FR2921664A1 - Composition, useful as foaming agent in manufacturing polyurethane foams/polyisocyanurate, and as solvents, aerosols and/or refrigerants, comprises trans-1,2 dichloroethylene and hydrofluoroolefin - Google Patents
Composition, useful as foaming agent in manufacturing polyurethane foams/polyisocyanurate, and as solvents, aerosols and/or refrigerants, comprises trans-1,2 dichloroethylene and hydrofluoroolefin Download PDFInfo
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- FR2921664A1 FR2921664A1 FR0757950A FR0757950A FR2921664A1 FR 2921664 A1 FR2921664 A1 FR 2921664A1 FR 0757950 A FR0757950 A FR 0757950A FR 0757950 A FR0757950 A FR 0757950A FR 2921664 A1 FR2921664 A1 FR 2921664A1
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- 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
- C08J2207/00—Foams characterised by their intended use
- C08J2207/04—Aerosol, e.g. polyurethane foam spray
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
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- Physics & Mathematics (AREA)
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- Thermal Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
La présente invention concerne des compositions aptes à être utilisées comme agent d'expansion dans la fabrication des polymères thermoplastiques et/ou thermodurcissables. Elle a plus particulièrement pour objet des compositions comprenant du trans-1,2 dichloroéthylène ( TDCE ) et au moins un hydrofluoro-oléfine et leur utilisations. 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. The present invention relates to compositions suitable for use as an expanding agent in the manufacture of thermoplastic and / or thermosetting polymers. More particularly, it relates to compositions comprising trans-1,2-dichloroethylene (TDCE) and at least one hydrofluoroolefin and their uses. 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.
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) 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. 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) Thus, the use of at least one HFC as blowing agent in the manufacture of isocyanate-based foams has been described in EP 381986. In view of the increasingly severe environmental constraints, the partial replacement of HFC 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.
L'objet de la présente invention vise à fournir une composition qui répond à la fois aux critères d'ODP négligeable et de bas GWP. La contribution à l'effet de serre d'un fluide est quantifiée par un critère, le GWP qui résume le pouvoir de réchauffement en prenant une valeur de référence de 1 pour le dioxyde de carbone. The object of the present invention is to provide a composition that meets both negligible ODP and low GWP criteria. The contribution to the greenhouse effect of a fluid is quantified by a criterion, the GWP which summarizes the heating power by taking a reference value of 1 for carbon dioxide.
Les méthodes de fabrication de mousses de polyuréthane ou de polyisocyanurate sont généralement connues et consistent en général à faire réagir un polyisocyanate organique (incluant le diisocyanate) avec un polyol ou un mélange de polyols en présence d'un agent d'expansion. Methods of making polyurethane or polyisocyanurate foams are generally known and generally involve reacting an organic polyisocyanate (including diisocyanate) with a polyol or a polyol blend in the presence of a blowing agent.
La réaction entre un polyisocyanate et un polyol ou un mélange de polyols peut être activée à l'aide d'une amine et/ou d'autres catalyseurs et des agents tensio-actifs. Dans beaucoup d'applications, les composants des mousses de polyuréthane ou polyisocyanurate 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 le mélange de polyols, l'agent tensio-actif, le ou les catalyseur(s), le ou les agent(s) d'expansion. Le composant B pose des problèmes d'inflammabilité, même lorsque l'agent d'expansion entrant dans la composition du prémélange est non inflammable. The reaction between a polyisocyanate and a polyol or a mixture of polyols can be activated with an amine and / or other catalysts and surfactants. In many applications, the components of the polyurethane or polyisocyanurate foams are premixes. More generally, the formulation of the foams is premixed into two components. The first component, better known as component A, comprises the isocyanate or polyisocyanate composition. The second component, better known under the name component B comprises the polyol or the mixture of polyols, the surfactant, the catalyst (s), or the agent (s) of expansion. Component B poses flammability problems, even when the blowing agent used in the premix composition is non-flammable.
En outre, les problèmes d'élévation de pression des conteneurs renfermant le composant B sont souvent rencontrés lors de leur stockage. Un autre objet de la présente invention vise à fournir des compositions qui permettent de résoudre tout ou en partie les problèmes précités. La présente invention concerne des compositions comprenant du trans- 1,2 dichloroéthylène et d'au moins une hydrofluorooléfine non inflammable, de préférence ayant un nombre de carbone compris entre 3 et 5. On entend par liquide non inflammable un liquide dont le point éclair, mesuré selon la norme ASTM D3828, est supérieur à 55°C. L'inflammabilité ou non-inflammabilité d'un gaz peut-être déterminée dans les conditions définies dans la norme ASTM E681-01. Les tests d'inflammabilité des gaz sont conduits dans des conditions de température, de pression et de concentration en air conformes à la norme. Cette méthode de test est basée sur une source de chaleur électrique et sur l'observation de la propagation de la flamme. In addition, pressure elevation problems of containers containing component B are often encountered during storage. Another object of the present invention is to provide compositions that solve all or part of the aforementioned problems. The present invention relates to compositions comprising trans-1,2-dichloroethylene and at least one non-flammable hydrofluoroolefin, preferably having a carbon number of between 3 and 5. By non-flammable liquid is meant a liquid whose flash point, measured according to ASTM D3828, is greater than 55 ° C. The flammability or non-flammability of a gas may be determined under the conditions defined in ASTM E681-01. Gas flammability tests are conducted under conditions of temperature, pressure and air concentration in accordance with the standard. This test method is based on an electrical heat source and the observation of flame propagation.
Les compositions selon la présente invention comprennent de préférence de 50 à 89 % en poids du trans-1,2 dichloroéthylène et de 11 à 50 0/0 en poids d'au moins un hydrofluoro-oléfine non inflammable. 3 The compositions according to the present invention preferably comprise from 50 to 89% by weight of trans-1,2-dichloroethylene and from 11 to 50% by weight of at least one non-flammable hydrofluoroolefin. 3
L'hydrofluorooléfine est choisie de préférence parmi le 1,1,1,2,3-pentafluoropropène ( HFO-1225ye ), le 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFO-1429myz) et le 1,1,1,4,4,5,5,5-octafluoro-2-pentene. Le 1,1,1,2,3-pentafluoropropène ( HFO-1225ye ) est avantageusement préféré. The hydrofluoroolefin is preferably chosen from 1,1,1,2,3-pentafluoropropene (HFO-1225ye), 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFO-1429myz) and 1,1,1,4,4,5,5,5-octafluoro-2-pentene. 1,1,1,2,3-Pentafluoropropene (HFO-1225ye) is advantageously preferred.
Lorsque l'hydrofluorooléfine existe sous la forme d'isomères, il peut être sous la forme E et Z. Les compositions selon la présente invention peuvent comprendre en outre au moins un composé choisi parmi les hydrofluorocarbures et / ou les hydrofluoroéthers. When the hydrofluoroolefin exists in the form of isomers, it may be in the E and Z form. The compositions according to the present invention may further comprise at least one compound chosen from hydrofluorocarbons and / or hydrofluoroethers.
Comme hydrofluorocarbures, on peut citer notamment le 1,1,1,3,3-pentafluoropropane (245 fa), le 1,1,1,3,3,3-hexafluoropropane (227ea) et le 1,1,1,3,3-pentafluorobutane (365 mfc). Les compositions particulièrement préférées comprennent du TDCE, au moins un hydrofluoroéther et au moins un hydrofluorooléfine non inflammable. As hydrofluorocarbons, there may be mentioned in particular 1,1,1,3,3-pentafluoropropane (245 fa), 1,1,1,3,3,3-hexafluoropropane (227ea) and 1,1,1,3 3-pentafluorobutane (365 mfc). Particularly preferred compositions include TDCE, at least one hydrofluoroether and at least one non-flammable hydrofluoroolefin.
Les compositions préférées comprennent de 60 à 89 % en poids de TDCE, de 29 à 1 % en poids d'au moins un hydrofluoroéther et de 40 à 10 % en poids d'au moins un hydrofluoro-oléfine non inflammable. Comme hydrofluoroéthers, on peut citer notamment le 1- méthoxy nonafluorobutane et le 1-éthoxy nonafluorobutane. The preferred compositions comprise 60 to 89% by weight of TDCE, 29 to 1% by weight of at least one hydrofluoroether and 40 to 10% by weight of at least one non-flammable hydrofluoroolefin. As hydrofluoroethers, there may be mentioned in particular 1-methoxy nonafluorobutane and 1-ethoxy nonafluorobutane.
Les compositions selon la présente invention ont un bas de GWP, de préférence inférieure à 1000 et avantageusement inférieure à 150. Les compositions selon la présente invention ne présentent pas de point éclair dans les conditions standard de détermination (norme ASTM D 3828). Elles peuvent être utilisées comme agent d'expansion dans la fabrication des mousses de polymères thermoplastiques ou thermodurcissables comme par exemple les condensats de phenol/formol ou le polyurethane. Elles conviennent tout particulièrement à la fabrication de mousses de polyuréthane ou de polyisocyanurate. La présente invention a également pour objet un agent d'expansion comprenant les compositions telles que définies précédemment. Un autre objet de la présente invention est un prémélange comprenant, outre les constituants des compositions définies précédemment, un polyol ou un mélange de polyols. The compositions according to the present invention have a base of GWP, preferably less than 1000 and advantageously less than 150. The compositions according to the present invention do not have a flash point under the standard conditions of determination (ASTM D 3828 standard). They can be used as an expansion agent in the manufacture of thermoplastic or thermosetting polymer foams such as, for example, phenol / formaldehyde condensates or polyurethane. They are particularly suitable for the manufacture of polyurethane foams or polyisocyanurate. The present invention also relates to an expansion agent comprising the compositions as defined above. Another object of the present invention is a premix comprising, in addition to the constituents of the compositions defined above, a polyol or a mixture of polyols.
Selon la présente invention, le prémélange renfermant un polyol ou un mélange de polyols ne présente pas de point éclair dans la gamme de température de -20 à 61 °C et suivant la norme ASTM D 3828. 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. Les polyétherpolyols obtenus par addition d'oxydes d'alkylènes, en particulier l'oxyde d'éthylène et/ou l'oxyde de propylène, sur les amines aromatiques en particulier le mélange de 2,4 et 2,6 de toluène diamine conviennent également. Les polyétherpolyols sont particulièrement préférés. De préférence, les prémélanges comprennent de 1 à 20 parties en poids de TDCE, de 2 à 10 parties en poids d'au moins un hydrofluorooléfines non inflammables, de 0 à 10 parties poids d'au moins un hydrofluoroéther pour 100 parties en poids de polyol ou mélange de polyols. Avantageusement, elle comprend de 1 à 12 parties en poids de TDCE, de 2 à 5 parties en poids d'au moins un hydrofluorooléfine non inflammable, de 0 à 6 parties poids d'au moins un hydrofluoroéther pour 100 parties en poids de polyol ou mélange de polyols. According to the present invention, the premix containing a polyol or a mixture of polyols does not have a flash point in the temperature range of -20 to 61 ° C and according to ASTM D 3828. As polyols, mention may in particular be made of glycerol ethylene glycol, trimethylolpropane, pentaerythritol, polyether polyols, for example those obtained by condensation of an alkylene oxide or a mixture of alkylene oxides with glycerol, ethylene glycol and trimethylolpropane. , pentaerythritol, polyesterspolyols, for example those obtained from polycarboxylic acids, in particular oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, acid, isophthalic, terephthalic acid, with glycerol, ethylene glycol, trimethylolpropane, pentaerythritol. 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. . Polyether polyols are particularly preferred. Preferably, the premixes comprise from 1 to 20 parts by weight of TDCE, from 2 to 10 parts by weight of at least one non-flammable hydrofluoroolefins, from 0 to 10 parts by weight of at least one hydrofluoroether per 100 parts by weight of polyol or mixture of polyols. Advantageously, it comprises from 1 to 12 parts by weight of TDCE, from 2 to 5 parts by weight of at least one non-flammable hydrofluoroolefin, from 0 to 6 parts by weight of at least one hydrofluoroether per 100 parts by weight of polyol or mixture of polyols.
Les compositions selon la présente invention peut comprendre en outre d'autre agent(s) d'expansion, d' un agent tensio-actif,et d'un ou plusieurs catalyseur(s). Les prémélanges décrits précédemment peuvent réagir avec un polyisocyanate organique, pour donner des mousses. The compositions according to the present invention may further comprise other blowing agent (s), a surfactant, and one or more catalyst (s). The premixes described above can be reacted with an organic polyisocyanate to give foams.
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 5 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, polymethylene polyphenyl 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.
Les compositions selon la présente invention peuvent également être utilisées comme solvants, aérosols et/ou réfrigérants. The compositions according to the present invention can also be used as solvents, aerosols and / or refrigerants.
PARTIE EXPERIMENTALE EXEMPLE 1 On prépare une composition (exemple 1) comprenant 100 parties en poids de TDCE et 20 parties en poids de HFO-1225ye, puis on détermine le point éclair dans les conditions standard (ASTM D3828). Le 1,2,3,3,3-pentafluoropropène (HFO-1225 ye) étant gazeux, il est préalablement refroidi avant de réaliser le mélange avec le TDCE qui est également refroidi. Le HFO-1225 ye utilisé est un mélange d'isomère de conformation Z et d'isomère de conformation E avec une part majoritaire d'isomère Z. DCE pur Exemple 1 Il n'a pas été observé de point éclair dans la gamme de température comprise entre -20 et 52°C alors qu'avec le TDCE pur, un point éclair a été observé entre -14 et ù 5°C. Au-dessus de 52°C, les compositions selon l'exemple 1 commence à passer à l'état gazeux. -14°C à -5°C Pas de point éclair25 6 EXPERIMENTAL PART EXAMPLE 1 A composition (Example 1) comprising 100 parts by weight of TDCE and 20 parts by weight of HFO-1225ye is prepared, then the flash point is determined under standard conditions (ASTM D3828). Since 1,2,3,3,3-pentafluoropropene (HFO-1225 ye) is gaseous, it is previously cooled before mixing with TDCE, which is also cooled. The HFO-1225 used is a mixture of Z conformation isomer and E conformation isomer with a major part of Z isomer. Pure DCE Example 1 No flash point in the temperature range was observed between -20 and 52 ° C whereas with pure TDCE, a flash point was observed between -14 and -5 ° C. Above 52 ° C, the compositions according to Example 1 begin to go into the gaseous state. -14 ° C to -5 ° C No flash point25 6
EXEMPLE 2 On prépare une composition d'agent d'expansion comprenant 10 parties en poids de TDCE, 3 parties en poids de HFO-1225ye, puis on la mélange avec 100 parties en poids d'un polyol STEPANPOL PS2412 ( un polyol de type polyester). Le prémelange ne présente pas de point éclair dans la gamme de température comprise entre ù 30 à 61 °C dans les conditions standards ( norme ASTM D3828). On fabrique ensuite une mousse en faisant réagir ce prémélange avec 110 parties en poids de DESMODUR 44V70L ( isocyanate) en présence de 2,82 parties en poids d'un catalyseur DABCO K-15 ( solution sel organique ) et de 0,18 parties en poids d'un catalyseur POLYCAT 5 ( aamine tertiaire ) et de 1,5 parties en poids d'un tensio-actif TEGOSTAB B 8465 ( polyether-modifié polysiloxane ). La mousse obtenue a une densité inférieure à 35kg/m3 et présente un taux de cellules fermées de 68 %. EXAMPLE 2 A blowing agent composition comprising 10 parts by weight of TDCE, 3 parts by weight of HFO-1225ye, and then mixing with 100 parts by weight of a polyol STEPANPOL PS2412 (a polyol of polyester type) is prepared. ). The premix has no flash point in the temperature range of 30 to 61 ° C under standard conditions (ASTM D3828). A foam is then made by reacting this premix with 110 parts by weight of DESMODUR 44V70L (isocyanate) in the presence of 2.82 parts by weight of a DABCO K-15 catalyst (organic salt solution) and 0.18 parts by weight of weight of a POLYCAT 5 catalyst (tertiary amine) and 1.5 parts by weight of a surfactant TEGOSTAB B 8465 (polyether-modified polysiloxane). The foam obtained has a density of less than 35 kg / m3 and has a closed cell level of 68%.
EXEMPLE 3 On prepare plusieurs compositions et prémélanges renfermant du TDCE, du 1- éthoxy nonafluorobutane (HFE-7200) et/ou du HFO-1225ye et éventuellement de polyol STEPANPOL PS2412 ; puis on détermine le point éclair dans la gamme de température comprise entre 25 à 61 °C dans les conditions standards ( norme ASTM D3828). Les résultats sont reportés dans le tableau ci-après. Exemple TDCE HFE- H FO- polyol 7200 1225ye 3 100 20 Non 4 10 2 100 38 à 44°C 5 10 2 100 Non 6 10 2 2 100 Non25 EXAMPLE 3 Several compositions and premixes containing TDCE, 1-ethoxy nonafluorobutane (HFE-7200) and / or HFO-1225ye and optionally polyol STEPANPOL PS2412 are prepared; then the flash point in the temperature range of 25 to 61 ° C is determined under standard conditions (ASTM D3828). The results are reported in the table below. Example TDCE HFE-H FO-polyol 7200 1225ye 3 100 20 No 4 10 2 100 38 at 44 ° C 5 10 2 100 No 6 10 2 2 100 Non25
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0757950A FR2921664A1 (en) | 2007-09-28 | 2007-09-28 | Composition, useful as foaming agent in manufacturing polyurethane foams/polyisocyanurate, and as solvents, aerosols and/or refrigerants, comprises trans-1,2 dichloroethylene and hydrofluoroolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0757950A FR2921664A1 (en) | 2007-09-28 | 2007-09-28 | Composition, useful as foaming agent in manufacturing polyurethane foams/polyisocyanurate, and as solvents, aerosols and/or refrigerants, comprises trans-1,2 dichloroethylene and hydrofluoroolefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| FR2921664A1 true FR2921664A1 (en) | 2009-04-03 |
Family
ID=39325907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR0757950A Pending FR2921664A1 (en) | 2007-09-28 | 2007-09-28 | Composition, useful as foaming agent in manufacturing polyurethane foams/polyisocyanurate, and as solvents, aerosols and/or refrigerants, comprises trans-1,2 dichloroethylene and hydrofluoroolefin |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2921664A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011069203A1 (en) * | 2009-12-08 | 2011-06-16 | Barry Branscombe Walker | Blowing agents for foams |
| US10731019B2 (en) | 2015-04-10 | 2020-08-04 | Dap Products Inc. | Stable two component spray foam compositions containing hydrohaloolefin propellant or blowing agent |
| GB2587617A (en) * | 2019-09-27 | 2021-04-07 | Kingspan Holdings Irl Ltd | Polyurethane and polyisocyanurate foam and method of manufacture thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020061935A1 (en) * | 1998-05-15 | 2002-05-23 | Kingspan Industrial Insulation Limited | Closed cell phenolic foam |
| WO2002099006A1 (en) * | 2001-06-01 | 2002-12-12 | Honeywell International, Inc. | Compositions of hydrofluorocarbons and trans-1,2-dichloroethylene |
| FR2882358A1 (en) * | 2005-02-23 | 2006-08-25 | Arkema Sa | Composition, useful e.g. as foaming agent to manufacture thermoplastic polymer foams, comprises trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane and 1,1,1,2-tetrafluoroethane |
| US20060266975A1 (en) * | 2005-05-27 | 2006-11-30 | Nappa Mario J | Compositions comprising 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene |
| WO2007109748A2 (en) * | 2006-03-21 | 2007-09-27 | Honeywell International Inc. | Foaming agents containing fluorine substituted unsaturated olefins |
-
2007
- 2007-09-28 FR FR0757950A patent/FR2921664A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020061935A1 (en) * | 1998-05-15 | 2002-05-23 | Kingspan Industrial Insulation Limited | Closed cell phenolic foam |
| WO2002099006A1 (en) * | 2001-06-01 | 2002-12-12 | Honeywell International, Inc. | Compositions of hydrofluorocarbons and trans-1,2-dichloroethylene |
| FR2882358A1 (en) * | 2005-02-23 | 2006-08-25 | Arkema Sa | Composition, useful e.g. as foaming agent to manufacture thermoplastic polymer foams, comprises trans-1,2-dichloroethylene, 1,1,1,3,3-pentafluoropropane and 1,1,1,2-tetrafluoroethane |
| US20060266975A1 (en) * | 2005-05-27 | 2006-11-30 | Nappa Mario J | Compositions comprising 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene |
| WO2007109748A2 (en) * | 2006-03-21 | 2007-09-27 | Honeywell International Inc. | Foaming agents containing fluorine substituted unsaturated olefins |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011069203A1 (en) * | 2009-12-08 | 2011-06-16 | Barry Branscombe Walker | Blowing agents for foams |
| US10731019B2 (en) | 2015-04-10 | 2020-08-04 | Dap Products Inc. | Stable two component spray foam compositions containing hydrohaloolefin propellant or blowing agent |
| GB2587617A (en) * | 2019-09-27 | 2021-04-07 | Kingspan Holdings Irl Ltd | Polyurethane and polyisocyanurate foam and method of manufacture thereof |
| GB2587617B (en) * | 2019-09-27 | 2022-02-23 | Kingspan Holdings Irl Ltd | Polyurethane and polyisocyanurate foam and method of manufacture thereof |
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