WO2007111828A2 - Mousse de polyurethane de basse densite a base d'huile naturelle sans additif de stabilisation de cellules a base de silicone - Google Patents

Mousse de polyurethane de basse densite a base d'huile naturelle sans additif de stabilisation de cellules a base de silicone Download PDF

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WO2007111828A2
WO2007111828A2 PCT/US2007/006187 US2007006187W WO2007111828A2 WO 2007111828 A2 WO2007111828 A2 WO 2007111828A2 US 2007006187 W US2007006187 W US 2007006187W WO 2007111828 A2 WO2007111828 A2 WO 2007111828A2
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polyol
weight
percent
foam
total
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PCT/US2007/006187
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WO2007111828A3 (fr
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Jean-Marie Sonney
Francois M. Casati
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Dow Global Technologies Inc.
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Publication of WO2007111828A3 publication Critical patent/WO2007111828A3/fr

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    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy 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
    • C08G18/28—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
    • C08G18/28—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
    • C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention pertains to natural oil based polyols and to their use in the production of toluene diisocyanate (TDI) based, low density, flexible polyurethane foams.
  • TDI toluene diisocyanate
  • Polyether polyols based on the polymerization of alkylene oxides, and/or polyester polyols, and/or combinations thereof, are the major components of a polyurethane system together with isocyanates.
  • Polyols can also be filled polyols, such as SAN (Styrene/Acrylonitrile) , PIPA (polyisocyanate polyaddition) or PHD (polyurea) polyols, as described in "Polyurethane Handbook", by G. Oertel, Hanser publisher.
  • polyols are those made from vegetable oils or • renewable feedstocks. Such polyols are described by Peerman et al . in U.S. Patents 4,423,162; 4,496,487 and 4,543,369. Peerman et al . describe hydroformylating and reducing esters of fatty acids as are obtained from vegetable oils and forming esters of the resulting hydroxylate materials with a polyol or polyamine. Higher functional polyester polyol materials derived from fatty acids are described in WO 2004/096882; WO 2004/096883. These polyester polyols are made by reacting a polyhydroxyl initiator with certain hydroxymethylated fatty acids . Others approaches for polyols based on renewable resources are described for example in Publications WO 2004/020497; WO 2004/099227; WO 2005/0176839; WO 2005/0070620 and in US Patent 4,640,801.
  • Polyurethane foams generally contain additional components such as surfactants, stabilizers, cell regulators, antioxidants, cross-linkers and/or chain extenders, as well as catalysts, such as tertiary amines and/or organometallic salts and depending on the end use application, flame retardant additives and/or fillers.
  • additional components such as surfactants, stabilizers, cell regulators, antioxidants, cross-linkers and/or chain extenders, as well as catalysts, such as tertiary amines and/or organometallic salts and depending on the end use application, flame retardant additives and/or fillers.
  • VOCs volatile organic compounds
  • efforts have been made to utilize additives which reduce the level of VOCs.
  • VOCs volatile organic compounds
  • efforts have been made to reduce the level of volatile amine catalysts by utilizing amine catalysts which contain a hydrogen isocyanate reactive group, i.e. a hydroxyl or a primary and/or a secondary amine.
  • amine catalysts which contain a hydrogen isocyanate reactive group, i.e. a hydroxyl or a primary and/or a secondary amine.
  • Such catalysts are disclosed in EP 747,407.
  • Other types of reactive monol catalysts are described in U.S. Patents 4,122,038, 4,368,278 and 4,510,269.
  • Use of specific amine-initiated polyols is proposed in EP 539,819, in U.S. Patent 5,672,636 and in WO 01/ 58,976.
  • Polyols containing tertiary amino groups are described in US 3,428,708,
  • Another example for the reduction of VOCs is the replacement of the antioxidant BHT (Butylated Hydroxy-Toluene) with less migrating molecules such as those disclosed in EP 1,437,372.
  • BHT Butylated Hydroxy-Toluene
  • polyurethane materials produced using a substantial amount of the polyol from a renewable resource in the polyol formulation have a tendency to have low air flow values, see for example, WO 2004/096883.
  • the low air flow values indicate the foams are not well suited for such uses as automotive seating as poor airflow negatively influences resistance to dynamic fatigue.
  • foams produced using high levels of materials from natural resources in the formulation have been shown to have poorer compression set values, see for example, U.S. Publication 2005/007620.
  • NOBP natural oil based polyol
  • the present invention is a process for the production of a flexible polyurethane foam by reaction of a mixture of (a) an isocyanate component containing at least 60 weight percent TDI ;
  • the present invention is a flexible polyurethane foam, having a density below 50 kg/m 3 , which is the reaction product of an isocyanate component containing at least 60 percent by weight of TDI and a polyol component comprising (i) up to 80 percent by weight of the total polyol of at least one polyol compound other than (ii) having a nominal starter functionality of 2 to 8 and a hydroxyl number from 15 to 200;
  • the present invention is a process whereby polyol (bl) is totally or partially amine based, i.e. contains nitrogen in the starter or in the chain and preferably has autocatalytic characteristics for the polyurethane reaction.
  • the present invention is a process whereby polyol (bl) and/or (b2) contain primary and/or secondary hydroxyl groups .
  • the present invention is a process whereby polyol (bl) and/or (b2) contains primary and/or secondary amine groups .
  • the polyol (b2) based on renewable resources is referred to herein as natural oil based polyols (NOBP) .
  • the polyols (b2) are liquid at room temperature and have multiple active sites.
  • the addition of polyol (b2) to a one-shot polyurethane reaction mixture eliminates the need to include a silicone based cell stabilizing surfactant in a flexible, and/or viscoelastic foam formulation.
  • substantially no silicone based cell stabilizing surfactant means the absence of a silicone based cell stabilizing surfactant or a level of such surfactant below detectable changes in the foam property measured against the properties of the foam prepared in the absence of a silicone based surfactant.
  • polyurethane foams can be produced using in the polyol component 20 percent by weight or more of a NOBP to obtain foam wherein the foam has sufficient open cell structure such that comparable to conventional formulations based on polyols from petroleum based feedstocks the foam has air flow properties and compression set properties comparable to conventional formulations based on polyols from petroleum based feedstocks.
  • foams are produced by omitting from the formulation a silicone based cell stabilizing surfactant, or a substantial reduction in the amount of such surfactants in the formulation, however; the formulation does include the presence of a cell regulating agent.
  • the air flow is generally at least 2.5 cfm as measured by ASTM 3574-95.
  • the air flow is 3.0 cfm or greater. More preferably the air flow is 3.5 cfm or greater.
  • the foam has a 75 % CS value of 20 % CD or less as measured by OPEL 60283-4-96.
  • the foam has a CS of less than 18 percent. More preferably the foam has a CS of less than 15 percent.
  • CD is a means of calculating the CS, i.e., dividing by the sample thickness loss by the thickness of the sample under compression. For instance a 50 % CS is divided by 0.5 x original thickness, and a 75 % CS is divided by 0.75 X the original thickness.
  • the present invention provides for polyurethane products containing reduced levels of VOCs.
  • a further reduction in the level of VOCs can also be achieved by replacing, or partial replacement of fugitive amine catalysts generally used in the production of polyurethane foam with an autocatalytic polyol as described herein.
  • polyols are those materials having at least one group containing an active hydrogen atom capable of undergoing reaction with an isocyanate.
  • Preferred among such compounds are materials having at least two hydroxyls, primary or secondary, or at least two amines, primary or secondary, carboxylic acid, or thiol groups per molecule.
  • Compounds having at least two hydroxyl groups or at least two amine groups per molecule are especially preferred due to their desirable reactivity with polyisocyanates .
  • Suitable polyols (bl) of the present invention are well known in the art and include those described herein and any other commercially available polyol and/or SAN, PIPA or PHD copolymer polyols. Such polyols are described in "Polyurethane Handbook", by G. Oertel, Hanser publishers. Mixtures of one or more polyols and/or one or more copolymer polyols may also be used to produce polyurethane products according to the present invention.
  • polyols include polyether polyols, polyester polyols, polyhydroxy-terminated acetal resins, hydroxyl- terminated amines and polyamines . Examples of these and other suitable isocyanate-reactive materials are described more fully in U.S. Patent 4,394,491.
  • Alternative polyols that may be used include polyalkylene carbonate-based polyols and polyphosphate- based polyols.
  • Catalysis for this polymerization can be either anionic or cationic, with catalysts such as KOH, CsOH, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate or quaternary phosphazenium compound.
  • catalysts such as KOH, CsOH, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate or quaternary phosphazenium compound.
  • DMC double cyanide complex
  • Suitable initiator molecules are water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic acid; and polyhydric, in particular dihydric to octohydric alcohols or dialkylene glycols.
  • Exemplary polyol initiators include, for example, ethanediol , 1,2- and 1 , 3-propanediol , diethylene glycol, dipropylene glycol, 1, 4-butanediol , 1, 6-hexanediol, glycerol, pentaerythritol , sorbitol, sucrose, neopentylglycol ; 1,2-propylene glycol; trimethylolpropane glycerol; 1, 6-hexanediol; 2,5- hexanediol; 1 , 4 -butanediol ; 1, 4-cyclohexane diol; ethylene glycol; diethylene glycol; triethylene glycol; 9(1)- hydroxymethyloctadecanol , 1, 4-bishydroxymethylcyclohexane; 8,8- bis (hydroxymethyl) tricyclo [5, 2, 1, O 2 ' 6 ] decene; Dime
  • initiators include linear and cyclic compounds containing an amine.
  • Exemplary polyamine initiators include ethylene diamine, neopentyldiamine, 1, 6-diaminohexane,- bisaminomethyltricyclodecane; bisaminocyclohexane,- diethylene triamine,- bis-3-aminopropyl methylamine; triethylene tetramine various isomers of toluene diamine; diphenylmethane diamine; N- methyl-1, 2-ethanediamine, N-Methyl-1, 3-propanediamine, N, N- dimethyl-1, 3-diaminopropane, N,N-dimethylethanolamine, 3,3'- diamino-N-methyldipropylamine, N, N-dimethyldipropylenetriamine , aminopropyl-imidazole .
  • Exemplary aminoalcohols include ethanolamine , diethanolamine, and triethanolamine.
  • Polyol (bl) can also contain a tertiary nitrogen in the chain, by using for instance an alkyl-aziridine as co-monomer with PO and EO.
  • Polyols with tertiary amine end-cappings are those which contain a tertiary amino group linked to at least one tip of a polyol chain.
  • These tertiary amines can be N,N-dialkylamino, N- alkyl, aliphatic or cyclic, amines, polyamines.
  • poly(propylene oxide) homopolymers random copolymers of propylene oxide and ethylene oxide in which the poly(ethylene oxide) content is, for example, from about 1 to about 30% by weight
  • ethylene oxide-capped poly(propylene oxide) polymers and ethylene oxide-capped random copolymers of propylene oxide and ethylene oxide.
  • polyether ⁇ preferably contain 2-5, especially 2-4, and preferably 2-3, mainly secondary hydroxyl groups per molecule and have an equivalent weight per hydroxyl group of from about 400 to about 3000, especially from about 800 to about 1750.
  • such polyethers preferably contain 2-6, especially 2- 4, and in some applications preferably 2-5, mainly primary hydroxyl groups per molecule and have an equivalent weight per hydroxyl group of from about 1000 to about 3000, especially from about 1200 to about 2000.
  • the nominal average functionality number of hydroxyl groups per molecule will be preferably in the ranges specified.
  • the polyether polyols may contain low terminal unsaturation (for example, less that 0.02 meq/g or less than 0.01 meq/g) , such as those made using so-called double metal cyanide (DMC) catalysts, as described for example in US Patent Nos . 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334, 3,427,335, 5,470,813 and 5,627,120.
  • Polyester polyols typically contain about 2 hydroxyl groups per molecule and have an equivalent weight per hydroxyl group of about 400-1500. Polymer polyols of various sorts may be used as well.
  • Polymer polyols include dispersions of polymer particles, such as polyurea, polyurethane- urea, polystyrene, polyacrylonitrile and polystyrene-co- acrylonitrile polymer particles in a polyol, typically a polyether polyol .
  • Suitable polymer polyols are described in US Patent Nos . 4,581,418 and 4,574,137.
  • (bl) contains at least one polyol which contains autocatalytic activity and can replace a portion or all of the amine and/or organometallic catalyst generally used in the production of polyurethane foams.
  • Autocatalytic polyols are those made from an initiator containing a tertiary amine, polyols containing a tertiary amine group in the polyol chain or a polyol partially capped with a tertiary amine group.
  • (b2) is added to replace at least 10 percent by weight of amine catalyst while maintaining the same reaction profile.
  • an autocatalytic polyol is added to replace at least 20 percent by weight of the conventional amine catalyst while maintaining the same reaction profile.
  • Such autocatalytic polyols may also be added to replace at least 50 percent by weight of the amine catalyst while maintaining the same reaction profile.
  • such autocatalytic polyols may be added to enhance the demold time.
  • the autocatalytic polyol has a molecular weight of from about 1000 to about 12,000 and is prepared by alkoxylation of at least one initiator molecule of the formula
  • a at each occurrence is independently oxygen, nitrogen, sulfur or hydrogen, with the proviso that only one of A can be hydrogen at one time,
  • R is a C 1 to C 3 alkyl group
  • m is equal to 0 when A is hydrogen, is 1 when A is oxygen and is 2 when A is nitrogen, or H 2 N- (CH 2 ) m -N- (R) -H Formula (II) where m is an integer from 2 to 12 and R is a C 1 to C 3 alkyl group.
  • Preferred initiators for the production of an autocatalytic polyol include, 3 , 3 ' -diamino-N-methyldipropylamine, 2,2' -diamino-N-methyldiethylamine , 2 , 3-diamino-N-methyl-ethyl- propylamine N-methyl-1 , 2-ethanediamine and N-methyl-1, 3- propanediamine .
  • the aforementioned autocatalytic polyols will constitute up to 50 weight percent of the total polyol, preferably up to 40 weight percent of the polyol. Generally when used, such autocatalytic polyols will constitute at least 1 weight percent of the polyol. More preferably such polyols will represent 5 percent of greater of the total polyol.
  • Autocatalytic polyols containing at least one imine linkage and one tertiary amine group as disclosed in WO Publication 2005063840, the disclosure of which is incorporated herein by reference may also be used.
  • such polyols are based on the reaction between an aldehyde, or a ketone, and a molecule containing both primary amine and tertiary amine groups.
  • imine based polyols When such imine based polyols are used, they will generally constitute from 0.5 to 2 parts of the polyol component.
  • a combination of the autocatalytic polyols may also be used.
  • Polyols of (b2) are polyols based on or derived from renewable resources such as natural and/or genetically modified (GMO) plant vegetable seed oils and/or animal source fats.
  • Such oils and/or fats are generally comprised of triglycerides, that is, fatty acids linked together with glycerol.
  • Preferred are vegetable oils that have at least about 70 percent unsaturated fatty acids in the triglyceride.
  • the natural product contains at least about 85 percent by weight unsaturated fatty acids.
  • preferred vegetable oils include, for example, those from castor, soybean, olive, peanut, rapeseed, corn, sesame, cotton, canola, safflower, linseed, palm, sunflower seed oils, or a combination thereof.
  • animal products include lard, beef tallow, fish oils and mixtures thereof.
  • a combination of vegetable and animal based oils/fats may also be used.
  • the iodine value of these natural oils range from about 40 to 240.
  • polyols (b2) are derived from soybean and/or castor and/or canola oils.
  • Such modifications of a renewable resource include, for example, epoxidation, as described in US Patent 6,107,433 or in US Patent 6,121,398; hydroxylation, such as described in WO 2003/029182; esterification such as described in US 6,897,283; 6,962,636 or 6,979,477,- hydroformylation as described in WO 2004/096744; grafting such as described in US 4,640,801; or alkoxylation as described in US 4,534,907 or in WO 2004/020497.
  • the above cited references for modifying the natural products are incorporated herein by reference. After the production of such polyols by modification of the natural oils, the modified products may be further alkoxylated.
  • the modified product undergoes alkoxylation with sufficient EO to produce a polyol (b2) with from 10 to 60 weight percent EO; preferably 20 to 40 weight percent EO.
  • the polyols (b2) are obtained by a combination of the above modification techniques as disclosed in PCT Publications WO 2004/096882 and 2004/096883, and Applicant's copending application Serial No. 60/676,348 entitled "Polyester Polyols Containing Secondary alcohol Groups and Their Use in Making Polyurethanes Such as Flexible Polyurethane Foams", the disclosures of which are incorporated herein by reference.
  • the process involves a multi-step process wherein the animal or vegetable oils/fats is subjected to transesterification and the constituent fatty acids recovered.
  • This step is followed by hydroformylating carbon-carbon double bonds in the constituent fatty acids to form hydroxymethyl groups, and then forming a polyester or polyether/polyester by reaction of the hydroxymethylated fatty acid with an appropriate initiator compound.
  • This later technologies is favored since as it allows the production of a polyol (b2) with both hydrophobic and hydrophilic moieties.
  • the hydrophobic moiety is provided by the natural oils since those contain C4 to C24 saturated and/or unsaturated chain lengths, preferably C8 to Cl8 chain lengths, while the hydrophilic moiety is obtained by the use of proper polyol chains present on the initiator, such as those containing high levels of ethylene oxide.
  • the initiator for use in the multi-step process for the production of polyol (b2) may be any of the initiators given above used in the production of polyol (bl) .
  • the initiator is selected from the group consisting of neopentylglycol ,- 1 , 2-propylene glycol; trimethylolpropane ; pentaerythritol ; sorbitol; sucrose; glycerol; diethanolamine,- alkanediols such as 1, 6-hexanediol , 1, 4-butanediol ; 1, 4-cyclohexane diol; 2, 5-hexanediol,- ethylene glycol; diethylene glycol, triethylene glycol; bis-3-a ⁇ inopropyl methylamine,- ethylene diamine; diethylene triamine,- 9 (1) -hydroxymethyloctadecanol, 1,4- bishydroxymethylcyclohexane; 8,8- bis (hydroxymethyl) tricyclo [5, 2, 1, 0 3S ] decene; Dimerol alcohol; hydrogenated bisphenol,- 9,9(10,10) -bishydroxymethylocta
  • the initiator is selected from the group consisting of glycerol; ethylene glycol; 1, 2-propylene glycol; trimethylolpropane; ethylene diamine; pentaerythritol; diethylene triamine; sorbitol; sucrose; or any of the aforementioned where at least one of the alcohol or amine groups present therein has been reacted with ethylene oxide, propylene oxide or mixture thereof; and combination thereof.
  • the initiator is glycerol, trimethylopropane, pentaerythritol, sucrose, sorbitol, and/or mixture thereof .
  • such initiators are alkoxlyated with ethylene oxide or a mixture of ethylene and at least one other alkylene oxide to give an alkoxylated initiator with a molecular weight of 200 to 6000, especially from 400 to 2000.
  • the alkoxylated initiator has a molecular weight from 500 to IOOO .
  • polyol (b2) contains from 10 to 60 weight percent ethylene oxide.
  • polyol (b2) will contain from 15 to 50 weight percent EO. More preferably polyol (b2) contains from 20 to 40 weight percent ethylene oxide.
  • polyol (b2) The functionality of polyol (b2) , or blend of such polyols, is above 1.5 and generally not higher than 6. Preferably the functionality is below 4.
  • the hydroxyl number of polyol (b2) , or blend of such polyols, is below 300 mg KOH/g, and preferably below 100.
  • the weight ratio of NOBP (b2) to polyol (bl) is adjusted to give foam stability without the need for a silicone based cell stabilizing surfactant.
  • the level of polyol (b2) is at least 20 PPHP (part per hundred parts polyol) in a foam formulation, and preferably at least 30 PPHP. More preferably (b2) is present in an amount of at least 40 PPHP.
  • Polyol (b2) may constitute 75% or more, 85% or more, 90% or more, 95% or more or even 100% of the total weight of the polyol. The higher levels are particularly applicable for specific applications, such as high density, visco-elastic foams.
  • Combination of two types of polyols (b2) can also be used, either to maximize the level of seed oil in the foam formulation, or to optimize foam processing and/or specific foam characteristics, such as resistance to humid aging.
  • the viscosity of the polyol (b2) measured at 25°C is generally less than 6,000 mPa.s.
  • the viscosity of polyol (b2) at 25°C is less than 5,000 mPa.s.
  • a cell regulator is included in the reaction mix.
  • the cell regulator is added in the polyol component .
  • Cell regulators have no bulk stabilization effect during foaming and act as antifoaming agents, see for example, Polyurethane Handbook, G ⁇ ther Oertels ed. , 2 nd edition, page 108. Such regulators are generally low-molecular weight, low-viscosity organopolysiloxane ⁇ as disclosed in U.S. Patent 4,042,540 and GB Patent 1 381 571 the disclosures of which are incorporated herein by reference. Preferred cell regulators are methylpolysiloxanes . It is unexpected these cell regulators would help in providing good foam properties with the composition of the present invention as these cell regulating surfactants are generally recommended for use in MDI based foams.
  • Tegostab B 4113 Tegostab B 8715 LF, from Degussa, Niax L 3001 from GE Specialties, Dabco DC 2525 from Air Products.
  • These cell regulating surfactants are generally added at less than 2 PPHP and preferably below 1.5 PPHP. More preferably the cell regulating agent is added at below 1 PPHP with the present invention. Generally the cell regulator is added in at least 0.01 PPHP and preferably at greater than 0.02 PPHP .
  • TDI reactivity isocyanate groups
  • TDI comprises at least 70 percent of the polyisocyanate. More preferably TDI comprises at least 80 percent of the polyisocyanate.
  • TDI is the sole isocyanate used for producing the polyurethane foam. When TDI does not constitute all of the isocyanate present, aliphatic, cycloaliphatic, arylaliphatic and other aromatic isocyanates may be used.
  • suitable additional aromatic isocyanates include the 4,4'-, 2,4' and 2,2' -isomers of diphenylmethane diisocyante (MDI) , blends thereof and polymeric and monomeric MDI blends, m- and p-phenylenediisocyanate, chlorophenylene-2 , 4- diisocyanate, diphenylene-4 , 4 ' -diisocyanate, 4, 4 ' -diisocyanate- 3,3' -ditnehtyldiphenyl , 3-methyldiphenyl-methane-4 , 4 ' -diisocyanate and diphenyletherdiisocyanate and 2, 4 , 6-triisocyanatotoluene and 2,4,4' -triisocyanatodiphenylether .
  • MDI diphenylmethane diisocyante
  • a crude polyisocyanate may also be used in the practice of this invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamine or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine .
  • TDI/MDI blends are used.
  • aliphatic polyisocyanates examples include ethylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4 -diisocyanate, 4,4'- dicyclohexylmethane diisocyanate, saturated analogues of the above mentioned aromatic isocyanates and mixtures thereof.
  • the amount of polyisocyanate used in making the flexible foam is commonly expressed in terms of isocyanate index, i.e. 100 times the ratio of NCO groups to reactive hydrogens-contained in the reaction mixture.
  • the isocyanate index typically ranges from about 75-140, especially from about 80 to 115.
  • the isocyanate index typically ranges from about 50 to about 150, especially from about 75 to about 110.
  • a blowing agent For producing a polyurethane-based foam, a blowing agent is generally required.
  • water is preferred as a blowing agent.
  • the amount of water is preferably in the range of from 0.5 to 10 parts by weight, more preferably from 2 to 7 parts by weight based on 100 parts by weight of the polyol.
  • Carboxylic acids or salts are also used as reactive blowing agents.
  • Other blowing agents can be liquid or gaseous carbon dioxide, methylene chloride, acetone, pentane, isopentane, methylal or dimethoxymethane, dimethylcarbonate. Use of artificially reduced or increased atmospheric pressure can also be contemplated with the present invention.
  • polyurethane polymers In addition to the foregoing critical components, it is often desirable to employ certain other ingredients in preparing polyurethane polymers.
  • additional ingredients are preservatives, flame retardants, colorants, antioxidants, reinforcing agents, fillers, including recycled polyurethane foam in form of powder.
  • One or more catalysts for the reaction of the polyol (and water, if present) with the polyisocyanate can be used. Any suitable urethane catalyst may be used, including tertiary amine compounds, amines with isocyanate reactive groups and organometallic compounds. Preferably the reaction is carried out in the absence of an amine or an organometallic catalyst or a reduced amount as described above.
  • Exemplary tertiary amine compounds include triethylenediamine, N-methylmorpholine, N, N-dimethylcyclohexylamine , pentamethyldiethylenetriamine , tetramethylethylenediamine, bis (dimethylaminoethyl) ether, 1-methyl-4 -dimethylaminoethyl -piperazine , 3 -methoxy-N- dimethylpropylamine, N-ethylmorpholine, dimethylethanolamine, N-cocomorpholine, N,N-dimethyl-N' ,N 1 -dimethyl isopropylpropylenediamine, N,N-diethyl-3-diethylamino- propylamine and dimethylbenzylamine .
  • organometallic catalysts include organomercury, organolead, organoferric and organotin catalysts, with organotin catalysts being preferred among these.
  • Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyltin di-laurate, as well as other organometallic compounds such as are disclosed in U.S. Patent 2,846,408.
  • a catalyst for the trimerization of polyisocyanates , resulting in a polyisocyanurate, such as an alkali metal alkoxide may also optionally be employed herein.
  • the amount of amine catalysts can vary from 0.02 to 5 percent in the formulation or organometallic catalysts from 0.001 to 1 percent in the formulation can be used.
  • the foams are produced in the absence of a tin catalyst.
  • One or more crosslinkers may be present in the flexible foam formulation, in addition to the polyols (bl) and (b2) described above. This is particularly the case when making high resilience slabstock or molded foam. If used, suitable amounts of crosslinkers are from about 0.1 to about 1 part by weight, especially from about 0.25 to about 0.5 parts by weight, per 100 parts by weight of polyols.
  • crosslinkers are materials having three or more isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 400.
  • Crosslinkers preferably contain from 3-8, especially from 3-4 hydroxyl, primary amine or secondary amine groups per molecule and have an equivalent weight of from 30 to about 200, especially from 50-125.
  • suitable crosslinkers include diethanol amine, monoethanol amine, triethanol amine, mono- di- or tri (isopropanol) amine, glycerine, trimethylol propane, pentaerythritol, sorbitol and the like.
  • a chain extender is a material having two isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 400, especially from 31-125.
  • the isocyanate reactive groups are preferably hydroxyl, primary aliphatic or aromatic amine or secondary aliphatic or aromatic amine groups.
  • chain extenders include amines ethylene glycol, diethylene glycol, 1, 2-propylene glycol, dipropylene glycol, tripropylene glycol, ethylene diamine, phenylene diamine, bis (3-chloro-4- aminophenyl) methane and 2 , 4-diamino-3 , 5-diethyl toluene. If used, chain extenders are typically present in an amount from about 1 to about 50, especially about 3 to about 25 parts by weight per 100 parts by weight of polyols.
  • crosslinkers and chain extenders are known in the art as disclosed in U.S. Patent 4,863,979 and EP Publication 0 549 120.
  • an emulsifier is generally added to help compatibilize the reaction components.
  • emulsifiers are known in the art and examples of non silicone based emulsifier include sulfonated natural oils, fatty acid esters and ethylene oxide condensates of phenol or octylphenol .
  • examples of commercially available emulsifiers include Span 80, a sorbitan monooleate, and sodium salts of sulfonated ricinoleic acid.
  • emulsifiers include the reaction product of an oc, ⁇ -diol oligomer with a diisocyanate as disclosed in US Patent 5,057,573, the disclosure of which is incorporated herein by reference.
  • the emulsifier is generally from 0.1 to 10 weight percent of the total polyol , more preferably from 1 to 8 parts and even more preferably from 2 to 6 percent .
  • a polyether polyol may be included in the formulation, i.e, as part of polyol (bl) , to promote the formation of an open-celled or softened polyurethane foam.
  • Such cell openers are disclosed in U.S. Patent 4, 863,976, the disclosure of which is incorporated here by reference.
  • Such cell openers generally have a functionality of 2 to 12, preferably 3 to 8, and a molecular weight of at least 5,000 up to about 100,000.
  • Such polyether polyols contains at least 50 weight percent oxyethylene units, and sufficient oxypropylene units to render it compatible with the components.
  • the cell openers when used, are generally present in an amount from 0.2 to 5, preferably from 0.2 to 3 parts by weight of the total polyol.
  • Examples of commercially available cell openers are VORANOL*Polyol CP 1421 and VORANOL* Polyol 4053; VORANOL is a trademark of The Dow Chemical Company.
  • the applications for foams produced by the present invention are those known in the industry. Flexible and viscoelastic foams are mainly used in applications such as furniture and automobile seating. Other applications may include sun visors, steering wheels, packaging applications, armrests, door panels, noise insulation parts, other cushioning and energy management applications, carpet backing, dashboards and other applications for which conventional flexible polyurethane foams are used.
  • polyurethane-forming reaction mixture may be mixed together in any convenient manner, for example by using any of the mixing equipment described in the prior art for the purpose such as described in "Polyurethane Handbook", by G. Oertel, Hanser publisher.
  • the polyurethane foam is prepared by mixing the polyisocyanate and polyol composition in the presence of the blowing agent, catalyst (s) and other optional ingredients as desired, under conditions such that the polyisocyanate and polyol composition react to form a polyurethane and/or polyurea polymer while the blowing agent generates a gas that expands the reacting mixture.
  • the foam may be formed by the so-called prepolymer method, as described in U.S. Pat. No.
  • Slabstock foam is conveniently prepared by mixing the foam ingredients and dispensing them into a trough or other region where the reaction mixture reacts, rises freely against the atmosphere (sometimes under a film or other flexible covering) and. cures.
  • the foam ingredients or various mixtures thereof
  • the foam ingredients are pumped independently to a mixing head where they are mixed and dispensed onto a conveyor that is lined with paper or plastic. Foaming and curing occurs on the conveyor to form a foam bun.
  • the resulting foams are typically from about from about 10 kg/m 3 to 80 kg/m 3 , especially from about 15 kg/m 3 to 60 kg/m 3 , preferably from about 17 kg/m 3 to 50 kg/m 3 in density.
  • a preferred slabstock foam formulation contains from about 3 to about 6 , preferably about 4 to about 5 parts by weight water are used per 100 parts by weight high equivalent weight polyol at atmospheric pressure. At reduced pressure these levels are reduced.
  • High resilience slabstock (HR slabstock) foam is made in methods similar to those used to make conventional slabstock foam but using higher equivalent weight polyols.
  • HR slabstock foams are characterized in exhibiting a Ball rebound score of 45% or higher, per ASTM 3574.03. Water levels tend to be from about 2 to about 6, especially from about 3 to about 5 parts per 100 parts (high equivalent) by weight of polyols.
  • Molded foam can be made according to the invention by transferring the reactants (polyol composition including copolyester, polyisocyanate, blowing agent, and surfactant) to a closed mold where the foaming reaction takes place to produce a shaped foam.
  • reactants polyol composition including copolyester, polyisocyanate, blowing agent, and surfactant
  • a closed mold where the foaming reaction takes place to produce a shaped foam.
  • Cold-molding processes in which the mold is not preheated significantly above ambient temperatures
  • a hot-molding process in which the mold is heated to drive the cure
  • Densities for molded foams generally range from 30 to 50 kg/m 3 .
  • DEOA is 99 % pure diethanolamine.
  • Dabco DC 5169 is a silicone-based cell stabilizing surfactant available from Air Products and Chemicals Inc.
  • Dabco DC 5164 is a silicone-based cell stabilizing surfactant available from Air Products and Chemicals Inc.
  • TEGOSTAB B-8715 LF is a silicone-based cell regulating surfactant available from Degussa-
  • TEGOSTAB B-8719 LF is a silicone-based surfactant with both cell stabilizing and cell regulating effect, available from Degussa-
  • Dabco DC 2525 is silicone-based surfactant with cell regulating effect available from Air
  • Span 80 is sorbitan monooleate available from
  • Dabco 33 LV is a tertiary amine catalyst available from Air Products and Chemicals Inc .
  • Niax A-I is a tertiary amine catalyst available from GE Specialties .
  • Niax A-300 is a (delayed action) tertiary amine catalyst . available from GE Specialties,
  • SPECFLEX NC 632 is a 1,700 EW polyoxypropylene polyoxyethylene polyol initiated with a blend of glycerol and sorbitol available from The Dow Chemical Company.
  • Voranol CP 4702 is a PO/EO triol with an OH number of 35 available from The Dow Chemical Company.
  • Polyol A is a 1,700 equivalent weight propoxylated tetrol initiated with 3,3'- diamino-N-methyl-dipropylamine and capped with 20 % ethylene oxide.
  • Polyol B is the reaction product of D. E. R. 732 epoxy resin, available from The Dow Chemical Company, salicylaldehyde, and 3- (N,N-dimethylamino)propylamine, as described in WO 05/063840
  • SPECFLEX NC-700 is a 40 percent SAN based copolymer pblyol with an average hydroxyl number of 20 available from The Dow Chemical Company.
  • VORANATE T-80 is TDI 80/20 (2,4-/2,6- isomers) isocyanate available from The Dow Chemical Company.
  • NOBP A Soybean oil based polyol prepared according to examples 19-22 of WO 2004/096882 having an OH number of 88 and a viscosity at 25 deg C of 1,900 mPa. s
  • foams are made in the laboratory by preblending polyols and other additives such as emulsifiers, surfactants, crosslinkers, catalysts and water, conditioned at 25°C.
  • the isocyanate is also conditioned at 25°C.
  • Bench made foam is made by hand-mixing and machine made foam is produced using a high pressure impingement mix-head equipped KM-40 from Krauss- Maffei. At demold, the foam is crushed to avoid shrinkage.
  • Free rise reactivity and density are recorded by pouring the reacta ⁇ ts in a bucket and letting the foam rise without any constraint. Molded parts are produced in a 300 x 300 x 100 mm aluminum mold heated at 60 0 C for bench foam and a 400 x 400 x 115 mm mold for machine made foams. All molds are equipped with vent holes. Release agent is Kluber 41-2013, available from Chem-Trend, is used to coat the mold prior to pouring the reactants. Foam properties are measured according to ASTM D 3574-83 test methods, unless otherwise indicated.
  • molded flexible HR foam having high airflow and low compression sets values are produced using the formulations in Table 1.
  • the foams are produced by hand-mixing.
  • a cell regulating surfactant is combined with NOBP, while comparative Example 1C uses a cell stabilizing surfactant.
  • the properties of the produced foams are also given in Table 1.
  • 4C is a comparative example, not part of th s nvent on.
  • HACS Humid Aged Compression Set.
  • Wet compression set (with skin) is measured according to Renault RP 1637 test method. These data show foam produced with NOBP A and a cell regulating surfactant have compression sets (dry, wet and after humid aging) comparable to a conventional HR molded system currently used by the industry. Comparative Example 2C and Example 4
  • Molded foams are produced by hand-mixing, using the formulations given in Table 2 where the NOBP is fifty percent of the polyol component.
  • Comparative Example 2C contains a Dabco DC 5169, a cell-stabilizing silicones-based surfactant and Example 4 contains Tegostab B8715 LF, a cell regulating additive.
  • Example 2C produces a sponge foam with large cells across the entire pad. Such a foam is generally unsuitable for automotive seating. Utilizing a cell regulating additive as per Example 4, gives a good foam with small, irregular cells typical of HR foam, and the foam has no visible surface defects.
  • Molded foams are made with a formulation containing 40 PPHP of NOBP as given in Table 5.
  • the properties of the foams are also given in Table 5.
  • the results show when a cell regulating surfactant is used in the formulation (Example 7) , foams with proper physical characteristics, especially compression sets, are obtained. Without the addition of a cell regulating surfactant (4C) foam is overstabilized by the high level of NOBP (40 PHP) and compression sets suffer. In addition, the bottom surface of the part is improved by the addition of the cell regulating additive.
  • Example 4C is a comparat ve example, not part of th s nvent on Examples 8 and 9
  • the bottom surface shows a layer of 1 mm sized, large cells.
  • Two molded foams are produced using 40 PPHP of NOBP A and two different catalyst compositions.
  • the formulations are given in Table 2.
  • a molded foam with acceptable properties is produced when using as the polyisocyanate component, a blend of 80 % TDI 80/20 and 20 % Voranate M-229, a polymeric MDI, with the following polyol composition given in Table 8.
  • the demold time is 6 minutes and the foam has a density of 37.4 kg/m 3 and an airflow of 4.5 cfm.

Abstract

La présente invention concerne des polyols à base d'huile naturelle et leur utilisation dans la production en une phase de mousse de polyuréthane de basse densité flexible à base de diisocyanate de toluène (DIT). Les mousses sont produites à partir de formulations dans lesquelles le polyol à base d'huile naturelle comprend au moins 20 pour cent en poids du composant polyol et les mousses sont produites en l'absence d'un agent tensioactif de stabilisation de cellules à base de silicone.
PCT/US2007/006187 2006-03-23 2007-03-09 Mousse de polyurethane de basse densite a base d'huile naturelle sans additif de stabilisation de cellules a base de silicone WO2007111828A2 (fr)

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