WO2007003726A1 - Method of preparing polyurethane-moulded articles - Google Patents

Method of preparing polyurethane-moulded articles Download PDF

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Publication number
WO2007003726A1
WO2007003726A1 PCT/FR2006/001116 FR2006001116W WO2007003726A1 WO 2007003726 A1 WO2007003726 A1 WO 2007003726A1 FR 2006001116 W FR2006001116 W FR 2006001116W WO 2007003726 A1 WO2007003726 A1 WO 2007003726A1
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WO
WIPO (PCT)
Prior art keywords
hydrofluorocarbon
dichloroethylene
weight
mixture
trans
Prior art date
Application number
PCT/FR2006/001116
Other languages
French (fr)
Inventor
Vincent Enaux
Christiaan Geert Marie-Ghislaine Debien
Original Assignee
Arkema France
Huntsman International Llc
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, Huntsman International Llc filed Critical Arkema France
Priority to JP2008518893A priority Critical patent/JP2008545036A/en
Priority to EP06764642A priority patent/EP1904562A1/en
Publication of WO2007003726A1 publication Critical patent/WO2007003726A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • 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
    • 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
    • C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a process for the preparation of polyurethane molded articles having a dense periphery (skin) with a certain hardness and a cellular core (so-called integral skin foam) and foams prepared by means thereof. this.
  • Polyurethane foam manufacturing processes generally involve reacting an organic polyisocyanate with a polyol or a polyol mixture in the presence of a blowing agent.
  • Chlorofluorocarbon compounds such as trichlorofluoromethane (CFC-11) have most often been used as blowing agents. These compounds, however, present a danger for the ozone layer.
  • HCFC 141b 1,1-dichloro-1-fluoroethane
  • HCFC 141b 1,1-dichloro-1-fluoroethane
  • hydrofluorocarbons including 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,2,2-tetrafluoroethane (HFC-134) as blowing agents in the manufacture of foams polyurethane integral skin is known (US 5506275, US 6010649).
  • document EP 1345987 teaches the use of a mixture of 1, 1, 1, 3,3-pentafluorobutane (HFC 365mfc) and of 1, 1, 1, 2,3,3,3-heptafluoropropane (HFC 227ea) as blowing agents in the manufacture of polyurethane molded articles having a dense periphery and a cellular core.
  • HFC 365mfc 1, 1, 1, 3,3-pentafluorobutane
  • HFC 227ea 1, 1, 1, 2,3,3,3-heptafluoropropane
  • the subject of the present invention is a process for producing polyurethane molded articles having a dense periphery and a cellular central part, comprising a reaction stage of an organic polyisocyanate composition with a polyfunctional composition reactive with isocyanates, characterized in that a mixture of transi, 2- dichloroethylene (TDCE) and at least one hydrofluorocarbon as blowing agents.
  • TDCE transi, 2- dichloroethylene
  • the transi, 2-dichloroethylene is present in the blowing agent mixture in an amount such that the mass ratio transi, 2-dichloroethylene / hydrofluorocarbon (s) is between 4.5 and 20.
  • hydrofluorocarbons mention may in particular be made of 1, 1, 1, 3, 3-pentafluoropropane (HFC-245fa), 1, 1, 1, 3,3-pentafluorobutane (HFC 365mfc), 1, 1, 1, 2, 3,3,3-heptafluoropropane (HFC 227ea) and 1,1,1,3,3,3-hexafluoropropane, or a mixture thereof.
  • HFC-245fa 1, 1, 1, 1, 3,3-pentafluorobutane
  • HFC 365mfc 1, 1, 1, 2, 3,3,3-heptafluoropropane
  • HFC 227ea 1,1,1,3,3,3-hexafluoropropane
  • use is preferably made between 2 and 15% by weight of mixture of transi, 2-dichloroethylene and at least one hydrofluorocarbon relative to the weight of the composition reactive with isocyanates.
  • use is made between 4 and 15% by weight of mixture of transi, 2-dichloroethylene and
  • aromatic polyisocyanates such as diphenylmethane diisocyanate in the form of its isomers 2,4 ', 2,2' and 4,4 'and mixtures thereof, mixtures of diphenylmethane diisocyanates (MDI) and oligomers thereof known under the name MDI "crude” or polymeric (polymethylene-polyphenylene).
  • polyisocyanates having an isocyanate functionality greater than 2, toluene diisocyanate in the form of its 2,4 and 2,6 isomers and mixtures thereof, 1,5-naphthalenediisocyanate and 1,4-diisocyanatobenzene.
  • organic polyisocyanates include aliphatic diisocyanates such as isophorone diisocyanate, 1,6-diisocyanatohexane and 4,4'-diisocyanatodicyclohexylmethane.
  • modified polyisocyanates for example containing urethane, urea, biuret, allophonate, carbodiimide or uretdione groups, or isocyanate-terminated prepolymers.
  • the polyfunctional isocyanate-reactive compositions suitable in the process of the present invention include all those known in the prior art for the preparation of integral skin polyurethane foams. Particularly important for the preparation of semi-rigid full skin polyurethane foams are polyols and polyol mixtures having average hydroxyl numbers of from 20 to 200, in particular from 20 to 50 mg KOH / g, and hydroxyl functionalities of 2 to 3.
  • polyether polyols the molecular weight is preferably between 2000 and 8000; for the polyester polyols it is preferably between 2000 and 4000.
  • Particularly preferred polyols for the preparation of rigid polyurethane integral skin foams are polyether polyols having average hydroxyl numbers of between 300 and 1850, preferably between 350 and 650 mg KOH / g, and hydroxyl functionalities of 2 to 6, preferably 3 to 4. It is also possible to use mixtures of different polyols; the mixing ratio depends on the application of the integral skin foam and the desired surface hardness of the skin.
  • the polyether polyols which are suitable for the process of the present invention are, in particular, the reaction products of alkylene oxides, for example ethylene oxide and / or alkylene oxide, for example oxide of ethylene and / or propylene oxide, with initiators containing from 2 to 8 active hydrogen atoms per molecule.
  • alkylene oxides for example ethylene oxide and / or alkylene oxide, for example oxide of ethylene and / or propylene oxide
  • polyols for example ethylene glycol, propylene glycol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose
  • polyamines for example ethylenediamine, tolylenediamine (TDA), diaminodiphenylmethane (DADPM) and polymethylenepolyphenylene polyamines
  • aminoalcohols for example ethanolamine and diethanolamine; and their mixtures.
  • Suitable polyester polyols are those obtained by condensing appropriate amounts of higher functionality polyols and polyols with dicarboxylic or polycarboxylic acids such as adipic acid, glutaric acid and phthalic acid.
  • dicarboxylic or polycarboxylic acids such as adipic acid, glutaric acid and phthalic acid.
  • Other types of polyols that may be mentioned include hydroxyl terminated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes.
  • polyisocyanate compounds and polyfunctional isocyanate-reactive compounds to be reacted depend on the nature of the integral skin polyurethane foam to be prepared and will be readily determined by one skilled in the art.
  • water or other carbon dioxide-releasing compounds are used in conjunction with the blowing agent mixture of the present invention.
  • water is used in an amount generally less than 1%, preferably less than 0.5% by weight relative to the compounds reactive with isocyanates.
  • the reaction mixture may include customary additives included in the formulations for the production of integral skin polyurethane foams.
  • optional additives include crosslinking agents, for example low molecular weight polyols such as ethylene glycol, 1,4-butanediol, glycerol, trimethylolpropane and triethanolamine, urethane catalysts, for example tin compounds such as stannous octoate or dibutyltin dilaurate, or tertiary amines such as 1,4-diaza- (2,2,2) -bicyclooctane, bis (2-dimethylaminoethyl) ether, dimethylcyclohexylamine or triethylene diamine, surfactants, flame retardants, for example halogenated alkyl phosphates such as tris-chloropropyl phosphate, and fillers such as carbon black
  • the method according to the present invention has the advantage of having a lesser effect on global warming, which is interesting in an emissive application such as foams flexible vis-à-vis the circular F-gas in Europe. Implementation is also facilitated by better flow of the mixture comprising both reactive components due to a lowering of viscosity.
  • the subject of the present invention is also a premix comprising a polyfunctional composition reactive with isocyanates, trans-2-dichloroethylene and at least one hydrofluorocarbon.
  • the mass ratio of trans-2-dichloroethylene relative to (x) hydrofluorocarbon (s) in the premix is advantageously between 4.5 - 20: 1.
  • the amount of trans-2-dichloroethylene and hydrofluorocarbon or hydrofluorocarbons present in the premix represents between 0.1 and 15 parts by weight, preferably between 0.3 and 12 parts by weight relative to
  • the premix according to the present invention on the one hand has the advantage of having a much higher flash point compared to the premix comprising only the hydrocarbons as blowing agents and on the other hand the overall cost of the premix is lower than premix comprising hydrofluorocarbons alone.
  • the premix has a near zero ozone depletion potential (ODP).
  • the present invention further relates to an integral skin foam capable of being obtained according to the method described above.
  • Bayfit ® PU 10WF15 polyol marketed by Bayer 55.7 parts by weight
  • Daltocel ® XF417 polyol marketed by Huntsman 34.35 parts by weight
  • Tegostab ® B8715LF surfactant marketed by 0.2 parts by weight
  • Dabco EG (catalyst marketed by Air Products) 0.1 part by weight
  • composition (I) To 100 parts by weight of the composition (I) and at room temperature, 1 part by weight of a hydrofluorocarbon 245 and 6 parts by weight of trans 1, 2 dichloroethylene, premixed, are added.
  • composition (II) The mixture is then vigorously mixed to give a composition (II).
  • the foam obtained has a density of 190 kg / m 3 , according to the ISO 845 standard.
  • Another part of the resulting mixture is poured into an aluminum mold and then kept at a temperature between 40 and 45 ° C. The mold is then closed and after reaction, a foam with an overall density of 350 kg / m 3 is obtained. according to ISO 845. In addition, the integral skin foam is of good quality.
  • blowing agents (Examples 2 - 4, 7) or a mixture of blowing agents with trans 1, 2 is added to 100 parts by weight of the composition (I). dichloroethylene (TDCE) and then reacting 100 parts by weight of the resulting mixture with 50 parts by weight of Suprasec ® 2030 in an aluminum mold to a temperature between 40 and 45 ° C.
  • TDCE dichloroethylene
  • Suprasec ® 2030 in an aluminum mold to a temperature between 40 and 45 ° C.
  • the single table summarizes the properties of the foam obtained.
  • the flash point of each blowing agent alone or in mixture with TDCE has also been reported.

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

Abstract

The invention relates to a method of preparing polyurethane-moulded articles comprising a dense periphery (skin) having a certain hardness and a cellular central part and to foams prepared using same. The invention also relates to a premix comprising an isocyanate-reactive functional composition.

Description

PROCÉDÉ DE PRÉPARATION D'ARTICLES MOULÉS EN POLYURÉTHANE PROCESS FOR THE PREPARATION OF MOLDED POLYURETHANE ARTICLES
La présente invention concerne un procédé de préparation d'articles moulés en polyuréthane ayant une périphérie dense (peau) avec une certaine dureté et une partie centrale cellulaire (ce qu'on appelle une mousse peau intégrale) et des mousses préparées au moyen de celui-ci.The present invention relates to a process for the preparation of polyurethane molded articles having a dense periphery (skin) with a certain hardness and a cellular core (so-called integral skin foam) and foams prepared by means thereof. this.
Les procédés de fabrication de mousses de polyuréthane consistent en général à faire réagir un polyisocyanate organique avec un polyol ou un mélange de polyols en présence d'un agent d'expansion. Les composés chlorofluorocarbones tels que le trichlorofluorométhane (CFC-11) ont été le plus souvent utilisés comme agents d'expansion. Ces composés présentent toutefois un danger pour la couche d'ozone.Polyurethane foam manufacturing processes generally involve reacting an organic polyisocyanate with a polyol or a polyol mixture in the presence of a blowing agent. Chlorofluorocarbon compounds such as trichlorofluoromethane (CFC-11) have most often been used as blowing agents. These compounds, however, present a danger for the ozone layer.
Des composés moins dangereux pour l'environnement ont été proposés en remplacement des chlorofluorocarbones. Ainsi, le 1 ,1 -dichloro-1 - fluoroéthane (HCFC 141 b) a été utilisé comme agent d'expansion dans la fabrication des mousses de polyuréthane pour donner des mousses avec une peau densifiée ayant une grande dureté superficielle. Cependant, le HCFC 141b est considéré comme nuisible à l'environnement.Compounds that are less dangerous for the environment have been proposed as alternatives to chlorofluorocarbons. Thus, 1,1-dichloro-1-fluoroethane (HCFC 141b) has been used as an expanding agent in the manufacture of polyurethane foams to provide foams with densified skin having a high surface hardness. However, HCFC 141b is considered to be harmful to the environment.
L'utilisation des hydrofluorocarbures, notamment le 1 ,1 ,1 ,3,3- pentafluoropropane (HFC-245fa) et le 1 ,1 ,2,2-tétrafluoroéthane (HFC-134) comme agents d'expansion dans la fabrication des mousses de polyuréthane à peau intégrale est connue (US 5506275, US 6010649) .The use of hydrofluorocarbons, including 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,2,2-tetrafluoroethane (HFC-134) as blowing agents in the manufacture of foams polyurethane integral skin is known (US 5506275, US 6010649).
Par ailleurs, le document EP 1345987 enseigne l'utilisation d'un mélange de 1 ,1 ,1 ,3,3-pentafluorobutane (HFC 365mfc) et de 1 ,1 ,1 ,2,3,3,3- heptafluoropropane (HFC 227ea) comme agents d'expansion dans la fabrication des articles moulés en polyuréthane ayant une périphérie dense et une partie centrale cellulaire.Furthermore, document EP 1345987 teaches the use of a mixture of 1, 1, 1, 3,3-pentafluorobutane (HFC 365mfc) and of 1, 1, 1, 2,3,3,3-heptafluoropropane (HFC 227ea) as blowing agents in the manufacture of polyurethane molded articles having a dense periphery and a cellular core.
La présente invention a pour objet un procédé de fabrication des articles moulés en polyuréthane ayant une périphérie dense et une partie centrale cellulaire, comprenant une étape réactionnelle d'une composition polyisocyanate organique avec une composition polyfonctionnelle réactive avec les isocyanates caractérisé en ce qu'on utilise un mélange de transi ,2- dichloroéthylène (TDCE) et d'au moins un hydrofluorocarbure comme agents d'expansion.The subject of the present invention is a process for producing polyurethane molded articles having a dense periphery and a cellular central part, comprising a reaction stage of an organic polyisocyanate composition with a polyfunctional composition reactive with isocyanates, characterized in that a mixture of transi, 2- dichloroethylene (TDCE) and at least one hydrofluorocarbon as blowing agents.
De préférence, le transi ,2-dichloroéthylène est présent dans te mélange d'agents d'expansion en quantité telle que le rapport massique transi ,2- dichloroéthylène/ hydrofluorocarbure(s) est compris entre 4,5 et 20.Preferably, the transi, 2-dichloroethylene is present in the blowing agent mixture in an amount such that the mass ratio transi, 2-dichloroethylene / hydrofluorocarbon (s) is between 4.5 and 20.
Comme hydrofluorocarbures, on peut citer notamment le 1 ,1 ,1 ,3,3- pentafluoropropane (HFC-245fa), 1 ,1 ,1 ,3,3-pentafluorobutane (HFC 365mfc), le 1 ,1 ,1 ,2,3,3,3-heptafluoropropane (HFC 227ea) et le 1 ,1 ,1 ,3,3,3- hexafluoropropane, ou leur mélange. Dans le procédé selon la présente invention, on utilise de préférence entre 2 et 15 % en poids de mélange de transi ,2-dichloroéthylène et d'au moins un hydrofluorocarbure par rapport au poids de la composition réactive avec les isocyanates. Avantageusement, on utilise entre 4 et 15 % en poids de mélange de transi ,2-dichloroéthylène et d'au moins un hydrofluorocarbure par rapport au poids de la composition réactive avec les isocyanates.As hydrofluorocarbons, mention may in particular be made of 1, 1, 1, 3, 3-pentafluoropropane (HFC-245fa), 1, 1, 1, 3,3-pentafluorobutane (HFC 365mfc), 1, 1, 1, 2, 3,3,3-heptafluoropropane (HFC 227ea) and 1,1,1,3,3,3-hexafluoropropane, or a mixture thereof. In the process according to the present invention, use is preferably made between 2 and 15% by weight of mixture of transi, 2-dichloroethylene and at least one hydrofluorocarbon relative to the weight of the composition reactive with isocyanates. Advantageously, use is made between 4 and 15% by weight of mixture of transi, 2-dichloroethylene and at least one hydrofluorocarbon relative to the weight of the composition reactive with isocyanates.
Les polyisocyanates organiques qui conviennent au procédé de la présente invention comprennent tous ceux qui sont connus de l'état de la technique pour la préparation de mousses de polyuréthanne à peau intégrale et en particulier les polyisocyanates aromatiques comme le diphénylméthane- diisocyanate sous la forme de ses isomères 2,4', 2,2' et 4,4' et leurs mélanges, les mélanges de diphénylméthane-diisocyanates (MDI) et les oligomères de ceux-ci connus sous la dénomination MDI « bruts » ou polymériques (polyméthylène-polyphénylène-polyisocyanates) ayant une fonctionnalité isocyanate supérieure à 2, le toluène-diisocyanate sous la forme de ses isomères 2,4 et 2,6 et leurs mélanges, le 1 ,5-naphtalène-diisocyanate et le 1 ,4- diisocyanatobenzène. On peut citer d'autres polyisocyanates organiques, notamment les diisocyanates aliphatiques comme l'isophorone-diisocyanate, le 1 ,6-diisocyanatohexane et le 4,4'-diisocyanatodicyclohexylméthane. On peut également utiliser des polyisocyanates modifiés, par exemple contenant des groupes uréthane, urée, biuret, allophonate, carbodiimide ou uretdione, ou des prépolymères à terminaison isocyanate. Les compositions polyfonctionnelles réactives avec les isocyanates qui conviennent dans le procédé de la présente invention comprennent tous ceux qui sont connus dans i'art antérieur pour ia préparation de mousses de polyuréthanne à peau intégrale. Sont particulièrement importants pour la préparation de mousses de polyuréthane semi-rigides à peau intégrale, les polyols et les mélanges de polyols ayant des indices moyens d'hydroxyle de 20 à 200, en particulier de 20 à 50 mg de KOH/g, et des fonctionnalités hydroxyle de 2 à 3. Pour les polyéther-polyols, le poids moléculaire est compris de préférence entre 2000 et 8000 ; pour les polyester-polyols, il est de préférence entre 2000 et 4000. Les polyols particulièrement préférés pour la préparation de mousses rigides de polyuréthane à peau intégrale sont les polyéther-polyols ayant des indices moyens d'hydroxyle compris entre 300 et 1850, de préférence entre 350 et 650 mg de KOH/g, et des fonctionnalités hydroxyle de 2 à 6, de préférence de 3 à 4. On peut également utiliser des mélanges de différents polyols ; le rapport de mélange dépend de l'application de la mousse à peau intégrale et de la dureté superficielle désirée de la peau.The organic polyisocyanates which are suitable for the process of the present invention include all those known from the state of the art for the preparation of integral skin polyurethane foams and in particular aromatic polyisocyanates such as diphenylmethane diisocyanate in the form of its isomers 2,4 ', 2,2' and 4,4 'and mixtures thereof, mixtures of diphenylmethane diisocyanates (MDI) and oligomers thereof known under the name MDI "crude" or polymeric (polymethylene-polyphenylene). polyisocyanates) having an isocyanate functionality greater than 2, toluene diisocyanate in the form of its 2,4 and 2,6 isomers and mixtures thereof, 1,5-naphthalenediisocyanate and 1,4-diisocyanatobenzene. Other organic polyisocyanates include aliphatic diisocyanates such as isophorone diisocyanate, 1,6-diisocyanatohexane and 4,4'-diisocyanatodicyclohexylmethane. It is also possible to use modified polyisocyanates, for example containing urethane, urea, biuret, allophonate, carbodiimide or uretdione groups, or isocyanate-terminated prepolymers. The polyfunctional isocyanate-reactive compositions suitable in the process of the present invention include all those known in the prior art for the preparation of integral skin polyurethane foams. Particularly important for the preparation of semi-rigid full skin polyurethane foams are polyols and polyol mixtures having average hydroxyl numbers of from 20 to 200, in particular from 20 to 50 mg KOH / g, and hydroxyl functionalities of 2 to 3. For polyether polyols, the molecular weight is preferably between 2000 and 8000; for the polyester polyols it is preferably between 2000 and 4000. Particularly preferred polyols for the preparation of rigid polyurethane integral skin foams are polyether polyols having average hydroxyl numbers of between 300 and 1850, preferably between 350 and 650 mg KOH / g, and hydroxyl functionalities of 2 to 6, preferably 3 to 4. It is also possible to use mixtures of different polyols; the mixing ratio depends on the application of the integral skin foam and the desired surface hardness of the skin.
Les polyéther-polyols qui conviennent au procédé de la présente invention sont notamment les produits de réaction d'oxydes d'alkylène, par exemple d'oxyde d'éthylène et/ou d'oxyde d'alkylène, par exemple d'oxyde d'éthylène et/ou d'oxyde de propylène, avec des initiateurs contenant de 2 à 8 atomes d'hydrogène actif par molécule. Comme initiateurs, on peut citer notamment les polyols, par exemple éthylèneglycol, propylèneglycol, glycérol, triméthylolpropane, triéthanolamine, pentaéry-thritol, sorbitol et saccharose ; les polyamines, par exemple éthylènediamine, tolylènediamine (TDA), diaminodiphénylméthane (DADPM) et polyméthylènepolyphénylène- polyamines ; et les amino-alcools, par exemple l'éthanolamine et la diéthanolamine ; et leurs mélanges. Les polyester-polyols qui conviennent sont ceux obtenus par condensation de quantités appropriées de glycols et de polyols à fonctionnalité supérieure avec des acides dicarboxyliques ou polycarboxyliques comme l'acide adipique, l'acide glutarique et l'acide phtalique. 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 polysiloxanes.The polyether polyols which are suitable for the process of the present invention are, in particular, the reaction products of alkylene oxides, for example ethylene oxide and / or alkylene oxide, for example oxide of ethylene and / or propylene oxide, with initiators containing from 2 to 8 active hydrogen atoms per molecule. As initiators, mention may be made in particular of polyols, for example ethylene glycol, propylene glycol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose; polyamines, for example ethylenediamine, tolylenediamine (TDA), diaminodiphenylmethane (DADPM) and polymethylenepolyphenylene polyamines; and aminoalcohols, for example ethanolamine and diethanolamine; and their mixtures. Suitable polyester polyols are those obtained by condensing appropriate amounts of higher functionality polyols and polyols with dicarboxylic or polycarboxylic acids such as adipic acid, glutaric acid and phthalic acid. Other types of polyols that may be mentioned include hydroxyl terminated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins and polysiloxanes.
Les quantités de composés de poiyisocyanates et de composés polyfonctionnels réactifs avec les isocyanates à faire réagir dépendent de la nature de la mousse de polyuréthanne à peau intégrale à préparer et seront facilement déterminées par l'homme de l'art.The amounts of polyisocyanate compounds and polyfunctional isocyanate-reactive compounds to be reacted depend on the nature of the integral skin polyurethane foam to be prepared and will be readily determined by one skilled in the art.
Généralement, on utilise de l'eau ou d'autres composés libérant du dioxyde de carbone conjointement avec le mélange d'agents d'expansion de la présente invention. Lorsque l'eau est présente comme co-agent d'expansion, elle est mise en œuvre en quantité généralement inférieure à 1 %, de préférence inférieure à 0,5 % en poids par rapport aux composés réactifs avec les isocyanates.Generally, water or other carbon dioxide-releasing compounds are used in conjunction with the blowing agent mixture of the present invention. When water is present as a co-blowing agent, it is used in an amount generally less than 1%, preferably less than 0.5% by weight relative to the compounds reactive with isocyanates.
En plus des compositions de poiyisocyanates et des compositions polyfonctionnelles réactives avec les isocyanates et des agents d'expansion, le mélange réactionnel peut comprendre des additifs usuels entrant dans les formulations pour la production de mousses de polyuréthane à peau intégrale. De tels additifs facultatifs comprennent des agents de réticulation, par exemple des polyols de poids moléculaire bas tels que éthylèneglycol, 1 ,4-butanediol, glycérol, triméthylolpropane et triéthanolamine, des catalyseurs d'uréthane, par exemple des composés de l'étain comme l'octoate stanneux ou le dilaurate de dibutylétain, ou des aminés tertiaires comme le 1 ,4-diaza-(2,2,2)-bicyclooctane, l'éther bis-(2-diméthylamino-éthylique), la diméthylcyclohexylamine ou la triéthylène-diamine, des agents tensio-actifs, des ignifugeants, par exemple des phosphates d'alkyle halogènes comme le phosphate de tris-chloropropyle, et des charges comme le noir de carbone.In addition to polyisocyanate compositions and isocyanate-reactive polyfunctional compositions and blowing agents, the reaction mixture may include customary additives included in the formulations for the production of integral skin polyurethane foams. Such optional additives include crosslinking agents, for example low molecular weight polyols such as ethylene glycol, 1,4-butanediol, glycerol, trimethylolpropane and triethanolamine, urethane catalysts, for example tin compounds such as stannous octoate or dibutyltin dilaurate, or tertiary amines such as 1,4-diaza- (2,2,2) -bicyclooctane, bis (2-dimethylaminoethyl) ether, dimethylcyclohexylamine or triethylene diamine, surfactants, flame retardants, for example halogenated alkyl phosphates such as tris-chloropropyl phosphate, and fillers such as carbon black.
Pour la mise en œuvre du procédé de préparation de mousses à peau intégrale selon l'invention, on peut utiliser les techniques connues conjointement avec des procédés usuels de mélange.For the implementation of the process for the preparation of integral skin foams according to the invention, the known techniques can be used together with usual mixing methods.
Le procédé selon la présente invention présente l'avantage d'avoir un moindre effet sur le réchauffement de la planète, ce qui est intéressant dans une application émissive comme les mousses flexibles vis-à-vis de la circulaire F-gas en Europe. La mise en œuvre est également facilitée par un meilleur écoulement du mélange comprenant les deux composants réactifs dû à un abaissement de viscosité.The method according to the present invention has the advantage of having a lesser effect on global warming, which is interesting in an emissive application such as foams flexible vis-à-vis the circular F-gas in Europe. Implementation is also facilitated by better flow of the mixture comprising both reactive components due to a lowering of viscosity.
La présente invention a également pour objet un préméiange comprenant une composition polyfonctionnelle réactive avec les isocyanates, du trans 1 -2 dichloroéthylène et au moins un hydrofluorocarbure.The subject of the present invention is also a premix comprising a polyfunctional composition reactive with isocyanates, trans-2-dichloroethylene and at least one hydrofluorocarbon.
Le rapport massique du trans 1 -2 dichloroéthylène par rapport au(x) hydrofluorocarbure(s) dans le prémélange est avantageusement compris entre 4,5 - 20 : 1.The mass ratio of trans-2-dichloroethylene relative to (x) hydrofluorocarbon (s) in the premix is advantageously between 4.5 - 20: 1.
La quantité de trans 1 -2 dichloroéthylène et d' hydrofluorocarbure ou des hydrofluorocarbures présents dans le prémélange représente entre 0,1 et 15 parties en poids, de préférence entre 0,3 et 12 parties en poids par rapport àThe amount of trans-2-dichloroethylene and hydrofluorocarbon or hydrofluorocarbons present in the premix represents between 0.1 and 15 parts by weight, preferably between 0.3 and 12 parts by weight relative to
100 parties en poids de composition polyfonctionnelle réactive avec les isocyanates.100 parts by weight of polyfunctional composition reactive with isocyanates.
Le prémélange selon la présente invention offre d'une part l'avantage d'avoir un point éclair très supérieur par rapport au prémélange ne comprenant que les hydrocarbures comme agents d'expansion et d'autre part le coût global du prémélange est inférieur par rapport au prémélange comprenant des hydrofluorocarbures seuls.The premix according to the present invention on the one hand has the advantage of having a much higher flash point compared to the premix comprising only the hydrocarbons as blowing agents and on the other hand the overall cost of the premix is lower than premix comprising hydrofluorocarbons alone.
En outre, le prémélange a un potentiel d'appauvrissement de l'ozone (ODP) quasi nul.In addition, the premix has a near zero ozone depletion potential (ODP).
La présente invention a, en outre, pour objet une mousse à peau intégrale susceptible d'être obtenue selon le procédé décrit ci-dessus.The present invention further relates to an integral skin foam capable of being obtained according to the method described above.
PARTIE EXPERIMENTALE Les essais ont été effectués avec une composition (I) à base de polyols contenant :EXPERIMENTAL PART The tests were carried out with a composition (I) based on polyols containing:
Bayfit®PU 10WF15 (polyol commercialisé par Bayer) 55,7 parties en poidsBayfit ® PU 10WF15 (polyol marketed by Bayer) 55.7 parts by weight
Daltocel® XF417 (polyol commercialisé par Huntsman) 34,35 parties en poidsDaltocel ® XF417 (polyol marketed by Huntsman) 34.35 parts by weight
Ethylène glycol 8,5 parties en poidsEthylene glycol 8.5 parts by weight
Jeffcat® ZR 40 (catalyseur commercialisé par 0,85 partie en poids Huntsman)Jeffcat ® ZR 40 (marketed catalyst 0.85 parts by weight Huntsman)
Jeffcat® ZR 22 (catalyseur commercialisé par 0,2 partie en poids Huntsman)Jeffcat ® ZR 22 (catalyst marketed by 0.2 parts by weight Huntsman)
Tegostab® B8715LF (tensioactif commercialisé par 0,2 partie en poidsTegostab ® B8715LF (surfactant marketed by 0.2 parts by weight
Goldschmidt)Goldschmidt)
Dabco EG (catalyseur commercialisé par Air Products) 0,1 partie en poidsDabco EG (catalyst marketed by Air Products) 0.1 part by weight
Eau 0,1 partie en poidsWater 0.1 parts by weight
Exemple 1Example 1
On ajoute à 100 parties en poids de la composition (I), et à température ambiante 1 partie en poids d'un hydrofluorocarbure 245 fa et 6 parties en poids de trans 1 ,2 dichloroéthylène préalablement mélangé.To 100 parts by weight of the composition (I) and at room temperature, 1 part by weight of a hydrofluorocarbon 245 and 6 parts by weight of trans 1, 2 dichloroethylene, premixed, are added.
On mélange ensuite vigoureusement pour donner une composition (II).The mixture is then vigorously mixed to give a composition (II).
On mélange ensuite à température ambiante 100 parties en poids de la composition (II) avec 50 parties en poids de Suprasec®2030 (un polyisocyanate commercialisé par Huntsman), puis on laisse réagir une partie du mélange résultant à température ambiante dans un récipient. La mousse obtenue a une densité de 190 kg/m3, selon la norme ISO 845.Room temperature then mixed with 100 parts by weight of the composition (II) with 50 parts by weight of Suprasec ® 2030 (a polyisocyanate available from Huntsman) and then allowed to react a portion of the resulting mixture at room temperature in a container. The foam obtained has a density of 190 kg / m 3 , according to the ISO 845 standard.
Une autre partie du mélange résultant est versée dans un moule en aluminium, puis maintenu à une température comprise entre 40 et 450C. Le moule est ensuite fermé et après réaction, on obtient une mousse de densité globale de 350 kg/m3, selon la norme ISO 845. En outre, la mousse à peau intégrale est de bonne qualité.Another part of the resulting mixture is poured into an aluminum mold and then kept at a temperature between 40 and 45 ° C. The mold is then closed and after reaction, a foam with an overall density of 350 kg / m 3 is obtained. according to ISO 845. In addition, the integral skin foam is of good quality.
Daltocel, Jeffcat et Suprasec sont des marques déposées par Huntsman.Daltocel, Jeffcat and Suprasec are registered trademarks of Huntsman.
Exemples 2 à 7 On ajoute à 100 parties en poids de la composition (I), une quantité d'agents d'expansion (exemples 2 - 4, 7) ou un mélange d'agents d'expansion avec le trans 1 ,2-dichloroéthylène (TDCE), puis on fait réagir 100 parties en poids du mélange résultant avec 50 parties en poids de Suprasec®2030 dans un moule en aluminium à une température comprise entre 40 et 45°C. Le tableau unique résume les propriétés de la mousse obtenue. Par ailleurs, le point éclair de chaque agent d'expansion seul ou en mélange avec le TDCE a également été reporté.
Figure imgf000008_0001
Examples 2 to 7 A quantity of blowing agents (Examples 2 - 4, 7) or a mixture of blowing agents with trans 1, 2 is added to 100 parts by weight of the composition (I). dichloroethylene (TDCE) and then reacting 100 parts by weight of the resulting mixture with 50 parts by weight of Suprasec ® 2030 in an aluminum mold to a temperature between 40 and 45 ° C. The single table summarizes the properties of the foam obtained. In addition, the flash point of each blowing agent alone or in mixture with TDCE has also been reported.
Figure imgf000008_0001

Claims

REVENDICATIONS
i . Procédé de fabrication des articles mouiés en poiyuréthane ayant une périphérie dense et une partie centrale cellulaire, comprenant une étape réactionnelle d'une composition polyisocyanate organique avec une composition polyfonctionnelle réactive avec les isocyanates caractérisé en ce qu'on utilise un mélange de trans 1 ,2-dichloroéthylène et d'au moins un hydrofluorocarbure comme agents d'expansion.i. Process for the production of polyurethane-molded articles having a dense periphery and a cellular central part, comprising a reaction step of an organic polyisocyanate composition with a polyfunctional composition reactive with isocyanates, characterized in that a mixture of trans 1, 2 is used -dichloroethylene and at least one hydrofluorocarbon as blowing agents.
2. Procédé selon la revendication 1 caractérisé en ce que le rapport massique trans 1 ,2-dichloroéthylène/hydrofluorocarbure(s) est compris entre 4,5 et 20.2. Method according to claim 1 characterized in that the mass ratio trans 1, 2-dichloroethylene / hydrofluorocarbon (s) is between 4.5 and 20.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que i'hydrofluorocarbure peut être choisi parmi le 1 ,1 ,1 ,3,3-pentafluoropropane, le3. Process according to claim 1 or 2, characterized in that the hydrofluorocarbon may be chosen from 1, 1, 1, 3,3-pentafluoropropane,
1 ,1 ,1 ,3,3- pentafluorobutane et le 1 ,1 ,1 ,2,3,3,3-heptafluoropropane, ou leur mélange.1, 1, 1, 3,3-pentafluorobutane and 1,1,1,2,3,3,3-heptafluoropropane, or a mixture thereof.
4. Procédé selon l'une quelconque des revendications 1 à 3 caractérisé en ce que l'on utilise en outre de l'eau comme agent d'expansion.4. Process according to any one of Claims 1 to 3, characterized in that water is also used as blowing agent.
5. Prémélange comprenant une composition polyfonctionnelle réactive avec les polyisocyanates, du trans 1 ,2-dichloroéthylène et au moins un hydrofluorocarbure, caractérisé en ce que le rapport massique trans 1 ,2- dichloroéthylène/hydrofluorocarbure est compris entre 4,5 et 20.5. Premix comprising a polyfunctional composition reactive with polyisocyanates, trans-1,2-dichloroethylene and at least one hydrofluorocarbon, characterized in that the mass ratio trans 1, 2-dichloroethylene / hydrofluorocarbon is between 4.5 and 20.
6. Mousse susceptible d'être obtenue selon l'une quelconque des revendications 1 à 4. 6. Foam obtainable according to any one of claims 1 to 4.
PCT/FR2006/001116 2005-06-29 2006-05-18 Method of preparing polyurethane-moulded articles WO2007003726A1 (en)

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