CA2190583A1 - Process for preparing a flexible polyurethane foam - Google Patents
Process for preparing a flexible polyurethane foamInfo
- Publication number
- CA2190583A1 CA2190583A1 CA002190583A CA2190583A CA2190583A1 CA 2190583 A1 CA2190583 A1 CA 2190583A1 CA 002190583 A CA002190583 A CA 002190583A CA 2190583 A CA2190583 A CA 2190583A CA 2190583 A1 CA2190583 A1 CA 2190583A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- polyisocyanate
- polyol
- isocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- Chemical & Material Sciences (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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
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
WO 95134590 ',~ rt ~' (.'~ '~ t '.. ~ 2 9 0 5 8 3 PCT1EP95/02068 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 composition comprising a semi-prepolymer. The polyisocyanate composition is prepared by reacting a diphenylmethane diisocyanate and 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. li-22t by weight.
In EP-392788 flexible foams are prepared by reacting semi-prepolymera or prepolymera with an isocyanate-reactive composition containing a high amount of water.
In EP-269449 flexible foams are prepared by reacting polyisocyanatea, polyols and water at a relatively low NCO-index.
&urprisingly it was found that when part of the polymethylene polyphenylene polyisocyanate (polymeric MDI) is used to prepare a semi-prepolymer and the other part of the polymeric MDI is added to the semi-prepolymer so formed the polyisocyanate compositions according to the present invention are stable, clear liquids 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 WO 95134590 r ~ '.' ~ '~ - ~ ~ 9 ~ ~ g 3 PC'T/EP95102068 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 t~I while remaing stable and therefore flexible foams having a lower density can be prepared;
the lower density does not aignificantiy 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 20t 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 13-18t by weight, prepared by reacting an excessive amount of a polyisocyanate composition, consisting of 35-75t , by weight of diphenylmethane diisocyanate and 25-65~t 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 WO 95134590 , 1 . ~ j ~ PCTlEP95/02068 2a~a~~3 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 ;
fNCO1x100 (k) [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 WO 95134590 r ~~ ; (,, ~, ~ f ~ '~ 19 0 5 8 3 PCTIEP95102068 ~. ~
_q_ ingredients. Any isocyanate groups consumed is a preliminary step to produce the semi-prepolymer or other modified polyisocyanatea 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 hydrogenatoms" 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 , gmups 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 initiators) used in their preparation although in practice it will often be somewhat less because of some terminal unsaturation.
PGTIEP95f02068 _5_ 6y "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 aemi-prepolymer are also taken into account in detezmining 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 10t by weight of 2,2'-MDI and modified variants thereof containing carbodiimide, uretonimine, isocyanurate, urethane, allophanate, urea or biuret groups. Moat 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't by weight and urethane modified MDI obtained by reacting excess MDI and polyol (preferably having a molecular weight of at moat 999) and having as NCO content of at least 25t by weight.
The polymethylene polyphenylene polyisocyanates used in the preparation of semi-prepolymer ai) 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 polyiaocyaaate 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 diaminodiphenylmethane together with polymethyleHe polyphenylene polyaminea of higher functionality, the precise composition depending in known manner on the aniline/formaldehyde ratio. The polyisocyanatea are made by phosgenation of the polyamine mixtures and the various proportions of diaminea, triamines and higher polyaminea give rise to related proportions of diieocyanatea, ~19Q583 WO 95134590 ~ ' ~ ~ PCTIEP95102068 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 nverage 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 .~ .
W 0 95/3.1590 ' ' -"r -and/or cyclic oxides may be used.
Especially useful polyether polyola 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~t, block copolymers having oxyethylene contents of up to 50t, based on the total weight of oxyalkylene unite 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. &mall amounts of polyoxyethylene diols and triola may be used as well; the amount in general is less than 20t by weight on the amount of polyol 2) used.
Polyester polyols which may be used include hydroxyl-terminated reaction products of polyhydric alcohola 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 auccinic, 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.
Polyeateramides may be obtained by the inclusion of aminoalcohola such as ethanolamine in polyeaterification mixtures.
Polythioether polyols which may be used include products obtained by condensing thiodiglycol either alone or with other glycola, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols or aminocarboxylic acids.
W O 95/39590 ~~ C .' ~. y ) : ' ~ 3' PCTIEP95102068 -s-Polycarbonate polyols which may be used include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol ar tetraethylene glycol withdiaryl , carbonates, for example diphenyl carbonate, or with phosgene.
Polyacetal polyols which may be used include those prepared by reacting glycola such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Suitable polyacetals may also be prepared by polymerising cyclic acetals.
Suitable polyolefin polyola include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols and triols.
Other polyola which may be used as polyol 2) and/or in preparing semi-prepolymer a1) comprise dispersions or solutions of addition or condensation polymers in polyola 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 SO~t 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 polyola 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 moat 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, wo g5,3as9o ~~ ~ ~, rt, gv ~ ~~ ~'~
_g_ 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 polyola 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 well. 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 a1, 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 6D-100"C and in general the use of catalyst is sot 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 polyphenyleae polyisocyanate a2. is added and mixed. The "tmI-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 polyola 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, WO 95f34590 .. _ PCTIEP95102068 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 1)-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-BO kg/m' 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 15t by weight of 2,4'-diphenylmethane diisocyanate and 15 parts by weight of a polymethylene polyphenylene polyisocyanate having an Nc0 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 r ~?.:' i... w".:,. ,r;~s.
W 0 95134590 P~~P95/01068 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 l5.it 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 16.71 by weight and a viscosity of 1095 mPa.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 "hmI-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 A1 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'.
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 composition comprising a semi-prepolymer. The polyisocyanate composition is prepared by reacting a diphenylmethane diisocyanate and 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. li-22t by weight.
In EP-392788 flexible foams are prepared by reacting semi-prepolymera or prepolymera with an isocyanate-reactive composition containing a high amount of water.
In EP-269449 flexible foams are prepared by reacting polyisocyanatea, polyols and water at a relatively low NCO-index.
&urprisingly it was found that when part of the polymethylene polyphenylene polyisocyanate (polymeric MDI) is used to prepare a semi-prepolymer and the other part of the polymeric MDI is added to the semi-prepolymer so formed the polyisocyanate compositions according to the present invention are stable, clear liquids 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 WO 95134590 r ~ '.' ~ '~ - ~ ~ 9 ~ ~ g 3 PC'T/EP95102068 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 t~I while remaing stable and therefore flexible foams having a lower density can be prepared;
the lower density does not aignificantiy 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 20t 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 13-18t by weight, prepared by reacting an excessive amount of a polyisocyanate composition, consisting of 35-75t , by weight of diphenylmethane diisocyanate and 25-65~t 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 WO 95134590 , 1 . ~ j ~ PCTlEP95/02068 2a~a~~3 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 ;
fNCO1x100 (k) [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 WO 95134590 r ~~ ; (,, ~, ~ f ~ '~ 19 0 5 8 3 PCTIEP95102068 ~. ~
_q_ ingredients. Any isocyanate groups consumed is a preliminary step to produce the semi-prepolymer or other modified polyisocyanatea 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 hydrogenatoms" 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 , gmups 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 initiators) used in their preparation although in practice it will often be somewhat less because of some terminal unsaturation.
PGTIEP95f02068 _5_ 6y "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 aemi-prepolymer are also taken into account in detezmining 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 10t by weight of 2,2'-MDI and modified variants thereof containing carbodiimide, uretonimine, isocyanurate, urethane, allophanate, urea or biuret groups. Moat 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't by weight and urethane modified MDI obtained by reacting excess MDI and polyol (preferably having a molecular weight of at moat 999) and having as NCO content of at least 25t by weight.
The polymethylene polyphenylene polyisocyanates used in the preparation of semi-prepolymer ai) 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 polyiaocyaaate 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 diaminodiphenylmethane together with polymethyleHe polyphenylene polyaminea of higher functionality, the precise composition depending in known manner on the aniline/formaldehyde ratio. The polyisocyanatea are made by phosgenation of the polyamine mixtures and the various proportions of diaminea, triamines and higher polyaminea give rise to related proportions of diieocyanatea, ~19Q583 WO 95134590 ~ ' ~ ~ PCTIEP95102068 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 nverage 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 .~ .
W 0 95/3.1590 ' ' -"r -and/or cyclic oxides may be used.
Especially useful polyether polyola 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~t, block copolymers having oxyethylene contents of up to 50t, based on the total weight of oxyalkylene unite 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. &mall amounts of polyoxyethylene diols and triola may be used as well; the amount in general is less than 20t by weight on the amount of polyol 2) used.
Polyester polyols which may be used include hydroxyl-terminated reaction products of polyhydric alcohola 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 auccinic, 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.
Polyeateramides may be obtained by the inclusion of aminoalcohola such as ethanolamine in polyeaterification mixtures.
Polythioether polyols which may be used include products obtained by condensing thiodiglycol either alone or with other glycola, alkylene oxides, dicarboxylic acids, formaldehyde, amino-alcohols or aminocarboxylic acids.
W O 95/39590 ~~ C .' ~. y ) : ' ~ 3' PCTIEP95102068 -s-Polycarbonate polyols which may be used include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol ar tetraethylene glycol withdiaryl , carbonates, for example diphenyl carbonate, or with phosgene.
Polyacetal polyols which may be used include those prepared by reacting glycola such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Suitable polyacetals may also be prepared by polymerising cyclic acetals.
Suitable polyolefin polyola include hydroxy-terminated butadiene homo- and copolymers and suitable polysiloxane polyols include polydimethylsiloxane diols and triols.
Other polyola which may be used as polyol 2) and/or in preparing semi-prepolymer a1) comprise dispersions or solutions of addition or condensation polymers in polyola 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 SO~t 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 polyola 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 moat 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, wo g5,3as9o ~~ ~ ~, rt, gv ~ ~~ ~'~
_g_ 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 polyola 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 well. 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 a1, 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 6D-100"C and in general the use of catalyst is sot 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 polyphenyleae polyisocyanate a2. is added and mixed. The "tmI-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 polyola 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, WO 95f34590 .. _ PCTIEP95102068 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 1)-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-BO kg/m' 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 15t by weight of 2,4'-diphenylmethane diisocyanate and 15 parts by weight of a polymethylene polyphenylene polyisocyanate having an Nc0 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 r ~?.:' i... w".:,. ,r;~s.
W 0 95134590 P~~P95/01068 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 l5.it 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 16.71 by weight and a viscosity of 1095 mPa.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 "hmI-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 A1 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'.
Claims (10)
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 a1. 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.
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.
3. 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 a1. 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 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.
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 a1. 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 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.
5. 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 a1. 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.
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 is to 20% by weight and the semi-prepolymer has an NCO value of 13 to 18% by weight.
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 |
|---|---|
| CA2190583A1 true CA2190583A1 (en) | 1995-12-21 |
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ID=26136870
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| Application Number | Title | Priority Date | Filing Date |
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| CA002190584A Abandoned CA2190584A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing flexible foams |
| CA002190583A Abandoned CA2190583A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing a flexible polyurethane foam |
| CA002190585A Abandoned CA2190585A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing flexible foams |
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| Application Number | Title | Priority Date | Filing Date |
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| CA002190584A Abandoned CA2190584A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing flexible foams |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002190585A Abandoned CA2190585A1 (en) | 1994-06-16 | 1995-05-31 | Process for preparing flexible foams |
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| US (5) | US5491177A (en) |
| EP (3) | EP0765355B1 (en) |
| JP (3) | JP3995710B2 (en) |
| CN (3) | CN1150813A (en) |
| AU (3) | AU691623B2 (en) |
| CA (3) | CA2190584A1 (en) |
| DE (3) | DE69514659T2 (en) |
| ES (3) | ES2139216T3 (en) |
| MY (2) | MY130513A (en) |
| TW (3) | TW344750B (en) |
| WO (3) | WO1995034590A1 (en) |
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| JPH03124741A (en) * | 1989-09-29 | 1991-05-28 | Dow Chem Co:The | Flexible polyurethane foam and its manufacture |
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| 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 |
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| 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 |
-
1995
- 1995-05-23 TW TW084105188A patent/TW344750B/en not_active IP Right Cessation
- 1995-05-23 TW TW084105189A patent/TW358815B/en not_active IP Right Cessation
- 1995-05-23 TW TW084105175A patent/TW290564B/zh active
- 1995-05-31 DE DE69514659T patent/DE69514659T2/en not_active Expired - Fee Related
- 1995-05-31 CN CN95193615A patent/CN1150813A/en active Pending
- 1995-05-31 CA CA002190584A patent/CA2190584A1/en not_active Abandoned
- 1995-05-31 CA CA002190583A patent/CA2190583A1/en not_active Abandoned
- 1995-05-31 EP EP95921793A patent/EP0765355B1/en not_active Expired - Lifetime
- 1995-05-31 EP EP95921792A patent/EP0765354B1/en not_active Expired - Lifetime
- 1995-05-31 ES ES95921793T patent/ES2139216T3/en not_active Expired - Lifetime
- 1995-05-31 ES ES95921792T patent/ES2144613T3/en not_active Expired - Lifetime
- 1995-05-31 WO PCT/EP1995/002068 patent/WO1995034590A1/en active IP Right Grant
- 1995-05-31 AU AU26724/95A patent/AU691623B2/en not_active Ceased
- 1995-05-31 JP JP50155396A patent/JP3995710B2/en not_active Expired - Lifetime
- 1995-05-31 AU AU26723/95A patent/AU691301B2/en not_active Ceased
- 1995-05-31 EP EP95921791A patent/EP0765353B1/en not_active Expired - Lifetime
- 1995-05-31 WO PCT/EP1995/002067 patent/WO1995034589A1/en active IP Right Grant
- 1995-05-31 CN CN95193614A patent/CN1070874C/en not_active Expired - Fee Related
- 1995-05-31 JP JP50155496A patent/JP3995711B2/en not_active Expired - Lifetime
- 1995-05-31 CA CA002190585A patent/CA2190585A1/en not_active Abandoned
- 1995-05-31 CN CN95193611A patent/CN1069325C/en not_active Expired - Fee Related
- 1995-05-31 AU AU26725/95A patent/AU691002B2/en not_active Ceased
- 1995-05-31 JP JP50155296A patent/JP3995709B2/en not_active Expired - Lifetime
- 1995-05-31 ES ES95921791T patent/ES2141944T3/en not_active Expired - Lifetime
- 1995-05-31 DE DE69512911T patent/DE69512911T2/en not_active Expired - Fee Related
- 1995-05-31 DE DE69516517T patent/DE69516517T2/en not_active Expired - Fee Related
- 1995-05-31 WO PCT/EP1995/002069 patent/WO1995034591A1/en active IP Right Grant
- 1995-06-05 US US08/464,195 patent/US5491177A/en not_active Expired - Lifetime
- 1995-06-05 US US08/464,493 patent/US5521225A/en not_active Expired - Lifetime
- 1995-06-05 US US08/462,093 patent/US5491176A/en not_active Expired - Lifetime
- 1995-06-14 MY MYPI95001594A patent/MY130513A/en unknown
- 1995-06-14 MY MYPI95001590A patent/MY112722A/en unknown
-
1996
- 1996-01-25 US US08/591,073 patent/US5594040A/en not_active Expired - Lifetime
- 1996-01-25 US US08/591,047 patent/US5594039A/en not_active Expired - Lifetime
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| Date | Code | Title | Description |
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| FZDE | Discontinued |