethoxy nonafluorobutane.
Comme autre composition d'agent d'expansion particulièrement préférée, on peut citer notamment celle comprenant le diméthylcarbonate et au moins un hydrofluoroéther tels que le 1 méthoxy nonafluorobutane et le 1 éthoxy nonafluorobutane. La composition d'agent d'expansion selon la présente invention conduit avantageusement à des mousses thermoplastiques et thermodurcissables ayant une bonne stabilité dimensionnelle. Elle convient tout particulièrement à la fabrication des mousses polyuréthane et avantageusement à la fabrication des mousses polyuréthane rigides.As another particularly preferred blowing agent composition, there may be mentioned in particular that comprising dimethylcarbonate and at least one hydrofluoroether, such as 1-methoxy-nonafluorobutane and 1-ethoxy-nonafluorobutane. The blowing agent composition according to the present invention advantageously leads to thermoplastic and thermosetting foams having a good dimensional stability. It is particularly suitable for the manufacture of polyurethane foams and advantageously to the manufacture of rigid polyurethane foams.
Dans beaucoup d'applications, les composants des mousses polyuréthane sont des prémélanges. Plus généralement, la formulation des mousses est prémélangée en deux composants. Le premier composant, plus connu sous la dénomination « composant A » comprend la composition isocyanate ou polyisocyanate. Le deuxième composant, plus connu sous la dénomination « composant B » comprend le polyol ou mélange de polyols, l'agent tensioactif, le ou les catalyseurs, et le ou les agents d'expansion. La présente invention a donc pour deuxième objet une composition comprenant un polyol ou mélange de polyols et l'agent d'expansion du premier objet. La composition selon le deuxième objet est de préférence sous forme d'émulsion.In many applications, polyurethane foam components are premixes. More generally, the formulation of the foams is premixed into two components. The first component, better known under the name "component A" comprises the isocyanate or polyisocyanate composition. The second component, better known under the name "component B" comprises the polyol or polyol mixture, the surfactant, the catalyst (s), and the blowing agent (s). The subject of the present invention is therefore a composition comprising a polyol or mixture of polyols and the blowing agent of the first object. The composition according to the second object is preferably in emulsion form.
L'agent d'expansion représente de préférence entre 1 et 60 parties en poids pour 100 parties en poids de polyol ou mélange de polyols dans la composition du deuxième objet. Avantageusement, il représente entre 5 et 35 parties en poids pour 100 parties en poids de polyol ou mélange de polyols.The blowing agent is preferably from 1 to 60 parts by weight per 100 parts by weight of polyol or mixture of polyols in the composition of the second article. Advantageously, it represents between 5 and 35 parts by weight per 100 parts by weight of polyol or mixture of polyols.
Comme polyols, on peut citer notamment le glycérol, l'éthylène glycol, le triméthylolpropane, le pentaérythritol, les polyétherpolyols, par exemple ceux obtenus par condensation d'un oxyde d'alkylène ou d'un mélange d'oxydes d'alkylène avec le glycérol, l'éthylène glycol, le triméthylolpropane, le pentaérythritol, les polyesterspolyols, par exemple ceux obtenus d'acides polycarboxyliques, notamment l'acide oxalique, l'acide malonique, l'acide succinique, l'acide adipique, l'acide maléïque, l'acide fumarique, l'acide isophtalique, l'acide téréphtalique, avec le glycérol, l'éthylène glycol, le triméthylolpropane, le pentaérythritol.As polyols, there may be mentioned glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, polyether polyols, for example those obtained by condensation of an alkylene oxide or a mixture of alkylene oxides with the glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, polyesterspolyols, for example those obtained from polycarboxylic acids, in particular oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, , fumaric acid, isophthalic acid, terephthalic acid, with glycerol, ethylene glycol, trimethylolpropane, pentaerythritol.
Les polyétherpolyols obtenus par addition d'oxydes d'alkylènes, en particulier l'oxyde d'éthylène et/ou l'oxyde de propylène, sur les aminés aromatiques en particulier le mélange de 2,4 et 2,6 de toluène diamine conviennent également. Comme autres types de polyols, on peut citer notamment les polythioéthers à terminaison hydroxyle, les polyamides, les polyesteramides, les polycarbonates, les polyacétals, les polyoléfines et les polysiloxannes.The polyether polyols obtained by the addition of alkylene oxides, in particular ethylene oxide and / or propylene oxide, to the aromatic amines, in particular the mixture of 2,4 and 2,6 toluene diamine, are also suitable. . Other types of polyols that may be mentioned include hydroxyl-terminated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes.
La présente invention a également pour objet un procédé de fabrication de mousses polyuréthane. Ce procédé consiste à faire réagir un polyisocyanate organique (incluant le diisocyanate) avec la composition selon le deuxième objet. Cette réaction peut être activée à l'aide d'une aminé et/ou d'autres catalyseurs et des agents tensio-actifs.The present invention also relates to a process for manufacturing polyurethane foams. This process comprises reacting an organic polyisocyanate (including diisocyanate) with the composition according to the second object. This reaction can be activated using an amine and / or other catalysts and surfactants.
Outre l'agent d'expansion selon la présente invention, le procédé de fabrication de mousses polyuréthane peut être mis en œuvre en présence d'agent d'expansion chimique tel que l'eau.In addition to the blowing agent according to the present invention, the process for producing polyurethane foams can be carried out in the presence of a chemical blowing agent such as water.
Comme polyisocyanate, on peut citer notamment les polyisocyanates aliphatiques avec un groupement hydrocarboné pouvant aller jusqu'à 18 atomes de carbone, les polyisocyanates cycloaliphatiques avec un groupement hydrocarboné pouvant aller jusqu'à 15 atomes de carbone, les polyisocyanates aromatiques avec un groupement hydrocarboné aromatique ayant de 6 à 15 atomes de carbone et les polyisocyanates arylaliphatiques avec un groupement hydrocarboné arylaliphatique ayant de 8 à 15 atomes de carbone. Les polyisocyanates préférés sont le diisocyanato-2,4 et 2,6 toluyle, le diisocyanate de diphénylméthane, l'isocyanate de polyméthylènepolyphényle et leur mélange. Les polyisocyanates modifiés, tels que ceux contenant des groupements carbodiimides, des groupements uréthanes, des groupements isocyanurates, des groupements urée ou des groupements biurée peuvent également convenir.As polyisocyanate, there may be mentioned in particular aliphatic polyisocyanates with a hydrocarbon group of up to 18 carbon atoms, cycloaliphatic polyisocyanates with a hydrocarbon group of up to 15 carbon atoms, aromatic polyisocyanates with an aromatic hydrocarbon group having from 6 to 15 carbon atoms and arylaliphatic polyisocyanates with an arylaliphatic hydrocarbon group having 8 to 15 carbon atoms. The preferred polyisocyanates are 2,4-diisocyanato and 2,6-toluyl, diphenylmethane diisocyanate, polymethylenepolyphenyl isocyanate and mixtures thereof. Modified polyisocyanates, such as those containing carbodiimide groups, urethane groups, isocyanurate groups, urea groups or biurea groups may also be suitable.
PARTIE EXPERIMENTALEEXPERIMENTAL PART
Mode opératoire pour la réalisation d'une mousse polyuréthane rigide. On introduit dans un bêcher, 100 parties en poids de polyol Stepanpol PS2412 (type polyester), 1 ,5 parties en poids d'agent tensio-actif Tegostab B8465, 3 parties en poids d'eau et 10 parties en poids de la composition d'agent d'expansion conforme à l'invention. Puis, on agite pendant une minute, à l'aide d'un agitateur mécanique vertical à vitesse moyenne de 2000 tr/mn, le mélange résultant.Procedure for producing a rigid polyurethane foam. 100 parts by weight of polyol Stepanpol PS2412 (polyester type), 1.5 parts by weight of surfactant Tegostab B8465, 3 parts by weight of water and 10 parts by weight of the composition of the composition are introduced into a beaker. expansion agent according to the invention. Then, we shake for a minute, using a vertical mechanical stirrer at a medium speed of 2000 rpm, the resulting mixture.
On introduit ensuite 110 parties en poids de Desmodur 44V70L (isocyanate) dans le bêcher et on agite pendant 15 secondes avec une vitesse moyenne de 3500 tr/mn.Then 110 parts by weight of Desmodur 44V70L (isocyanate) are introduced into the beaker and stirred for 15 seconds with an average speed of 3500 rpm.
Tout en agitant le mélange, on injecte à l'aide d'une seringue en plastique le catalyseur constitué de 2,82 parties en poids de Dabco K15 (mélange de sel d'acide Potassium 2-ethyl hexanoïque et de Diéthylène glycol) et 0,18 partie en poids de Polycat 5 (Pentaméthyldiéthylène triamine). Au bout de 25 secondes d'agitation (total), on verse le mélange dans un moule rectangulaire recouvert de papier. On attend alors 5 minutes avant le démoulage de la mousse et au bout de 24 h, on découpe la mousse à l'aide d'une scie à ruban. On mesure le volume de la mousse découpée avant passage à l'étuve et après 72 h à 70°C à l'étuve. La différence entre le volume de la mousse après et avant passage à l'étuve donne une indication de la stabilité dimensionnelle et les données sont reportées dans le tableau ci-dessous.While stirring the mixture, the catalyst consisting of 2.82 parts by weight of Dabco K15 (mixture of potassium salt 2-ethyl hexanoic acid and diethylene glycol) is injected with a plastic syringe and 0 18 parts by weight of Polycat 5 (Pentamethyldiethylenetriamine). After stirring for 25 seconds (total), the mixture is poured into a rectangular mold covered with paper. It is then waited 5 minutes before demolding the foam and after 24 hours, the foam is cut with a band saw. The volume of the cut foam is measured before passing to the oven and after 72 hours at 70 ° C. in an oven. The difference between the volume of the foam after and before the oven gives an indication of the dimensional stability and the data are reported in the table below.
La différence de volume exprimée en pourcentage est calculée de la façon suivante : différence de volume (%) = (Volume final - Volume initial)/Volume initial.The difference in volume expressed as a percentage is calculated as follows: Volume difference (%) = (Final volume - Initial volume) / Initial volume.
L'agent d'expansion utilisé pour les exemples sont les suivants :The blowing agent used for the examples are as follows:
- exemple 1 (conforme à l'invention) : 75 % en poids de diméthylcarbonate (DMC) et 25 % en poids de 1 -methoxy-nonafluorobutaneExample 1 (according to the invention): 75% by weight of dimethyl carbonate (DMC) and 25% by weight of 1-methoxy-nonafluorobutane
- exemple 2 (conforme à l'invention) : 75 % en poids de 1 ,3-dioxolane et 25 % en poids de 1 -methoxy-nonafluorobutane .Example 2 (according to the invention): 75% by weight of 1,3-dioxolane and 25% by weight of 1-methoxy-nonafluorobutane.

Claims

REVENDICATIONS
1 ) Composition d'agent d'expansion comprenant un solvant organique de point d'ébullition, à pression atmosphérique, supérieur à 0° C et ayant un bas GWP, de préférence inférieur à 100, ou mieux encore inférieur à 20, et au moins un composé (C) choisi parmi les halocétones, les fluoroacides, les fluoroesters, les fluoroamines, les (hydro)fluoroéthers, les (hydro)fluorothioéthers, les (hydro)fluorooléfines, les (hydro)fluorocarbures cycliques et les iodofluoro(hydro)carbures. 2) Composition selon la revendication 1 caractérisée en ce qu'elle comprend 1 à 99 % en poids de solvant organique et 99 à 1 % en poids de composé(s) C, de préférence 50 à 99 parties en poids de solvant organique et 1 à 50 % en poids de composé(s) C, et avantageusement 70 à 99 % en poids de solvant pour 1 à 30 % en poids de composé(s) C. 3) Composition selon la revendication 1 ou 2 caractérisée en ce qu'elle comprend en outre un polyol ou un mélange de polyols.1) Expansion agent composition comprising an organic solvent with a boiling point, at atmospheric pressure, greater than 0 ° C. and having a low GWP, preferably less than 100, more preferably less than 20, and at least one a compound (C) chosen from haloketones, fluoroacids, fluoroesters, fluoroamines, (hydro) fluoroethers, (hydro) fluorothioethers, (hydro) fluoroolefins, cyclic (hydro) fluorocarbons and iodofluoro (hydro) carbides . 2) Composition according to claim 1 characterized in that it comprises 1 to 99% by weight of organic solvent and 99 to 1% by weight of compound (s) C, preferably 50 to 99 parts by weight of organic solvent and 1 50% by weight of compound (s) C, and advantageously 70 to 99% by weight of solvent for 1 to 30% by weight of compound (s) C. 3) Composition according to claim 1 or 2, characterized in that it further comprises a polyol or a mixture of polyols.
4) Composition selon l'une quelconque des revendications précédentes caractérisée en ce que le solvant organique est choisi parmi le dioxolane et le diméthylcarbonate. 5) Composition selon l'une quelconque des revendications précédentes caractérisée en ce que le composé C est le 1 -méthoxy- nonafluorobutane et/ou le 1 - éthoxy- nonafluorobutane.4) Composition according to any one of the preceding claims, characterized in that the organic solvent is chosen from dioxolane and dimethylcarbonate. 5) Composition according to any one of the preceding claims, characterized in that compound C is 1-methoxy-nonafluorobutane and / or 1-ethoxy-nonafluorobutane.
6) Composition selon l'une quelconque des revendications précédentes caractérisée en ce l'agent d'expansion est présent à raison de 1 à 60 parties en poids, de préférence à raison de 5 à 35 parties en poids pour 100 parties en poids de polyol.6) Composition according to any one of the preceding claims, characterized in that the blowing agent is present in a proportion of 1 to 60 parts by weight, preferably in a proportion of 5 to 35 parts by weight per 100 parts by weight of polyol. .
7) Procédé de fabrication de mousses caractérisé en ce que l'on utilise l'agent d'expansion selon la revendication 1 , 2, 4 ou 5.7) A method of manufacturing foams characterized in that one uses the blowing agent according to claim 1, 2, 4 or 5.
8) Procédé de fabrication de mousses polyuréthane caractérisé en ce que l'on utilise une composition selon l'une quelconque des revendications 1 à 6. 8) A method of manufacturing polyurethane foams characterized in that a composition according to any one of claims 1 to 6 is used.
EP07731822A 2006-03-31 2007-03-26 Blowing agent composition Withdrawn EP2010596A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0602796A FR2899233B1 (en) 2006-03-31 2006-03-31 EXPANSION AGENT COMPOSITION
US80036606P 2006-05-15 2006-05-15
PCT/FR2007/051010 WO2007113434A2 (en) 2006-03-31 2007-03-26 Blowing agent composition

Publications (1)

Publication Number Publication Date
EP2010596A2 true EP2010596A2 (en) 2009-01-07

Family

ID=37569243

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07731822A Withdrawn EP2010596A2 (en) 2006-03-31 2007-03-26 Blowing agent composition

Country Status (10)

Country Link
US (1) US20100222443A1 (en)
EP (1) EP2010596A2 (en)
JP (1) JP2009531508A (en)
KR (1) KR20090012210A (en)
CN (1) CN101443394B (en)
AU (1) AU2007232495A1 (en)
CA (1) CA2643855A1 (en)
FR (1) FR2899233B1 (en)
MX (1) MX2008012349A (en)
WO (1) WO2007113434A2 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105505323A (en) * 2008-03-07 2016-04-20 阿科玛股份有限公司 Halogenated alkene heat transfer composition with improved oil return
JP6134470B2 (en) 2008-03-07 2017-05-24 アーケマ・インコーポレイテッド Stable formulation system with chloro-3,3,3-trifluoropropene
CA2944302C (en) 2008-06-20 2017-11-21 E. I. Du Pont De Nemours And Company Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluoro-2-butene
WO2010055146A2 (en) * 2008-11-13 2010-05-20 Solvay Fluor Gmbh Hydrofluoroolefins, manufacture of hydrofluoroolefins and methods of using hydrofluoroolefins
JP2013504656A (en) * 2009-09-09 2013-02-07 アーケマ・インコーポレイテッド Improved polyurethane foaming process using halogenated olefin blowing agents and foam properties
MX2012012390A (en) * 2010-04-28 2012-11-30 Arkema Inc Method of improving stability of polyurethane polyol blends containing halogenated olefin blowing agent.
JP5731008B2 (en) 2010-11-17 2015-06-10 エフオーエムオー、プロダクツ、インク Method for filling wall cavities with expanded foam insulation
EP3176206A1 (en) * 2015-12-01 2017-06-07 Evonik Degussa GmbH Method for the preparation of fine cell foams using a cell aging inhibitor
CN111264898B (en) * 2018-12-04 2022-03-04 北京航天试验技术研究所 Tobacco shred expanding agent
KR102258805B1 (en) * 2019-06-26 2021-05-31 한국가스공사 Rigid urethane foam and process for preparing same

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3903336A1 (en) * 1989-02-04 1990-08-09 Bayer Ag USING C (ARROW DOWN) 3 (DOWN ARROW) - UP TO C (DOWN ARROW) 5 (DOWN ARROW) -POLYFLUOROUS CANS AS PRESSURE GASES
US5238970A (en) * 1991-04-03 1993-08-24 Imperial Chemical Industries, Plc Manufacture of rigid foams and compositions therefor
US5194325A (en) * 1992-02-25 1993-03-16 Renosol Corporation Molded polyurethane foam system utilizing HFC blowing agents
US5611210A (en) * 1993-03-05 1997-03-18 Ikon Corporation Fluoroiodocarbon blends as CFC and halon replacements
US5539008A (en) * 1993-12-29 1996-07-23 Minnesota Mining And Manufacturing Company Foamable composition containing unsaturated perfluorochemical blowing agent
JPH08169976A (en) * 1994-09-07 1996-07-02 Matsushita Electric Ind Co Ltd Heat-insulating resin foam and its production
KR0180613B1 (en) * 1994-09-07 1999-05-15 Matsushita Electric Ind Co Ltd Thermal insulating foamed material and method for manufacturing the same
US5827446A (en) * 1996-01-31 1998-10-27 E. I. Du Pont De Nemours And Company Nonafluoromethoxybutane compositions
US5851436A (en) * 1996-06-13 1998-12-22 E. I. Du Pont De Nemours And Company Nonafluoromethoxybutane compositions
IT1304179B1 (en) * 1998-12-17 2001-03-08 Enichem Spa PROCEDURE FOR THE PREPARATION OF FLEXIBLE POLYURETHANE FOAMS FROM LOW DENSITY BLOCK.
US6951835B1 (en) * 1999-03-22 2005-10-04 E.I. Du Pont De Nemours And Company Azeotrope-like compositions of 1,1,1,3,3-pentafluorobutane
US6646020B2 (en) * 2001-05-23 2003-11-11 Vulcan Chemicals A Division Of Vulcan Materials Company Isopropyl chloride with hydrofluorocarbon or hydrofluoroether as foam blowing agents
US6790820B2 (en) * 2001-06-01 2004-09-14 Honeywell International, Inc. Compositions of hydrofluorocarbons and trans-1,2-dichloroethylene
JP4159315B2 (en) * 2001-09-20 2008-10-01 セントラル硝子株式会社 Premix for the preparation of rigid polyurethane foam or polyisocyanurate foam, process for producing the foam and the foam
JP4215553B2 (en) * 2002-06-28 2009-01-28 セントラル硝子株式会社 Foaming agent composition, premix for the preparation of rigid polyurethane foam or polyisocyanurate and process for producing said foam

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007113434A2 *

Also Published As

Publication number Publication date
MX2008012349A (en) 2009-03-06
KR20090012210A (en) 2009-02-02
CN101443394B (en) 2012-05-16
FR2899233B1 (en) 2010-03-12
CN101443394A (en) 2009-05-27
JP2009531508A (en) 2009-09-03
AU2007232495A1 (en) 2007-10-11
CA2643855A1 (en) 2007-10-11
WO2007113434A2 (en) 2007-10-11
US20100222443A1 (en) 2010-09-02
FR2899233A1 (en) 2007-10-05
WO2007113434A3 (en) 2008-11-13

Similar Documents

Publication Publication Date Title
WO2007113435A2 (en) Blowing agent composition
EP2010596A2 (en) Blowing agent composition
JP6148365B2 (en) Hydrochlorofluoroolefin blowing agent composition
US5539008A (en) Foamable composition containing unsaturated perfluorochemical blowing agent
US20140058003A1 (en) Polymeric foams including fluorinated oxiranes, methods of preparation, and use of same
WO1994011329A1 (en) Hydrofluorohalocarbon decomposition inhibitor and method
JP4215553B2 (en) Foaming agent composition, premix for the preparation of rigid polyurethane foam or polyisocyanurate and process for producing said foam
FR2913425A1 (en) Blowing agent composition, useful for manufacturing foam, preferably polyurethane foam and thermoplastics and thermosetting foam, comprises dioxolane, and compounds having e.g. haloketones, fluoroacids, fluoroesters and fluoroamines
JP2002528584A (en) Method for producing polymer foam using perfluorochemical compound dissolved or dispersed in hydrofluoroether
EP1851301B1 (en) Trans-1,2 dichloroethylene composition
JP2007501885A (en) Production method of polymer foam
WO1996037540A1 (en) Foamable composition containing unsaturated perfluorochemical blowing agent
JP3952185B2 (en) Method for producing foaming agent, premix and foam having low vapor pressure
WO2007003726A1 (en) Method of preparing polyurethane-moulded articles
BE1006443A3 (en) Method for preparing a cellular polymeric substance and premixtures thatcan be used for the preparation of said substance
WO1994014882A1 (en) Mixtures useful for preparing a cellular polymeric material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080825

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130516

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20130927