WO1995034590A1 - Process for preparing a flexible polyurethane foam - Google Patents

Process for preparing a flexible polyurethane foam Download PDF

Info

Publication number
WO1995034590A1
WO1995034590A1 PCT/EP1995/002068 EP9502068W WO9534590A1 WO 1995034590 A1 WO1995034590 A1 WO 1995034590A1 EP 9502068 W EP9502068 W EP 9502068W WO 9534590 A1 WO9534590 A1 WO 9534590A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
parts
polyisocyanate
polyol
nco value
Prior art date
Application number
PCT/EP1995/002068
Other languages
French (fr)
Inventor
Mireille Berthine Albert De Witte
Original Assignee
Imperial Chemical Industries Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB9412105A external-priority patent/GB9412105D0/en
Application filed by Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to JP50155396A priority Critical patent/JP3995710B2/en
Priority to DE69516517T priority patent/DE69516517T2/en
Priority to EP95921792A priority patent/EP0765354B1/en
Priority to AU26724/95A priority patent/AU691623B2/en
Publication of WO1995034590A1 publication Critical patent/WO1995034590A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0008Foam properties flexible
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0041Foam properties having specified density
    • C08G2110/005< 50kg/m3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0041Foam properties having specified density
    • C08G2110/0058≥50 and <150kg/m3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0083Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention is concerned with a process for preparing flexible polyurethane foams and with a polyisocyanate composition for preparing such flexible foams.
  • flexible foams are prepared by reacting semi- prepolymers or prepolymers with an isocyanate-reactive composition containing a high amount of water.
  • flexible foams are prepared by reacting polyisocyanates, polyols and water at a relatively low NCO-index.
  • polyisocyanate compositions may contain higher amounts of polymeric MDI while remaing stable and therefore flexible foams having a lower density can be prepared; the lower density does not significantly effect the other physical properties of the foam in a negative way.
  • the present invention is concerned with a process for preparing a flexible polyurethane foam by reacting
  • the polyisocyanate is a polyisocyanate composition having an NCO value of 11-22, preferably of 13-20% by weight and most preferably of more than 15 to 20% by weight which is a blend of al.
  • the present invention is concerned with a reaction system comprising the above mentioned ingredients with the proviso that the polyisocyanate is kept in a container separate from the isocyanate- reactive compounds.
  • the present invention is concerned with the aforementioned polyisocyanate.
  • isocyanate index or NCO index or index the ratio of NCO-groups over isocyanate-reactive hydrogen atoms present in a fornulation, given as a percentage :
  • the NCO-index expresses the percentage of isocyanate actually used in a formulation with respect to the amount of isocyanate theoretically required for reacting with the amount of isocyanate-reactive hydrogen used in a formulation.
  • the isocyanate index as used herein is considered from the point of view of the actual foaming process involving the isocyanate ingredient and the isocyanate-reactive ingredients. Any isocyanate groups consumed in a preliminary step to produce the semi-prepolymer or other modified polyisocyanates or any active hydrogens reacted with isocyanate to produce modified polyols or polyamines, are not taken into account in the calculation of the isocyanate index. Only the free isocyanate groups and the free isocyanate-reactive hydrogens (including those of the water) present at the actual foaming stage are taken into account.
  • isocyanate-reactive hydrogen atoms refers to the total of hydroxyl and amine hydrogen atoms present in the reactive compositions in the form of polyols, polyamines and/or water; this means that for the purpose of calculating the isocyanate index at the actual foaming process one hydroxyl group is considered to comprise one reactive hydrogen and one water molecule is considered to comprise two active hydrogens.
  • Reaction system a combination of components wherein the polyisocyanate component is kept in a container separate from the isocyanate-reactive components.
  • polyurethane foam as used herein generally refers to cellular products as obtained by reacting polyisocyanates with isocyanate-reactive hydrogen containing compounds, using foaming agents, and in particular includes cellular products obtained with water as reactive foaming agent (involving a reaction of water with isocyanate groups yielding urea linkages and carbon dioxide and producing polyurea-urethane foams) .
  • average nominal hydroxyl functionality is used herein to indicate the number average functionality (number of hydroxyl groups per molecule) of the polyol composition on the assumption that this is the number average functionality (number of active hydrogen atoms per molecule) of the initiator(s) used in their preparation although in practice it will often be somewhat less because of some terminal unsaturation.
  • MDI functionality is the number average isocyanate functionality of all diphenylmethane diisocyanate and all polymethylene polyphenylene polyisocyanate used in preparing the polyisocyanate composition according to the present invention with the proviso that the NCO groups used in the preparation of the semi- prepolymer are also taken into account in determining this functionality.
  • the diphenylmethane diisocyanate (MDI) used may be selected from pure 4,4'-MDI and isomeric mixtures of 4,4' -MDI and 2,4'-MDI and less than 10% by weight of 2,2'-MDI and modified variants thereof containing carbodiimide, uretonimine, isocyanurate, urethane, allophanate, urea or biuret groups.
  • polymethylene polyphenylene polyisocyanates used in the preparation of semi-prepolymer al) and used as polyisocyanate a2) are known as such and are polyisocyanates comprising MDI and MDI homologues having isocyanate functionalities of 3 or more.
  • These polyisocyanates are often referred to as "crude MDI” or "polymeric MDI” and are made by the phosgenation of a mixture of polyamines obtained by the acid condensation of aniline and formaldehyde. The manufacture of both the polyamine mixtures and the polyisocyanate mixtures is well known.
  • the condensation of aniline with formaldehyde in the presence of strong acids such as hydrochloric acid gives a reaction product containing diaminodiphenyl ethane together with polymethylene polyphenylene polyamines of higher functionality, the precise composition depending in known manner on the aniline/formaldehyde ratio.
  • the polyisocyanates are made by phosgenation of the polyamine mixtures and the various proportions of diamines, triamines and higher polyamines give rise to related proportions of diisocyanates, triisocyanates and higher polyisocyanates.
  • the relative proportions of diisocyanate, triisocyanate and higher polyisocyanates in the crude diphenylmethane diisocyanate compositions determine the average functionality of the compositions, that is the average number of isocyanate groups per molecule.
  • the average functionality of the polyisocyanate compositions can be varied from little more than 2 to 3 or even higher. In practice, however, the number average isocyanate functionality preferably ranges from 2.35-2.9.
  • the NCO value of these polymeric MDIs is at least 30% by weight.
  • compositions contain from 30 to 65% by weight of diphenylmethane diisocyanate, the remainder being polymethylene polyphenylene polyisocyanates of functionality greater than two together with by-products formed in the manufacture of such polyisocyanates by phosgenation.
  • diphenylmethane diisocyanate the remainder being polymethylene polyphenylene polyisocyanates of functionality greater than two together with by-products formed in the manufacture of such polyisocyanates by phosgenation.
  • the polyols having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000 (polyol 2) and the polyol used in preparing semi-prepolymer al) may be selected from polyester polyols, polyesteramide polyols, polythioether polyols, polycarbonate polyols, polyacetal polyols, polyolefin polyols, polysiloxane polyols and especially polyether polyols.
  • Polyether polyols which may be used include products obtained by the polymerisation of a cyclic oxide, for example ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran in the presence, where necessary, of polyfunctional initiators.
  • Suitable initiator compounds contain a plurality of active hydrogen atoms and include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, cyclohexane diamine, cyclohexane dimethanol, glycerol, trimethylolpropane and 1,2,6-hexanetriol. Mixtures of initiators and/or cyclic oxides may be used.
  • Especially useful polyether polyols include polyoxypropylene diols and triols and polyoxyethylene-polyoxypropylene diols and triols obtained by the simultaneous or sequential addition of ethylene and propylene oxides to di- or trifunctional initiators as fully described in the prior art. Random copolymers having oxyethylene contents of 10-80%, block copolymers having oxyethylene contents of up to 50%, based on the total weight of oxyalkylene units may be mentioned, in particular those having at least part of the oxyethylene groups at the end of the polymer chain. Mixtures of the said diols and triols can be particularly useful. Small amounts of polyoxyethylene diols and triols may be used as well; the amount in general is less than 20% by weight on the amount of polyol 2) used.
  • Polyester polyols which may be used include hydroxyl-terminated reaction products of polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane dimethanol, glycerol, trimethylolpropane or polyether polyols or mixtures of such polyhydric alcohols, and polycarboxylic acids, especially dicarboxylic acids or their ester-forming derivatives, for example succinic, glutaric and adipic acids or their dimethyl esters, sebacic acid, phtalic anhydride, tetrachlorophthalic anhydride or dimethyl terephathalate or mixtures thereof. Polyesters obtained by the polymerisation of lactones, for example caprolactaone, in conjunction with a polyol, or of hydroxy carboxylic acids such as hydroxy caproic acid, may also be used.
  • Polyesteramides may be obtained by the inclusion of aminoalcohols such as ethanolamine in polyesterification mixtures.
  • Polythioether polyols which may be used include products obtained by condensing thiodiglycol either alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols or aminocarboxylic acids.
  • Polycarbonate polyols which may be used include products obtained by reacting diols such as l,3-propanediol, 1,4-butanediol, 1,6- hexanediol, diethylene glycol or tetraethylene glycol with diaryl carbonates, for example diphenyl carbonate, or with phosgene.
  • Polyacetal polyols which may be used include those prepared by reacting glycols such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Suitable polyacetals may also be prepared by polymerising cyclic acetals.
  • Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols and triols.
  • polystyrene and/or acrylonitrile examples of modified polyols
  • polymeric polyols for example polyether polyols
  • polyisocyanate an amino- and/or hydroxy-functional compound, such as triethanolamine
  • polyoxyalkylene polyols containing from 5 to 50% by weight of dispersed polymer are particularly useful. Particle sizes of the dispersed polymers of less than 50 microns are preferred.
  • the number average molecular weight of polyols 2) and the polyols used in preparing semi-prepolymer al) preferably is 1000-8000 and most preferably 1500-7000; the hydroxyl value preferably ranges from 15-200 and most preferably from 20-100.
  • polyoxyethylene polyoxypropylene polyols having a number average molecular weight of 2000-7000, an average nominal functionality of 2-3 and an oxyethylene content of 10-25% by weight, preferably having the oxyethylene groups at the end of the polymer chain.
  • polyether polyols having a low level of unsaturation may be used as *?ell.
  • high molecular weight polyols having a low level of unsaturation may be used for preparing flexible foams having a high ball rebound.
  • the isocyanate-terminated semi-prepolymer al. is prepared by first mixing the diphenylmethane diisocyanate and the polymethylene polyphenylene polyisocyanate. Subsequently the polyol is added and the mixture is allowed to react. Such reaction is allowed to take place at 60-100°C and in general the use of catalyst is not necessary.
  • the relative amount of polyisocyanate and polyol depends on the desired NCO-value of the semi-prepolymer, the NCO-value of the polyisocyanate used and the OH value of the polyol and can be easily calculated by those skilled in the art. After completion of the above reaction the polymethylene polyphenylene polyisocyanate a2. is added and mixed.
  • the "MDI-functionality" of the polyisocyanate composition according to the present invention is
  • the chain-extending and cross-linking agents which optionally may be used may be selected from amines and polyols containing 2-8 and preferably 2-4 amine and/or hydroxy groups like ethanolamine, diethanolamine, triethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, trimethylolpropane, pentaerithritol, sorbitol, sucrose, polyethylene glycol having a molecular weight of at most 999, toluene diamine, diethyl toluene diamine, cyclohexane diamine, phenyl diamine, diphenylmethane diamine, alkylated diphenylmethane diamine and ethylene diamine.
  • the amount of chain-extending and cross-linking agents is, if applied, up to 25 and preferably up to 10 parts by weight per 100 parts by weight of polyol 2) .
  • auxiliaries and additives which amongst others may be used are formation of urea and urethane enhancing catalysts like tertiary amines and tin compounds, surfactants, stabilisers, flame retardants, fillers and anti-oxidants.
  • the flexible polyurethane foams are prepared by combining and mixing ingredients l)-6) and allowing the mixture to foam.
  • ingredients 2)-6) are premixed and subsequently combined with the polyisocyanate.
  • the relative amounts of polyisocyanate on the one hand and ingredients 2) -6) on the other hand depend on the desired index and can be calculated easily by those skilled in the art.
  • the process may be used to make slab-stock or moulded flexible foams.
  • the foams in general have a density of 15-80 kg/m 3 and may be used as cushioning material in furniture , car seats and mattresses.
  • the present invention is illustrated by the following Example.
  • a semi-prepolymer was prepared by 1) mxing 29.6 parts by weight of a diphenylmethane diisocyanate containing 85% by weight of 4,4'- diphenylmethane diisocyanate and 15% by weight of 2,4'- diphenylmethane diisocyanate and 15 parts by weight of a polymethylene polyphenylene polyisocyanate having an NCO value of 30.7% by weight and a number average isocyanate functionality of 2.7, 2) adding to this mixture 45.4 parts by weight of a polyoxyethylene polyoxypropylene polyol having a nominal functionality of 3, a number average molecular weight of 6000 and an oxyethylene content of 15% by weight (all tip) followed by mixing, and 3) allowing this mixture to react at 85°C for 4 hours.
  • the composition obtained was an isocyanate composition according to the present invention; had an NCO value of 16.7% by weight and a viscosity of 1095 Pa.s at 25°C; the composition was clear and stable for more than 2 weeks at 0°C and room temperature (stability was determined visually; when solids and turbidity were visually absent the composition was regarded as stable) and had an "MDI- functionality" of 2.25.
  • a flexible foam was prepared by mixing in a cup 100 parts of the above isocyanate composition according to the invention and an isocyanate-reactive composition (index 77) comprising 50 parts by weight (pbw) of the above polyol, 4.3 pbw of water, 4.3 pbw of a polyoxyethylene polyol having a nominal functionality of 3 and a number average molecular weight of 1200, 1.45 pbw of SH210 surfactant, 0.85 pbw of 1,2-dimethyl imidazole as catalyst and 0.03 pbw of Niax Al as catalyst.
  • the mixture was allowed to react and to foam under free rise conditions.
  • the foam obtained was a flexible foam having a free rise density of 32 kg/m 3 .

Abstract

Process for preparing a flexible foam by reacting a polyisocyanate composition having an NCO value of 11-22 % by weight with an isocyanate-reactive compound having a number average molecular weight of 1000-12000 using water as blowing agent.

Description

Title : Process for preparing a flexible polyurethane foam.
The present invention is concerned with a process for preparing flexible polyurethane foams and with a polyisocyanate composition for preparing such flexible foams.
It is widely known to prepare flexible polyurethane foams by reacting an organic polyisocyanate and a high molecular weight isocyanate-reactive compound in the presence of a blowing agent. More in particular it has been disclosed in EP-111121 to prepare flexible polyurethane foams from a polyisocyanate co-position comprising a semi-prepolymer. The polyisocyanate composition is prepared by reacting a diphenylmethane diisocyanate ari a polyol; a polymethylene polyphenylene polyisocyanate (polymeric MDI) is used as well. This polyisocyanate is either completely used in the preparation of the semi-prepolymer or added after the semi- prepolymer has been made. We have found that the use of polymeric MDI as proposed in EP-111121 does not provide satisfactory stability combined with low viscosity in particular for those polyisocyanate compositions having a relatively low NCO value, e.g. 11-22% by weight.
In EP-392788 flexible foams are prepared by reacting semi- prepolymers or prepolymers with an isocyanate-reactive composition containing a high amount of water. In EP-269449 flexible foams are prepared by reacting polyisocyanates, polyols and water at a relatively low NCO-index.
Surprisingly it was found that when part of the p .ymethylene polyphenylene polyisocyanate (polymeric MDI) is aeΛ prepare a semi-prepolymer and the other part of the polymeric *C ,..s added to the semi-prepolymer so formed the polyisocyanate compositions according to the present invention are stable, clear ... quids having a low viscosity; consequently their processing in preparing the foams is improved as well. When the polymeric MDI is either completely used in the preparation of the semi-prepolymer or completely added after the semi-prepolymer has been made the stability and/or viscosity are adversely effected.
Further it was found that the polyisocyanate compositions may contain higher amounts of polymeric MDI while remaing stable and therefore flexible foams having a lower density can be prepared; the lower density does not significantly effect the other physical properties of the foam in a negative way.
Accordingly the present invention is concerned with a process for preparing a flexible polyurethane foam by reacting
1) an organic polyisocyanate with
2) a polyol having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000; and optionally with
3) an isocyanate-reactive compound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular weight of 60 to 999; using
4) a blowing agent; and optionally 5) a catalyst; and optionally
6) other auxiliairies and additives known per se, characterised in that a) the polyisocyanate is a polyisocyanate composition having an NCO value of 11-22, preferably of 13-20% by weight and most preferably of more than 15 to 20% by weight which is a blend of al. 75-95 parts by weight of an isocyanate-terminated semi-prepolymer having an NCO value of 9-20, preferably 11-18 and most preferably 13-18% by weight, prepared by reacting an excessive amount of a polyisocyanate composition, consisting of 35-75% by weight of diphenylmethane diisocyanate and 25- 65% by weight of polymethylene polyphenylene polyisocyanate, with a polyol having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000; and a2. 5-25 parts by weight of a polymethylene polyphenylene polyisocyanate; b) 25-120 and preferably 35-100 parts by weight of polyol 2) is used per 100 parts by weight of organic polyisocyanate; c) water is used as blowing agent in an amount of 3-15, preferably 5-12 parts by weight and most preferably more than 8 to 12 parts by weight per 100 parts by weight of polyol 2) ; and d) the reaction is conducted at an index of 40-130 and preferably above 70 to 100.
Further the present invention is concerned with a reaction system comprising the above mentioned ingredients with the proviso that the polyisocyanate is kept in a container separate from the isocyanate- reactive compounds.
Still further the present invention is concerned with the aforementioned polyisocyanate.
In the context of the present invention the following terms have the following meaning :
1) isocyanate index or NCO index or index : the ratio of NCO-groups over isocyanate-reactive hydrogen atoms present in a fornulation, given as a percentage :
ΓNCOI IOO (%)
[active hydrogen]
In other words the NCO-index expresses the percentage of isocyanate actually used in a formulation with respect to the amount of isocyanate theoretically required for reacting with the amount of isocyanate-reactive hydrogen used in a formulation.
It should be observed that the isocyanate index as used herein is considered from the point of view of the actual foaming process involving the isocyanate ingredient and the isocyanate-reactive ingredients. Any isocyanate groups consumed in a preliminary step to produce the semi-prepolymer or other modified polyisocyanates or any active hydrogens reacted with isocyanate to produce modified polyols or polyamines, are not taken into account in the calculation of the isocyanate index. Only the free isocyanate groups and the free isocyanate-reactive hydrogens (including those of the water) present at the actual foaming stage are taken into account.
2) The expression "isocyanate-reactive hydrogen atoms" as used herein for the purpose of calculating the isocyanate index refers to the total of hydroxyl and amine hydrogen atoms present in the reactive compositions in the form of polyols, polyamines and/or water; this means that for the purpose of calculating the isocyanate index at the actual foaming process one hydroxyl group is considered to comprise one reactive hydrogen and one water molecule is considered to comprise two active hydrogens.
3) Reaction system : a combination of components wherein the polyisocyanate component is kept in a container separate from the isocyanate-reactive components.
4) The expression "polyurethane foam" as used herein generally refers to cellular products as obtained by reacting polyisocyanates with isocyanate-reactive hydrogen containing compounds, using foaming agents, and in particular includes cellular products obtained with water as reactive foaming agent (involving a reaction of water with isocyanate groups yielding urea linkages and carbon dioxide and producing polyurea-urethane foams) .
5) The term "average nominal hydroxyl functionality" is used herein to indicate the number average functionality (number of hydroxyl groups per molecule) of the polyol composition on the assumption that this is the number average functionality (number of active hydrogen atoms per molecule) of the initiator(s) used in their preparation although in practice it will often be somewhat less because of some terminal unsaturation. 6) "MDI functionality" is the number average isocyanate functionality of all diphenylmethane diisocyanate and all polymethylene polyphenylene polyisocyanate used in preparing the polyisocyanate composition according to the present invention with the proviso that the NCO groups used in the preparation of the semi- prepolymer are also taken into account in determining this functionality.
The diphenylmethane diisocyanate (MDI) used may be selected from pure 4,4'-MDI and isomeric mixtures of 4,4' -MDI and 2,4'-MDI and less than 10% by weight of 2,2'-MDI and modified variants thereof containing carbodiimide, uretonimine, isocyanurate, urethane, allophanate, urea or biuret groups. Most preferred are pure 4,4'- MDI, isomeric mixtures 2,4'-MDI, and uretonimine and/or carbodiimide modified MDI having an NCO content of at least 25% by weight and urethane modified MDI obtained by reacting excess MDI and polyol (preferably having a molecular weight of at most 999) and having an NCO content of at least 25% by weight.
The polymethylene polyphenylene polyisocyanates used in the preparation of semi-prepolymer al) and used as polyisocyanate a2) are known as such and are polyisocyanates comprising MDI and MDI homologues having isocyanate functionalities of 3 or more. These polyisocyanates are often referred to as "crude MDI" or "polymeric MDI" and are made by the phosgenation of a mixture of polyamines obtained by the acid condensation of aniline and formaldehyde. The manufacture of both the polyamine mixtures and the polyisocyanate mixtures is well known. The condensation of aniline with formaldehyde in the presence of strong acids such as hydrochloric acid gives a reaction product containing diaminodiphenyl ethane together with polymethylene polyphenylene polyamines of higher functionality, the precise composition depending in known manner on the aniline/formaldehyde ratio. The polyisocyanates are made by phosgenation of the polyamine mixtures and the various proportions of diamines, triamines and higher polyamines give rise to related proportions of diisocyanates, triisocyanates and higher polyisocyanates.
The relative proportions of diisocyanate, triisocyanate and higher polyisocyanates in the crude diphenylmethane diisocyanate compositions determine the average functionality of the compositions, that is the average number of isocyanate groups per molecule. By varying the proportions of starting materials, the average functionality of the polyisocyanate compositions can be varied from little more than 2 to 3 or even higher. In practice, however, the number average isocyanate functionality preferably ranges from 2.35-2.9. The NCO value of these polymeric MDIs is at least 30% by weight.
Such compositions contain from 30 to 65% by weight of diphenylmethane diisocyanate, the remainder being polymethylene polyphenylene polyisocyanates of functionality greater than two together with by-products formed in the manufacture of such polyisocyanates by phosgenation. These products, being liquids, are convenient to use according to the present invention.
The polyols having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000 (polyol 2) and the polyol used in preparing semi-prepolymer al) may be selected from polyester polyols, polyesteramide polyols, polythioether polyols, polycarbonate polyols, polyacetal polyols, polyolefin polyols, polysiloxane polyols and especially polyether polyols.
Polyether polyols which may be used include products obtained by the polymerisation of a cyclic oxide, for example ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran in the presence, where necessary, of polyfunctional initiators. Suitable initiator compounds contain a plurality of active hydrogen atoms and include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, cyclohexane diamine, cyclohexane dimethanol, glycerol, trimethylolpropane and 1,2,6-hexanetriol. Mixtures of initiators and/or cyclic oxides may be used.
_ Especially useful polyether polyols include polyoxypropylene diols and triols and polyoxyethylene-polyoxypropylene diols and triols obtained by the simultaneous or sequential addition of ethylene and propylene oxides to di- or trifunctional initiators as fully described in the prior art. Random copolymers having oxyethylene contents of 10-80%, block copolymers having oxyethylene contents of up to 50%, based on the total weight of oxyalkylene units may be mentioned, in particular those having at least part of the oxyethylene groups at the end of the polymer chain. Mixtures of the said diols and triols can be particularly useful. Small amounts of polyoxyethylene diols and triols may be used as well; the amount in general is less than 20% by weight on the amount of polyol 2) used.
Polyester polyols which may be used include hydroxyl-terminated reaction products of polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane dimethanol, glycerol, trimethylolpropane or polyether polyols or mixtures of such polyhydric alcohols, and polycarboxylic acids, especially dicarboxylic acids or their ester-forming derivatives, for example succinic, glutaric and adipic acids or their dimethyl esters, sebacic acid, phtalic anhydride, tetrachlorophthalic anhydride or dimethyl terephathalate or mixtures thereof. Polyesters obtained by the polymerisation of lactones, for example caprolactaone, in conjunction with a polyol, or of hydroxy carboxylic acids such as hydroxy caproic acid, may also be used.
Polyesteramides may be obtained by the inclusion of aminoalcohols such as ethanolamine in polyesterification mixtures.
Polythioether polyols which may be used include products obtained by condensing thiodiglycol either alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols or aminocarboxylic acids. Polycarbonate polyols which may be used include products obtained by reacting diols such as l,3-propanediol, 1,4-butanediol, 1,6- hexanediol, diethylene glycol or tetraethylene glycol with diaryl carbonates, for example diphenyl carbonate, or with phosgene.
Polyacetal polyols which may be used include those prepared by reacting glycols such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Suitable polyacetals may also be prepared by polymerising cyclic acetals.
Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols and triols.
Other polyols which may be used as polyol 2) and/or in preparing semi-prepolymer al) comprise dispersions or solutions of addition or condensation polymers in polyols of the types described above. Such modified polyols, often referred to as "polymer polyols" have been fully described in the prior art and include products obtained by the in situ polymerisation of one or more vinyl monomers, for example styrene and/or acrylonitrile, in polymeric polyols, for example polyether polyols, or by the in situ reaction between a polyisocyanate and an amino- and/or hydroxy-functional compound, such as triethanolamine, in a polymeric polyol. Polyoxyalkylene polyols containing from 5 to 50% by weight of dispersed polymer are particularly useful. Particle sizes of the dispersed polymers of less than 50 microns are preferred.
The number average molecular weight of polyols 2) and the polyols used in preparing semi-prepolymer al) preferably is 1000-8000 and most preferably 1500-7000; the hydroxyl value preferably ranges from 15-200 and most preferably from 20-100.
Most preferred are polyoxyethylene polyoxypropylene polyols having a number average molecular weight of 2000-7000, an average nominal functionality of 2-3 and an oxyethylene content of 10-25% by weight, preferably having the oxyethylene groups at the end of the polymer chain.
During the last years several methods have been described to prepare polyether polyols having a low level of unsaturation. These developments have made it possible to use polyether polyols at the higher end of the molecular weight range since much polyols can now be prepared with an acceptably low level of unsaturation. According to the present invention polyols having a low level of unsaturation may be used as *?ell. In particular such high molecular weight polyols having a low level of unsaturation may be used for preparing flexible foams having a high ball rebound.
The isocyanate-terminated semi-prepolymer al. is prepared by first mixing the diphenylmethane diisocyanate and the polymethylene polyphenylene polyisocyanate. Subsequently the polyol is added and the mixture is allowed to react. Such reaction is allowed to take place at 60-100°C and in general the use of catalyst is not necessary. The relative amount of polyisocyanate and polyol depends on the desired NCO-value of the semi-prepolymer, the NCO-value of the polyisocyanate used and the OH value of the polyol and can be easily calculated by those skilled in the art. After completion of the above reaction the polymethylene polyphenylene polyisocyanate a2. is added and mixed. The "MDI-functionality" of the polyisocyanate composition according to the present invention is
2.15-2.35 and preferably 2.20-2.30.
The chain-extending and cross-linking agents which optionally may be used (isocyanate-reactive compound 3)) may be selected from amines and polyols containing 2-8 and preferably 2-4 amine and/or hydroxy groups like ethanolamine, diethanolamine, triethanolamine, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerol, trimethylolpropane, pentaerithritol, sorbitol, sucrose, polyethylene glycol having a molecular weight of at most 999, toluene diamine, diethyl toluene diamine, cyclohexane diamine, phenyl diamine, diphenylmethane diamine, alkylated diphenylmethane diamine and ethylene diamine.
The amount of chain-extending and cross-linking agents is, if applied, up to 25 and preferably up to 10 parts by weight per 100 parts by weight of polyol 2) .
The auxiliaries and additives which amongst others may be used are formation of urea and urethane enhancing catalysts like tertiary amines and tin compounds, surfactants, stabilisers, flame retardants, fillers and anti-oxidants.
The flexible polyurethane foams are prepared by combining and mixing ingredients l)-6) and allowing the mixture to foam. Preferably ingredients 2)-6) are premixed and subsequently combined with the polyisocyanate. The relative amounts of polyisocyanate on the one hand and ingredients 2) -6) on the other hand depend on the desired index and can be calculated easily by those skilled in the art.
The process may be used to make slab-stock or moulded flexible foams. The foams in general have a density of 15-80 kg/m3 and may be used as cushioning material in furniture , car seats and mattresses.
The present invention is illustrated by the following Example.
fixapple
A semi-prepolymer was prepared by 1) mxing 29.6 parts by weight of a diphenylmethane diisocyanate containing 85% by weight of 4,4'- diphenylmethane diisocyanate and 15% by weight of 2,4'- diphenylmethane diisocyanate and 15 parts by weight of a polymethylene polyphenylene polyisocyanate having an NCO value of 30.7% by weight and a number average isocyanate functionality of 2.7, 2) adding to this mixture 45.4 parts by weight of a polyoxyethylene polyoxypropylene polyol having a nominal functionality of 3, a number average molecular weight of 6000 and an oxyethylene content of 15% by weight (all tip) followed by mixing, and 3) allowing this mixture to react at 85°C for 4 hours. To the semi-prepolymer so obtained which had an NCO value of 15.1% by weight was added 10 parts by weight of the above polyisocyanate. The composition obtained was an isocyanate composition according to the present invention; had an NCO value of 16.7% by weight and a viscosity of 1095 Pa.s at 25°C; the composition was clear and stable for more than 2 weeks at 0°C and room temperature (stability was determined visually; when solids and turbidity were visually absent the composition was regarded as stable) and had an "MDI- functionality" of 2.25.
A flexible foam was prepared by mixing in a cup 100 parts of the above isocyanate composition according to the invention and an isocyanate-reactive composition (index 77) comprising 50 parts by weight (pbw) of the above polyol, 4.3 pbw of water, 4.3 pbw of a polyoxyethylene polyol having a nominal functionality of 3 and a number average molecular weight of 1200, 1.45 pbw of SH210 surfactant, 0.85 pbw of 1,2-dimethyl imidazole as catalyst and 0.03 pbw of Niax Al as catalyst. The mixture was allowed to react and to foam under free rise conditions. The foam obtained was a flexible foam having a free rise density of 32 kg/m3.

Claims

CliAIMS
1. A process for preparing a flexible polyurethane foam by reacting
1) an organic polyisocyanate with
2) a polyol having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000; and optionally with 3) an isocyanate-reactive compound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular weight of 60 to 999; using
4) a blowing agent; and optionally
5) a catalyst; and optionally 6) other auxiliaries and additives known per se characterised in that a) the polyisocyanate is a polyisocyanate composition having an NCO value of 11-22% by weight which is a blend of al. 75-95 parts by weight of an isocyanate-terminated semi-prepolymer having an NCO value of 9-20% by weight, prepared by reacting an excessive amount of a polyisocyanate composition, consisting of 35-75% by weight of diphenylmethane diisocyanate and 25- 65% by weight of polymethylene polyphenylene polyisocyanate, with a polyol having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000; and a2. 5-25 parts by weight of a polymethylene polyphenylene polyisocyanate; b) 25-120 parts by weight of polyol 2) is used per 100 parts by weight of organic polyisocyanate; c) water is used as blowing agent in an amount of 3-15 parts by weight per 100 parts by weight of polyol 2) ; and d) the reaction is conducted at an index of 40-130.
2. Process according to claim 1, wherein the organic polyisocyanate has an MDI functionality of 2.15-2.35.
Process according to claims 1-2, wherein the organic polyisocyanate has an NCO value of 13-20% by weight, the semi- prepolymer has an NCO value of 11-18% by weight, the amount of polyol 2) is 35-100 parts by weight per 100 parts by weight of organic polyisocyanate, the amount of water s 5-12 parts by weight per 100 parts by weight of polyol 2) and the index is above 70 to 100.
4. Reaction system comprising
1) an organic polyisocyanate;
2) a polyol having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000; and optionally
3) an isocyanate-reactive compound containing at least two isocyanate-reactive hydrogen atoms and having a number average molecular weight of 60 to 999;
4) a blowing agent; and optionally 5) a catalyst; and optionally
6) other auxiliaries and additives known per se characterised in that a) the polyisocyanate is a polyisocyanate composition having an NCO value of 11-22% by weight which is a blend of al. 75-95 parts by weight of an iεocyanate-terminated semi-prepolymer having an NCO value of 9-20% by weight, prepared by reacting an excessive amount of a polyisocyanate composition, consisting of 35-75% by weight of diphenylmethane diisocyanate and 25-
65% by weight of polymethylene polyphenylene polyisocyanate, with a polyol having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000; and a2. 5-25 parts by weight of a .polymethylene polyphenylene polyisocyanate; b) 25-120 parts by weight of polyol 2) is used per 1.00 parts by weight of organic polyisocyanate; c) water is used as blowing agent in an amount of 3-15 parts by weight per 100 parts by weight of polyol 2) ; and d) the relative amount of polyisocyanate 1) with respect to the other ingredients is such that when combined the index is 40-130; with the proviso that the polyisocyanate is kept in a container separate from the isocyanate- reactive compounds.
Reaction system according to claim 4 wherein the organic polyisocyanate has an MDI functionality of 2.15-2.35.
6. Reaction system according to claims 4-5 wherein the organic polyisocyanate has an NCO value of 13-20% by weight, the semi- prepolymer has an NCO value of 11-18% by weight, the amount of polyol 2) is 35-100 parts by weight per 100 parts by weight of organic polyisocyanate, the amount of water is 5-12 parts by weight per 100 parts by weight of polyol 2) and the index is above 70 to 100.
7. Organic polyisocyanate composition, characterised in that the composition has an NCO value of 11-22% by weight and is a blend of al. 75-95 parts by weight of an isocyanate-terminated semi- prepolymer having an NCO value of 9-20% by weight, prepared by reacting an excessive amount of a polyisocyanate composition, consisting of 35-75% by weight of diphenylmethane diisocyanate and 25-65% by weight of polymethylene polyphenylene polyisocyanate, with a polyol having an average nominal hydroxyl functionality of 2-3 and a number average molecular weight of 1000 to 12000; and a2. 5-25 parts by weight of a polymethylene polyphenylene polyisocyanate.
8. Composition according to claim 7 wherein the MDI functionality of the composition is 2.15-2.35.
9. Composition according to claims 7-8 wherein the composition has an NCO value of 13-20% by weight and the semi-prepolymer has an
NCO value of 11-18% by weight.
10. Composition according to claims 7-9 wherein the composition has an NCO value of more than 15 to 20% by weight and the semi- prepolymer has an NCO value of 13 to 18% by weight.
PCT/EP1995/002068 1994-06-16 1995-05-31 Process for preparing a flexible polyurethane foam WO1995034590A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP50155396A JP3995710B2 (en) 1994-06-16 1995-05-31 Method for producing flexible polyurethane foam
DE69516517T DE69516517T2 (en) 1994-06-16 1995-05-31 METHOD FOR PRODUCING A POLYURETHANE SOFT FOAM
EP95921792A EP0765354B1 (en) 1994-06-16 1995-05-31 Process for preparing a flexible polyurethane foam
AU26724/95A AU691623B2 (en) 1994-06-16 1995-05-31 Process for preparing a flexible polyurethane foam

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9412105A GB9412105D0 (en) 1994-06-16 1994-06-16 Process for preparing flexible foams
GB9412105.0 1994-06-16
EP94203786 1994-12-30
EP94203786.2 1994-12-30

Publications (1)

Publication Number Publication Date
WO1995034590A1 true WO1995034590A1 (en) 1995-12-21

Family

ID=26136870

Family Applications (3)

Application Number Title Priority Date Filing Date
PCT/EP1995/002067 WO1995034589A1 (en) 1994-06-16 1995-05-31 Process for preparing flexible foams
PCT/EP1995/002069 WO1995034591A1 (en) 1994-06-16 1995-05-31 Process for preparing flexible foams
PCT/EP1995/002068 WO1995034590A1 (en) 1994-06-16 1995-05-31 Process for preparing a flexible polyurethane foam

Family Applications Before (2)

Application Number Title Priority Date Filing Date
PCT/EP1995/002067 WO1995034589A1 (en) 1994-06-16 1995-05-31 Process for preparing flexible foams
PCT/EP1995/002069 WO1995034591A1 (en) 1994-06-16 1995-05-31 Process for preparing flexible foams

Country Status (11)

Country Link
US (5) US5491176A (en)
EP (3) EP0765353B1 (en)
JP (3) JP3995710B2 (en)
CN (3) CN1150813A (en)
AU (3) AU691301B2 (en)
CA (3) CA2190583A1 (en)
DE (3) DE69514659T2 (en)
ES (3) ES2144613T3 (en)
MY (2) MY112722A (en)
TW (3) TW358815B (en)
WO (3) WO1995034589A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5792998A (en) * 1993-04-19 1998-08-11 Cabot Safety Intermediate Corporation Acoustical hearing protective devices utilizing dynamically stiff foam and methods of producing same
US6774153B2 (en) 2000-01-17 2004-08-10 Huntsman International Llc Process for preparing a free rise or slabstock flexible polyurethane foam

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376698B1 (en) * 1991-12-17 2002-04-23 Imperial Chemical Industries Plc Prepolymers
CA2136463A1 (en) * 1994-02-03 1995-08-04 Sharon A. Free Very fine cell polyurethane foams and processes for producing the same
WO1997019971A1 (en) * 1995-11-30 1997-06-05 Imperial Chemical Industries Plc Process for preparing a flexible polyurethane foam
TR199900992T2 (en) * 1996-11-08 2000-07-21 Hunstman Ici Chemicals Llc New round polyurethane foam.
KR20000053116A (en) * 1996-11-08 2000-08-25 네바드 에드워드 죤 Process for making flexible polyurethane foams
US6090864A (en) * 1997-04-25 2000-07-18 Basf Corporation Polymeric MDI prepolymer composition and flexible foams prepared therefrom
US5874485A (en) * 1997-11-10 1999-02-23 Bayer Corporation Flexible foams and flexible molded foams based on allophanate-modified diphenylmethane diisocyanates and processes for the production of these foams
US5821275A (en) * 1997-11-10 1998-10-13 Bayer Corporation Flexible foams and flexible molded foams based on liquid isocyanate-terminated allophanate-modified MDI prepolymer blends and processes for the production of these foams
ES2218149T3 (en) * 1999-03-17 2004-11-16 Huntsman International Llc PROCEDURE FOR THE PREPARATION OF MOLDED POLYURETHANE MATERIAL.
US6482913B1 (en) * 2000-02-07 2002-11-19 Bayer Aktiengesellschaft Liquid MDI adducts wtih improved freeze stability
US6344494B1 (en) 2000-05-24 2002-02-05 Basf Corporation Use of low unsaturated polyether polyols in slabstock foam applications
US6201035B1 (en) 2000-05-24 2001-03-13 Basf Corporation Use of low unsaturated polyether polyols in high resilience slabstock foam applications
US6271279B1 (en) 2000-07-10 2001-08-07 Bayer Corporation High resilient flexible urethane foam and flexible molded foams based on allophanate modified isocyanates
EP1309642A1 (en) * 2000-08-01 2003-05-14 Huntsman International Llc Manufacture of mdi-tdi based flexible polyurethane foams
EP1178061A1 (en) * 2000-08-01 2002-02-06 Huntsman International Llc Process for preparing a polyurethane material
US6750367B2 (en) * 2002-05-09 2004-06-15 Bayer Polymers Llc Tetralin isocyanates
DE10303172A1 (en) * 2003-01-27 2004-07-29 Basf Ag Production of integral polyurethane foam for use in shoe soles and car manufacture involves reacting polyisocyanate with a special mixture of polyether-ol compounds plus chain extenders and other components
US7855240B2 (en) * 2003-08-20 2010-12-21 Basf Corporation Formulated resin component for use in spray-in-place foam system to produce a low density polyurethane foam
US8552078B2 (en) * 2006-10-17 2013-10-08 Air Products And Chemicals, Inc. Crosslinkers for improving stability of polyurethane foams
JP2008247996A (en) * 2007-03-29 2008-10-16 Nippon Polyurethane Ind Co Ltd Polyisocyanate composition and manufacturing method for soft polyurethane foam using it
US8901187B1 (en) 2008-12-19 2014-12-02 Hickory Springs Manufacturing Company High resilience flexible polyurethane foam using MDI
US8906975B1 (en) 2009-02-09 2014-12-09 Hickory Springs Manufacturing Company Conventional flexible polyurethane foam using MDI
JP4920051B2 (en) * 2009-02-25 2012-04-18 株式会社日立製作所 Oxyfuel combustion boiler plant and operation method of oxygen combustion boiler plant
DE10751971T8 (en) * 2009-10-07 2013-04-25 Huntsman International Llc METHOD FOR PRODUCING A FLEXIBLE POLYURETHANE FOAM
ES2715193T3 (en) * 2010-11-03 2019-06-03 Dow Global Technologies Llc Self-crushing polyurethane systems
CN105531296B (en) * 2013-07-16 2019-10-25 巴斯夫欧洲公司 Isocyanate prepolymer composition and the polyurethane of crosslinking prepared therefrom
CN104558509A (en) * 2015-01-05 2015-04-29 金华派对乳胶工艺品有限公司 Formula of polyurethane simulation weapon and preparation method thereof
JP6159036B1 (en) 2015-08-18 2017-07-05 三井化学株式会社 Foamed polyurethane material, molded article, and method for producing foamed polyurethane material
JP6741420B2 (en) * 2015-12-16 2020-08-19 株式会社ブリヂストン Flexible polyurethane foam for forming vehicle seat pads, and vehicle seat pads
CN106315282A (en) * 2016-08-20 2017-01-11 怀宁县马庙阳光塑料包装厂 Paper alignment rack device for printed matter
US20210269581A1 (en) * 2018-07-06 2021-09-02 Basf Se Elastomeric polyurethane foams and methods for producing the same
US10793692B2 (en) * 2018-10-24 2020-10-06 Covestro Llc Viscoelastic flexible foams comprising hydroxyl-terminated prepolymers
CN109679069A (en) * 2019-01-10 2019-04-26 广东也乐新材料制造有限公司 A kind of high recovery sponge of imitative latex ultra-soft and its production technology

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0010850A1 (en) * 1978-10-03 1980-05-14 Imperial Chemical Industries Plc Liquid polyisocyanate compositions
EP0111121A1 (en) * 1982-11-10 1984-06-20 BASF Aktiengesellschaft Liquid polysocyanate mixtures containing urethane groups on the basis of diphenylmethane diisocyanate, process for the preparation thereof and their use in the preparation of flexible polyurethane foams
EP0344551A2 (en) * 1988-06-02 1989-12-06 Bayer Ag Liquid polyisocyanate mixtures, process for their preparation and their use in the preparation of flexible polyurethane foams
WO1993008224A1 (en) * 1991-10-25 1993-04-29 The Dow Chemical Company Polyisocyanate compositions and rigid polyurethane foam therefrom

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS583488B2 (en) * 1978-05-15 1983-01-21 株式会社ブリヂストン Method for manufacturing soft polyether polyurethane foam
DE2945986A1 (en) * 1978-11-16 1980-06-04 Bridgestone Tire Co Ltd SECURITY TANK AND METHOD FOR THE PRODUCTION THEREOF
EP0022617B2 (en) * 1979-07-11 1991-09-25 Imperial Chemical Industries Plc Polyisocyanate compositions and their use in the preparation of polyurethane foams
JPH0621148B2 (en) * 1986-01-27 1994-03-23 三井東圧化学株式会社 Polyurethane elastic foam
DE3721058A1 (en) * 1987-06-26 1989-01-05 Bayer Ag METHOD FOR THE PRODUCTION OF COLD-CURING POLYURETHANE SOFT MOLDING FOAMS
DE3806476A1 (en) * 1988-03-01 1989-09-14 Bayer Ag METHOD FOR PRODUCING CALINARY POLYURETHANIC SOFT FORMULA MATERIALS WITH EXCELLENT DAWNING PROPERTIES
GB8908490D0 (en) * 1989-04-14 1989-06-01 Ici Plc Prepolymers
IT1229756B (en) * 1989-05-17 1991-09-10 Montedipe Spa FLEXIBLE POLYURETHANE FOAMS AND PROCEDURE FOR THEIR PREPARATION
JPH03124741A (en) * 1989-09-29 1991-05-28 Dow Chem Co:The Flexible polyurethane foam and its manufacture
JPH0733423B2 (en) * 1989-10-03 1995-04-12 日本ポリウレタン工業株式会社 Method for producing flexible polyurethane foam
JP2658463B2 (en) * 1989-12-28 1997-09-30 カシオ計算機株式会社 Automatic performance device
AU636191B2 (en) * 1990-02-01 1993-04-22 Huntsman Ici Chemicals Llc Manufacturing of polymeric foams from polyisocyanate compositions
JP3044261B2 (en) * 1990-04-11 2000-05-22 東ソー株式会社 Method for producing flexible polyurethane foam with excellent air permeability
US5240635A (en) * 1992-02-06 1993-08-31 The Dow Chemical Company Composition of flexible polyurethane foams blown using reduced amounts of chlorofluorocarbon blowing agents and method for preparation
DE4204395A1 (en) * 1992-02-14 1993-08-19 Bayer Ag METHOD FOR THE PRODUCTION OF CALTENING POLYURETHANIC SOFT FORMULA SUBSTANCES
US5236960A (en) * 1992-06-22 1993-08-17 Basf Corporation Water-blown polyurethane integral skin foam
GB9214372D0 (en) * 1992-07-07 1992-08-19 Ici Plc Process for making mdi based flexible foam
US5418261A (en) * 1993-01-25 1995-05-23 Imperial Chemical Industries Plc Polyurethane foams
DE4337012A1 (en) * 1993-10-29 1995-05-04 Bayer Ag Process for the production of semi-rigid foams containing urethane groups with improved flow properties
US5389693A (en) * 1994-05-31 1995-02-14 The Dow Chemical Company Integral skin polyurethane foams and process for the preparation thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0010850A1 (en) * 1978-10-03 1980-05-14 Imperial Chemical Industries Plc Liquid polyisocyanate compositions
EP0111121A1 (en) * 1982-11-10 1984-06-20 BASF Aktiengesellschaft Liquid polysocyanate mixtures containing urethane groups on the basis of diphenylmethane diisocyanate, process for the preparation thereof and their use in the preparation of flexible polyurethane foams
EP0344551A2 (en) * 1988-06-02 1989-12-06 Bayer Ag Liquid polyisocyanate mixtures, process for their preparation and their use in the preparation of flexible polyurethane foams
WO1993008224A1 (en) * 1991-10-25 1993-04-29 The Dow Chemical Company Polyisocyanate compositions and rigid polyurethane foam therefrom

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5792998A (en) * 1993-04-19 1998-08-11 Cabot Safety Intermediate Corporation Acoustical hearing protective devices utilizing dynamically stiff foam and methods of producing same
US6774153B2 (en) 2000-01-17 2004-08-10 Huntsman International Llc Process for preparing a free rise or slabstock flexible polyurethane foam

Also Published As

Publication number Publication date
AU2672595A (en) 1996-01-05
EP0765353A1 (en) 1997-04-02
EP0765354B1 (en) 2000-04-26
TW358815B (en) 1999-05-21
EP0765353B1 (en) 2000-01-19
TW344750B (en) 1998-11-11
CA2190583A1 (en) 1995-12-21
DE69516517T2 (en) 2000-09-14
US5594040A (en) 1997-01-14
AU691301B2 (en) 1998-05-14
MY112722A (en) 2001-08-30
US5521225A (en) 1996-05-28
US5491177A (en) 1996-02-13
WO1995034591A1 (en) 1995-12-21
US5594039A (en) 1997-01-14
CN1070874C (en) 2001-09-12
TW290564B (en) 1996-11-11
AU691002B2 (en) 1998-05-07
MX9605706A (en) 1998-06-30
CN1069325C (en) 2001-08-08
WO1995034589A1 (en) 1995-12-21
MX9605707A (en) 1998-05-31
DE69514659T2 (en) 2000-12-07
CA2190585A1 (en) 1995-12-21
JPH10501572A (en) 1998-02-10
JPH10501830A (en) 1998-02-17
ES2144613T3 (en) 2000-06-16
JPH10501571A (en) 1998-02-10
ES2139216T3 (en) 2000-02-01
AU2672495A (en) 1996-01-05
EP0765355B1 (en) 1999-10-20
MY130513A (en) 2007-06-29
DE69514659D1 (en) 2000-02-24
DE69512911T2 (en) 2000-04-27
CN1150813A (en) 1997-05-28
EP0765355A1 (en) 1997-04-02
AU2672395A (en) 1996-01-05
ES2141944T3 (en) 2000-04-01
CN1150811A (en) 1997-05-28
JP3995709B2 (en) 2007-10-24
JP3995711B2 (en) 2007-10-24
MX9605705A (en) 1998-05-31
DE69516517D1 (en) 2000-05-31
AU691623B2 (en) 1998-05-21
EP0765354A1 (en) 1997-04-02
CN1150812A (en) 1997-05-28
DE69512911D1 (en) 1999-11-25
JP3995710B2 (en) 2007-10-24
CA2190584A1 (en) 1995-12-21
US5491176A (en) 1996-02-13

Similar Documents

Publication Publication Date Title
EP0765354B1 (en) Process for preparing a flexible polyurethane foam
JP5122985B2 (en) Extremely soft polyurethane elastomer
EP0392788A2 (en) Isocyanate composition and process for making flexible foams therefrom
US5621016A (en) Polyisocyanate compositions and low density flexible polyurethane foams produced therewith
EP0863929B1 (en) Process for preparing a flexible polyurethane foam
AU2002257788A1 (en) Very soft polyurethane elastomer
US6433031B1 (en) Polymer-modified polyols, their use for the manufacture of polyurethane products
EP0566251B1 (en) Polyisocyanate composition
KR100232686B1 (en) Process for preparing flexible polyurethane foams
EP0956311A1 (en) New polyols and their use in polyurethane preparation
WO1998033833A1 (en) New polyols and their use in polyurethane preparation
KR20000070589A (en) New Polyols and Their Use in Polyurethane Preparation
MXPA96005706A (en) Process for preparing a polyuretanoflexi foam
MXPA99006891A (en) New polyols and their use in polyurethane preparation
MXPA96005705A (en) Processes for preparing flexib foams

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: PA/a/1996/005706

Country of ref document: MX

Ref document number: 95193615.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA CN JP MX SG

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1995921792

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2190583

Country of ref document: CA

WWP Wipo information: published in national office

Ref document number: 1995921792

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1995921792

Country of ref document: EP