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WO1998033833A1 - Nouveaux polyols et leur utilisation dans la preparation de polyurethane - Google Patents

Nouveaux polyols et leur utilisation dans la preparation de polyurethane Download PDF

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Publication number
WO1998033833A1
WO1998033833A1 PCT/EP1998/000128 EP9800128W WO9833833A1 WO 1998033833 A1 WO1998033833 A1 WO 1998033833A1 EP 9800128 W EP9800128 W EP 9800128W WO 9833833 A1 WO9833833 A1 WO 9833833A1
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WIPO (PCT)
Prior art keywords
weight
polyol
amount
aor
blocks
Prior art date
Application number
PCT/EP1998/000128
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English (en)
Inventor
Alain Parfondry
Pierre Gilbert Henri Jean Chaffanjon
Dirk Rene Leonie Ramael
Original Assignee
Huntsman Ici Chemicals Llc
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Publication date
Application filed by Huntsman Ici Chemicals Llc filed Critical Huntsman Ici Chemicals Llc
Priority to AU59875/98A priority Critical patent/AU5987598A/en
Priority to BR9807022-3A priority patent/BR9807022A/pt
Priority to JP53248098A priority patent/JP2001509829A/ja
Priority to EP98902997A priority patent/EP0956311A1/fr
Priority to PCT/EP1998/000128 priority patent/WO1998033833A1/fr
Priority to CA002284460A priority patent/CA2284460A1/fr
Publication of WO1998033833A1 publication Critical patent/WO1998033833A1/fr
Priority to NO993692A priority patent/NO993692L/no
Priority to BG103652A priority patent/BG103652A/xx

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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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
    • 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
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G2110/0075—Foam properties prepared with an isocyanate index of 60 or lower
    • 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

Definitions

  • the present invention is concerned with novel polyols, a process for making them and the use of such polyols in preparing polyurethanes.
  • Polyurethane materials are prepared by reacting polyisocyanates and polyols.
  • the polyols used are polyether polyols having a relatively high molecular weight, e.g. 2000-6000.
  • Such polyether polyols conventionally are polyoxypropylene polyols and polyoxypropylene polyoxyethylene copolymer polyols which may be block copolymers or random copolymers or a combination thereof.
  • a widely used type of polyether polyol is a polyol having a molecular weight of 3000-6000, a nominal hydroxy functionality of 3, a polyoxypropylene and a polyoxyethylene block wherein the polyoxyethylene block is at the end of the three tails of the polymer and constitutes 5-20% by weight of the weight of the polymer; see e.g. The ICI Polyurethanes Book by G. Woods, 1987, J.Wiley and sons, ISBN 0471914266, pages 35-41.
  • Such polyols have been used to make polyurethane materials and in particular elastomers and flexible foams of good quality. However further improvements would be desirable. In particular the stability of such materials as to hydrolysis could be improved as well as resilience and compression set properties.
  • EP-344540 discloses a blend of polypropyleneoxide polyol and polybutyleneoxide polyol, which may be a copolymer with ethylene oxide, propylene oxide and pentalene oxide.
  • the blends are used to make a prepolymer which is used in sealant and coating compositions.
  • the copolymers may be random or block, the amount of comonomer may be up to 60% by weight.
  • US 4,701,520 discloses the preparation of polybutyleneoxide.
  • US 4,465,663 discloses aqueous gels of polyoxybutylene-polyoxyethylene block copolymers having a molecular weight of at least 1200 and an oxyethylene content of 45to 85% by weight. They are used for topically applied cosmetic and pharmaceutical compositions.
  • WO95/16721 discloses the use of non-silicone polyether surfactants in the preparation of polyurethane, polyisocyanurate and polyurea foams. It has been disclosed in wide terms that the surfactants may be used to prepare elastomers, rigid foams or flexible foams. More specifically it has been disclosed that the surfactants act as compatibilisers of polyisocyanates with the other formulation components and as foam stabilisers in insulation and rigid foams. In the examples polyisocyanurate rigid foams are made.
  • the non-silicone polyether surfactnats are polymers comprising substantially no oxypropylene units, 10-90% by weight of oxyethylene units and 10-90% by weight of oxyalkylene units having at least 4 carbons e.g.
  • the surfactants may be capped or not, may have a functionality of 2-8 and are used in an amount of 0.25-20 parts by weight per 100 parts of active hydrogen including compounds. In the examples surfactants have been used which invariably have a nominal functionality of 1 or 2.
  • GB 1063278 discloses a process for preparing elastomers using copolymers of ethylene oxide and 1,2-, 2,3-, or iso-butylene oxide comprising 10-50 and preferably 35-50% by weight of oxyethylene units.
  • the copolymers used are random copolymers.
  • EP383544 discloses the use polyether polyols comprising isobutylene oxide and mono- or unsubstituted alkylene oxide. Only propylene oxide capped copolymers have been used.
  • US4301110 discloses the use of poly(oxybutylene oxyethylene) glycols in preparing reaction injection molded elastomers for improving heat distortion and tear properties. The glycols used have random oxybutylene / oxyethylene blocks.
  • JP57000118 discloses the use of copolymers of ethylene oxide and another 5 alkylene oxide like butylene oxide in preparing rigid polyurethane foams.
  • the copolymers have a low equivalent weight.
  • WO92/06846 discloses curable liquid resin compositions comprising a urethane (meth)acrylate polymer for coating materials.
  • the polymer is made amongst others from a polyol comprising ethylene oxide and 1,2 butylene oxide. As such o polyols copolymerized diols have been used.
  • non-ionic surfactants are described like butylene oxide/ ethylene oxide block copolymers having a functionality of 2.
  • Copending patent application EP-781791 discloses the use of polyether polyols 5 made from butylene oxide in the preparation of elastomers, sealants and adhesives.
  • a wide range of polyols made from butylene oxide may be used according to the description. In the examples their seems to be a trend to use either polyols having a functionality of 2 and an intermediate amount of ethylene oxide or polyols having a functionality of 3 and a low amount of ethylene oxide; 0 the polyols used invariably have an intermediate block of a mixture of butylene oxide and ethylene oxide
  • the polyols should have an oxypropylene block between the initiator and the butylene oxide.
  • 2,3 -BO for 2,3 -butylene oxide iso-BO for isobutylene oxide AO for alkylene oxide having 3 or more carbon atoms and preferably 3 or 4 carbon atoms
  • the present invention is concerned with a polyether polyol having an equivalent weight of 500-10000, an average nominal hydroxyl functionality of 2-8 and having per polymer chain an AOR block and an EOR block wherein the AOR block contains BOR and optionally POR and the amount of the AOR blocks is 70-95% by weight and the amount of the EOR blocks is 5-30% by weight both calculated on the weight of the AOR blocks and the EOR blocks and wherein the EOR blocks are at the end of the polymer chains.
  • the present invention is concerned with a process for preparing such polyether polyols by allowing a compound (hereinafter "initiator"), having 2-8 hydrogen atoms which are reactive with alkylene oxides, to react with BO and optionally with PO and by allowing the product so obtained to react with EO, wherein the amounts of BO, optionally PO, and EO are such that the above ranges as to equivalent weight and amounts of AOR and EOR blocks are met.
  • a compound hereinafter "initiator”
  • isocyanate index or NCO index or index the ratio of NCO-groups over isocyanate-reactive hydrogen atoms present in a formulation, 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 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 groups is considered 5 to comprise one reactive hydrogen and one water molecule is considered to comprise two active hydrogens.
  • Reaction system a combination of components wherein the poly isocyanate 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
  • 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
  • equivalent weight refers to the molecular weight per isocyanate reactive hydrogen atom in the molecule.
  • the equivalent weight of the polyol according to the present invention is 500-8000 and more preferably 750-5000; the nominal functionality preferably is 3-6 and more preferably 3-4.
  • the amount of POR in the AOR block may range from 0 to 95% by weight and preferably ranges from 20-80% by weight.
  • the amount of AOR and EOR blocks preferably is 75-92 and 8-25% by weight 5 respectively calculated on the total weight of the AOR and EOR blocks.
  • polyether polyols in general are made by allowing an initiator, having at least 2 hydrogen atoms which are capable of reacting with alkylene oxides, to react with such alkylene oxides. When only one alkylene oxide is used homopolymers are formed. When two or more alkylene oxides are o used copolymers are formed. Such copolymers may be block copolymers or random copolymers or combinations thereof. Block copolymers are obtained when different alkylene oxides are allowed to react in consecutive order. Random copolymers are formed when mixtures of different alkylene oxides are used. Polymerisation occurs from all reactive hydrogens bound to the initiator.
  • the final polyether polyol will have a number of polymeric tails corresponding to the original number of reactive hydrogens bound to the initiator.
  • such polyether polyols are prepared by charging a vessel with the required amount of initiator and optionally with a catalyst enhancing alkoxylation. Then the alkylene oxide or oxides are added, in mixed form or in consecutive order or a combination 0 thereof as discussed above, and allowed to react. The reaction generally is conducted under an inert gas blanket, at a pressure of 1-5 bar abs and a temperature of 50-130°C.
  • the amount of alkylene oxide used will depend on the molecular weight desired. The duration of the process depends on the other process conditions such as heat exchange, the desired molecular weight and the 5 type of alkylene oxide(s) used; in general the reaction time will vary of from a few hours to a few days.
  • the process for preparing the polyols according to the present invention does not differ materially from the above described general process.
  • BO tends to be less reactive than PO and therefore the reaction time may be somewhat longer. If PO is used to form the AOR block this may be done in admixture with BO or in any consecutive order or combinations thereof.
  • the order of addition of BO and PO is such that a polyol is obtained which has no POR block between the initiator and the BOR, which POR block constitutes more than 20 % by weight of the weight of all oxyalkylene groups in the final polyol.
  • the reaction of the initiator with the alkylene oxides starts with a mixture of BO and PO followed by reaction with EO.
  • o Initiators which may be used are those known in the art like water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, phenyl diamine, diphenylmethane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, 5 bisphenol A, glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, sorbitol and sucrose. Mixtures of initiators may be used as well.
  • BO 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or mixtures thereof may be used.
  • BO is used which comprises at least 50% by weight of 1,2-BO and most preferably is 1,2-BO.
  • Catalysts which may be used are those known in the art to enhance alkoxylation like alkali metal hydroxides or alkoxides, e.g. LiOH, NaOH, KOH, CsOH, Ba(OH) 2 and like organometallic compounds as described in e.g. Ring opening polymerisation of K.C. Frisch and S.L. Reegen, Marcel Dekker Publishers, 1969; Ring opening polymerisation of N. Spassky, vol. 8, no. 1 RAPRA Review (1995) 5 no. 85 and Alkylene oxides and their polymers of J.V. Koleske and F.E. Bailey, 1991, Wiley Publishers.
  • the catalysts are used in amounts sufficient to catalyse the reaction; typical levels are 20 ppm to 10000 ppm based on final product.
  • the present invention is further concerned with the use of the polyether polyols according to the present invention in preparing flexible polyurethane foams by reacting a polyisocyanate and a polyol according to the present invention and using a blowing agent.
  • Processes for preparing flexible polyurethane foams are generally known in the art. Such processes involve the reaction of a polyisocyanate and a polyol having a relatively high molecular weight and the use of a blowing agent, optionally using a catalyst, a chain extender, a crosslinker and/or additives. Such processes may be used to prepare free rise moulded foam, slabstock foam and foam in a closed mould. The process may be conducted according to the so called one-shot method, the semi- or quasi-prepolymer method or the prepolymer method. According to the one-shot method all the polyols having a relatively high molecular weight, i.e.
  • an equivalent weight of 500-10000 are combined with the polyisocyanate and allowed to react in the presence of a foaming agent. According to the semi- or quasi prepolymer process part of this polyol is prereacted with all or part of the polyisocyanate before foam formation is allowed to take place and according to the prepolymer process all this polyol is prereacted with all or part of the polyisocyanate before foam formation is allowed to take place.
  • the polyisocyanates, isocyanate-reactive ingredients, blowing agent and additives are combined and allowed to react and foam in order to prepare the flexible foam.
  • the isocyanate-reactive ingredients, the blowing agent and additives may be premixed.
  • the foam forming reaction is conducted at an index of 40-120, preferably of 50-110.
  • the process according to the present invention for making a flexible polyurethane foam may be conducted according to these known processes as long as at least 10% by weight and preferably at least 25% by weight of the conventional polyols having a relatively high equivalent weight are replaced by the polyol according to the present invention.
  • the present invention is concerned with a process for preparing a flexible polyurethane foam by reacting a polyisocyanate and an isocyanate-reactive composition comprising a polyol according to the present invention in an amount of at least 10 % by weight (on composition) and using a blowing agent.
  • Polyisocyanates which may be used may be selected from aliphatic, cycloaliphatic and araliphatic polyisocyanates, especially diisocyanates, like hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane- 1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and m- and p- tetramethylxylylene diisocyanate, and in particular aromatic polyisocyanates like tolylene diisocyanates (TDI), phenylene diisocyanates and most preferably, which MDI may be selected from pure 4,4'-MDI, isomeric mixtures of 4,4'-MDI and 2,4'-MDI and less than 10% by weight of 2,2'-MDI, crude and polymeric MDI having isocyanate functionalities above 2, and modified variants thereof containing carbodiimide, uretonimine, isocyanurate, urethane
  • diphenylmethane diisocyanate optionally comprising homologues having an isocyanate functionality of 3 or more (MDI) are pure 4,4'-MDI, isomeric mixtures with 2,4'-MDI optionally containing up to 50% by weight of polymeric 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 a low molecular weight polyol (MW less than 1000) and having an NCO content of at least 25% by weight. Mixtures of MDI with up to 25% by weight of other polyisocyanates mentioned above may be used if desired.
  • the polyisocyanate may contain dispersed urea particles and/or urethane particles prepared in a conventional way, e.g. by adding a minor amount of an isophorone diamine to the polyisocyanate.
  • the high molecular weight polyols used for preparing the flexible foams may be selected from polyesters, polyesteramides, polythioethers, polycarbonates, polyacetals, polyolefins, polysiloxanes and, especially, polyethers.
  • Polyether polyols which may be used include products obtained by the polymerisation of ethylene oxide and/or propylene oxide 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, phenyl diamine, diphenylmethane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, sorbitol and sucrose.
  • polyether polyols include polyoxypropylene diols and triols and poly(oxyethylene-oxypropylene) 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 25% and random/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.
  • 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, pentaerythritol 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, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof.
  • polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1 ,4-butanediol, ne
  • Polyesters obtained by the polymerisation of lactones, for example caprolactone, 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 1,3-propanediol, 1 ,4-butanediol, 1,6-hexanediol, diethylene glycol or tetraethylene glycol with diaryl carbonates, for examples 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. Suitablepolyacetals 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.
  • the number average equivalent weight of the high molecular weight polyols preferably is 500-8000 and most preferably 750-5000; the average nominal hydroxyl functionality preferably is 2-6 and more preferably 2-4.
  • at least 10% by weight of the high molecular weight polyol used should be a polyol according to the present invention; preferably this amount is at least 25% by weight.
  • the chain-extending and cross-linking agents which optionally may be used in preparing such foams 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 an equivalent weight of less than 500, toluene diamine, diethyl toluene diamine, cyclohexane diamine, phenyl diamine, diphenylmethane diamine, an 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 the high molecular weight polyol.
  • the blowing agent may be selected from physical blowing agents like chlorofluorocarbons, hydrogen chlorofluorocarbons, hydrogen fluorocarbons and preferably from chemical blowing agents, especially those which lead to CO liberation when reacted with the polyisocyanate under foam forming conditions. Most preferably water is used as blowing agent; if desirable an inert gas like CO 2 , air or N 2 may be used together with the water.
  • the amount of water may range from 2-20 preferably from 2-15 parts by weight per 100 parts by weight of isocyanate-reactive compound having a number average equivalent weight of 500 or more.
  • auxiliaries and additives which amongst others may be used are formation of urea and urethane enhancing catalysts like tertiary amines, imidazoles and tin compounds, surfactants, stabilisers, flame retardants, fillers and anti-oxidants. They may be premixed with the isocyanate-reactive materials before these materials are reacted with the polyisocyanate in order to prepare the foams.
  • the present invention is further concerned with isocyanate terminated prepolymers obtained by reacting an excessive amount of a polyisocyanate and a polyol composition comprising at least 10% by weight and preferably at least 25% by weight of a polyol according to the present invention.
  • polyisocyanate and polyol those may be used which have been mentioned before.
  • the NCO content of the prepolymer may range from 2-40% by weight. If MDI or polymeric MDI is used as the polyisocyanate the NCO content preferably is 5-30% by weight.
  • the prepolymers are made by combining and mixing the polyisocyanate and the polyol and allowing them to react at a temperature of 60-100°C; a catalyst may be used but often is not necessary.
  • the relative amount of polyisocyanate and polyol depends on the kind of polyisocyanate and polyol used and the desired NCO content; for those skilled in the art it is routine to determine these relative 5 amounts.
  • the flexible foams according to the present invention in general will have a density of 15-80 kg/m 3 and may be used as cushioning material, in furniture seating, car-seats and mattresses for instance.
  • polyol 1 The polyol so obtained (polyol 1) was cooled to ambient conditions. It has the physical properties given in Table 1.
  • Example 2 3080g of Intermediate 2, obtained in example 1, was added to a reactor which was flushed three times with N 2 and heated to 110°C. 5424 g of 1,2-butylene oxide was added starting from vacuum in 1 hour and allowed to react for 6 1/2 hours while maintaining the temperature at 110°C, followed by vacuum stripping at
  • the reactor was pressurised with N 2 to 2 bar abs and 1509 g of ethylene oxide was added in 60 minutes at 120°C.
  • the batch was allowed to react for 1 hour and vacuum stipped for 1/2 hour while maintaining the temperature at 120°C. Then the batch was cooled to 85°C, neutralised with an aqueous adipic
  • polyol 2 15 acid solution (32 g/ 250 adipic acid water) and dehydrated for 6 hours at 120°C under vacuum, followed by filtration in 1 hour at 120°C.
  • the polyol so obtained (polyol 2) was cooled to ambient conditions. It has the physical properties given in Table 1.
  • Prepolymers were made by reacting polyols 1-4 and 4,4'-diphenylmethane diisocyanate containing 10% by weight of the 2,4'-isomer in a relative amount of 75/25 w/w.
  • the polyols and polyisocyanate were preheated at 50°C and the reaction was conducted for 3.5 hours at 85°C.
  • prepolymers 2 and 4* were added an amount of 4,4'-diphenylmethane diisocyanate containing 20% by weight of the 2,4'-isomer in order to prepare prepolymers 5 and 6* both having an NCO content of 12% by weight.
  • Polyisocyanate 1 A prepolymer having an NCO content of 27.9% by weight, prepared by reacting 61.6 pbw of 4,4'-MDI containing 30% by weight of 2,4-MDI with 13.4 pbw of a glycerol initialized polyoxyethylene polyoxypropylene polyol (polyol 5) having a molecular weight of 4000 and an oxyethylene content of 75% by weight (random) and adding to this reaction product 25 pbw of a polymeric MDI (polyisocyanate 2) having an NCO content of 30.7% by weight and a diisocyanate content of 39% by weight.
  • polyol 5 A prepolymer having an NCO content of 27.9% by weight, prepared by reacting 61.6 pbw of 4,4'-MDI containing 30% by weight of 2,4-MDI with 13.4 pbw of a glycerol initialized polyoxyethylene polyoxypropylene polyol (polyol 5) having a mole
  • Polyisocyanate 2 The above polymeric MDI
  • Polyisocyanate 3 The reaction product of polyisocyanate 2 and polyol 5 (above) in a weight ratio of 98:2.
  • the NCO value was 30% by weight.
  • Polyol 5 The above polyol 5.
  • Polyol 6 A dipropylene glycol initiated polyoxyethylene polyoxypropylene polyol having an OH value of 30 mg KOH g and an oxyethylene content of 16% by weight (tipped).
  • Polyol 7 A sorbitol initiated polyoxyethylene polyol having an OH value of 190 mg KOH/g.
  • D33LV Dabco TM catalyst from Air Products
  • D8154 TegostabTM surfactant from Goldschmidt Al : Niax TM catalyst from Witco
  • DMEA dimemylethanolamine
  • DMI 1 ,2-dimethylimidazole TABLE 4
  • Foam formulations 2,4 and 6 are according to the present invention, using a polyol or prepolymer containing BOR.
  • Formulations 1, 3 and 5 are comparative examples using polyols and prepolymers containing POR instead of BOR.
  • the 5 foams according to the invention exhibit improved resilience, creep resistance, dynamic fatigue and compression set while density, hardness and tensile properties are hardly affected.
  • the polyols according to the present invention have a lower level of unsaturation and show an improved phase separation in polyurethane formulations, which o enhances the quality of the foam and broadens the accessible density/hardness range.
  • Example 7
  • glycerol initiated polyol was made having an OH value of 27 mg KOH/g by allowing a 50/50 w/w mixture of propylene oxide and butylene oxide to react with the initiator, followed by reaction with an amount of ethylene oxide so as to obtain a polyol having an amount of oxyethylene groups of 14 % by weight (all tipped).

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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)

Abstract

L'invention concerne des polyols comprenant des groupes oxybutylène, ainsi que des prépolymères de ces derniers et des procédés pour préparer des mousses de polyuréthane souples.
PCT/EP1998/000128 1997-01-30 1998-01-12 Nouveaux polyols et leur utilisation dans la preparation de polyurethane WO1998033833A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU59875/98A AU5987598A (en) 1997-01-30 1998-01-12 New polyols and their use in polyurethane preparation
BR9807022-3A BR9807022A (pt) 1997-01-30 1998-01-12 Poliéster poliol, processo para preparação e uso do mesmo, processo para a preparação de uma espuma poliuretano flexìvel, pré-polìmero com terminação de isocianato, e, mistura de polióis.
JP53248098A JP2001509829A (ja) 1997-01-30 1998-01-12 新規ポリオール類およびそれらのポリウレタンの製造における使用
EP98902997A EP0956311A1 (fr) 1997-01-30 1998-01-12 Nouveaux polyols et leur utilisation dans la preparation de polyurethane
PCT/EP1998/000128 WO1998033833A1 (fr) 1997-01-30 1998-01-12 Nouveaux polyols et leur utilisation dans la preparation de polyurethane
CA002284460A CA2284460A1 (fr) 1997-01-30 1998-01-12 Nouveaux polyols et leur utilisation dans la preparation de polyurethane
NO993692A NO993692L (no) 1997-01-30 1999-07-29 Nye polyolforbindelser og deres anvendelse ved fremstilling av polyuretan
BG103652A BG103652A (en) 1997-01-30 1999-08-10 New polyols and their application in polyurethane products

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP97101408.9 1997-01-30
PCT/EP1998/000128 WO1998033833A1 (fr) 1997-01-30 1998-01-12 Nouveaux polyols et leur utilisation dans la preparation de polyurethane

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WO1998033833A1 true WO1998033833A1 (fr) 1998-08-06

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008066809A1 (fr) * 2006-11-28 2008-06-05 Bayer Materialscience Llc Réduction des émissions de mdi associées aux mousses de polyuréthane de remplissage nvh
US9193654B2 (en) * 2004-10-06 2015-11-24 Nof Corporation Cosmetic bases and cosmetics containing the same
WO2017210001A1 (fr) * 2016-05-31 2017-12-07 Dow Global Technologies Llc Compositions de revêtement à faible décollement cathodique
WO2020020709A1 (fr) * 2018-07-25 2020-01-30 Basf Se Stabilisateurs en mousse sans silicone pour la fabrication de mousses en polyuréthane

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1063278A (en) * 1964-10-26 1967-03-30 Wyandotte Chemicals Corp Manufacture of polyurethane elastomers
US4301110A (en) * 1980-08-25 1981-11-17 Texaco Inc. Rim elastomers with improved heat distortion and tear properties
JPS57118A (en) * 1980-06-02 1982-01-05 Mitui Toatsu Chem Inc Polyether-polyol composition for production of rigid polyurethane foam
EP0383544A2 (fr) * 1989-02-14 1990-08-22 ARCO Chemical Technology, L.P. Polyols à partir d'oxyde d'isobutylène
WO1992006846A1 (fr) * 1990-10-19 1992-04-30 Dsm Desotech, Inc. Composition de resine liquide durcissable
WO1995016721A1 (fr) * 1993-12-17 1995-06-22 The Dow Chemical Company Polymeres a base de polyisocyanates prepares a partir de formulations comprenant des tensioactifs autres que silicone et leur procede de preparation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1063278A (en) * 1964-10-26 1967-03-30 Wyandotte Chemicals Corp Manufacture of polyurethane elastomers
JPS57118A (en) * 1980-06-02 1982-01-05 Mitui Toatsu Chem Inc Polyether-polyol composition for production of rigid polyurethane foam
US4301110A (en) * 1980-08-25 1981-11-17 Texaco Inc. Rim elastomers with improved heat distortion and tear properties
EP0383544A2 (fr) * 1989-02-14 1990-08-22 ARCO Chemical Technology, L.P. Polyols à partir d'oxyde d'isobutylène
WO1992006846A1 (fr) * 1990-10-19 1992-04-30 Dsm Desotech, Inc. Composition de resine liquide durcissable
WO1995016721A1 (fr) * 1993-12-17 1995-06-22 The Dow Chemical Company Polymeres a base de polyisocyanates prepares a partir de formulations comprenant des tensioactifs autres que silicone et leur procede de preparation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8207, Derwent World Patents Index; Class A25, AN 82-12390E, XP002040822 *
NACE V.M. ET A: "Nonionic Surfactant Polarity Index Determination by Inverse Gas Chromotography", J. AMER. OILL CHEM. SOC., vol. 72, no. 01, 1995, pages 89 - 95, XP002040821 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9193654B2 (en) * 2004-10-06 2015-11-24 Nof Corporation Cosmetic bases and cosmetics containing the same
WO2008066809A1 (fr) * 2006-11-28 2008-06-05 Bayer Materialscience Llc Réduction des émissions de mdi associées aux mousses de polyuréthane de remplissage nvh
US7678840B2 (en) 2006-11-28 2010-03-16 Bayer Materialscience Llc Reduction of MDI emissions in cavity filling NVH polyurethane foams
WO2017210001A1 (fr) * 2016-05-31 2017-12-07 Dow Global Technologies Llc Compositions de revêtement à faible décollement cathodique
RU2741595C2 (ru) * 2016-05-31 2021-01-27 Дау Глоубл Текнолоджиз, Ллк Покрывающие композиции с низким отслаиванием при катодной поляризации
WO2020020709A1 (fr) * 2018-07-25 2020-01-30 Basf Se Stabilisateurs en mousse sans silicone pour la fabrication de mousses en polyuréthane
CN112424249A (zh) * 2018-07-25 2021-02-26 巴斯夫欧洲公司 用于制备聚氨酯泡沫的不含硅酮的泡沫稳定剂
CN112424249B (zh) * 2018-07-25 2023-08-25 巴斯夫欧洲公司 用于制备聚氨酯泡沫的不含硅酮的泡沫稳定剂

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