US20030083394A1 - Polyurethane foams having improved heat sag and a process for their production - Google Patents

Polyurethane foams having improved heat sag and a process for their production Download PDF

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US20030083394A1
US20030083394A1 US09/876,778 US87677801A US2003083394A1 US 20030083394 A1 US20030083394 A1 US 20030083394A1 US 87677801 A US87677801 A US 87677801A US 2003083394 A1 US2003083394 A1 US 2003083394A1
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isocyanate
reactive component
weight
rigid
closed
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Jan Clatty
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Covestro LLC
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Priority to US09/876,778 priority Critical patent/US20030083394A1/en
Application filed by Individual filed Critical Individual
Priority to EP02011575A priority patent/EP1264850B1/en
Priority to AT02011575T priority patent/ATE373684T1/de
Priority to ES02011575T priority patent/ES2294064T3/es
Priority to DK02011575T priority patent/DK1264850T3/da
Priority to DE60222496T priority patent/DE60222496T2/de
Priority to CA2388585A priority patent/CA2388585C/en
Priority to IL14998302A priority patent/IL149983A0/xx
Priority to NZ519353A priority patent/NZ519353A/en
Priority to BR0202107-2A priority patent/BR0202107A/pt
Priority to KR1020020031565A priority patent/KR20020093586A/ko
Priority to JP2002165615A priority patent/JP2003026757A/ja
Priority to RU2002114915/04A priority patent/RU2002114915A/ru
Priority to CN02121817A priority patent/CN1390869A/zh
Priority to HU0201931A priority patent/HUP0201931A3/hu
Priority to AU45833/02A priority patent/AU4583302A/en
Priority to US10/336,111 priority patent/US6649667B2/en
Publication of US20030083394A1 publication Critical patent/US20030083394A1/en
Assigned to BAYER POLYMERS LLC reassignment BAYER POLYMERS LLC MASTER ASSIGNMENT OF PATENTS AGREEMENT AND ADDENDUM Assignors: BAYER CORPORATION
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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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • 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
    • C08G18/48—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • 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
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to polyurethane foams having a closed cell content of at least 90% and improved heat sag properties produced by reaction injection molding (“RIM”) and to a process for the production of such foams.
  • RIM reaction injection molding
  • an organic diisocyanate or polyisocyanate is reacted with an isocyanate-reactive component that includes at least one (generally more than one) polyol, a catalyst, a cross-linking agent and other processing aids.
  • the polyols used are those which are typically derived from sources such as sucrose, amines, glycerine, ethylene glycol, etc. Many of these starting materials are derived from increasingly expensive petrochemicals. It would therefore be advantageous to substitute some or all of these polyols with polyols derived from less expensive starting materials.
  • U.S. Pat. No. 2,787,601 discloses cellular, flexible polyurethanes made with hydroxyl-group containing fatty acid glycerides. More specifically, a simple (i.e., unmodified) and untreated hydroxyl-group containing fatty acid glyceride such as castor oil is reacted with an aromatic diisocyanate to form an isocyanate-terminated prepolymer. This prepolymer is then reacted with water to form a cellular foam having reported apparent densities of from 2.8 to 6.5 pounds per cubic foot.
  • U.S. Pat. No. 2,833,730 also discloses cellular polyurethanes produced from a polyol based on a fatty acid triglyceride which reportedly do not have the shrinkage problems encountered with similar, prior art polyurethanes made from such polyols. More specifically, a mixture of a low molecular weight polyhydroxyl compound and a hydroxyl group-containing triglyceride (unmodified and untreated) is reacted with an aromatic diisocyanate to form an isocyanate-terminated prepolymer. This prepolymer is then reacted with water to form the desired polyurethane product.
  • the ratio of the low molecular weight polyhydroxyl compound to the hydroxyl-group containing triglyceride should be at least 0.6 to 1 in order to obtain a polyurethane having the improved shrinkage property.
  • Unmodified vegetable oils have not, however, been used as a major reaction component to produce rigid polyurethane foams by a RIM process.
  • U.S. Pat. No. 5,482,980 discloses a process for the production of flexible open-celled, urethane foams in which epoxidized soybean oil is included in the polyether polyol reaction component.
  • Epoxidized vegetable oils have also been used in relatively minor amounts in polyurethane-forming reaction mixtures as emulsifiers. See, e.g., U.S. Pat. No. 5,750,583.
  • Such chemically modified oils have not, however, been used as a significant portion of the polyol component used to produce rigid, closed-cell polyurethane foams because at higher levels these types of materials would be expected to function in the same manner as internal mold release agents and increase the potential for de-lamination when molding composite articles.
  • modified vegetable oils is also commercially disadvantageous due to the energy, materials and time required for epoxidation and any subsequent conversion, e.g., to a polyester polyol.
  • urethane foams and elastomers are produced by reacting an isocyanate with a vegetable oil which has been treated by passing air through the oil to remove impurities and thicken the oil (referred to as “blown oil”) in the presence of a multi-functional alcohol crosslinking agent such as butanediol or ethylene glycol.
  • blown oil is used as the sole isocyanate-reactive component.
  • No petroleum-based polyester or polyether polyol is included. Rigid, closed-celled polyurethane foams are not, however, taught to be producible with the disclosed blown vegetable oils.
  • a blown bio-based oil also referred to herein as a “bio-based polyol” or “blown vegetable oil” or a “polymerized vegetable oil”
  • soybean oil in an isocyanate-reactive component to be used in a RIM process.
  • FIG. 1 is a graph on which Tan Delta (E′/E′′) is plotted vs Temperature for molded articles having a density of 45 pounds per cubic foot or 35 pounds per cubic foot made from systems containing 20% by weight blown soybean oil and systems made without blown soybean oil.
  • FIG. 2 is a graph on which the derivative of the % penetration of a probe is plotted against temperature for molded articles produced in accordance with each of Examples 31, 35 and 39.
  • FIG. 3 is a graph on which the derivative of the % penetration of a probe is plotted against temperature for molded articles produced in accordance with each of Examples 32, 36 and 40.
  • FIG. 4 is a graph on which the derivative of the % penetration of a probe is plotted against temperature for molded articles produced in accordance with each of Examples 33, 37 and 41.
  • FIG. 5 is a graph on which the derivative of the % penetration of a probe is plotted against temperature for molded articles produced in accordance with each of Examples 34, 38 and 42.
  • FIG. 6 is a graph on which the % penetration of a probe is plotted against time for molded articles produced in accordance with each of Examples 32, 36 and 40 at a constant temperature.
  • the present invention relates to a RIM process for the production of rigid, closed-cell polyurethane foams and particularly to the use of an isocyanate-reactive component in which up to 30% by weight is a blown bio-based oil such as soybean oil.
  • the invention also relates to the rigid, closed cell polyurethane foams produced by this process.
  • a key feature of the present invention is the use of a blown vegetable oil in the isocyanate-reactive component in an amount of from about 0.5 to 30% by weight, preferably from about 5 to 25% by weight, most preferably from about 10 to 20% by weight, based on total weight of isocyanate-reactive component.
  • a blown vegetable oil in the isocyanate-reactive component in an amount of from about 0.5 to 30% by weight, preferably from about 5 to 25% by weight, most preferably from about 10 to 20% by weight, based on total weight of isocyanate-reactive component.
  • suitable bio-based oils which may be used in the present invention after being blown include: vegetable oils such as soybean oil, rapeseed or canola oil, peanut oil, cottonseed oil, olive oil, grapeseed oil, coconut oil, palm oil, linseed oil, and castor oil; fish oils and oils derived from animal fats. Soybean oil and castor oil are preferred. Soybean oil is particularly preferred. Such blown oils are described in U.S. Pat. No. 6,180,686 and are commercially available from Urethane Soy Systems under the names SoyOyl P38.GC5 bio-based polyol and SoyOyl P38-05 bio-based polyol and SoyOyl P56.05 bio-based polyol.
  • vegetable oils such as soybean oil, rapeseed or canola oil, peanut oil, cottonseed oil, olive oil, grapeseed oil, coconut oil, palm oil, linseed oil, and castor oil
  • fish oils and oils derived from animal fats So
  • the other constituents of the isocyanate-reactive component useful in combination with the required blown vegetable oil include any of the known isocyanate-reactive materials, chain extenders, cross-linking agents, catalysts, foaming agents, additives and processing aids commonly used in RIM processes.
  • Suitable isocyanate-reactive compounds useful in combination with the required blown vegetable oil include compounds having a number average molecular weight of from 400 to about 10,000, preferably from about 470 to about 8,000, most preferably from about 1,000 to about 6,000 and contain amino groups, hydroxyl groups, thiol groups, or a combination thereof. These isocyanate-reactive compounds generally contain from about 1 to about 8 isocyanate-reactive groups, preferably from about 2 to about 6 isocyanate-reactive groups. Suitable such compounds include polyethers, polyesters, polyacetals, polycarbonates, polyesterethers, polyester carbonates, polythioethers, polyamides, polyesteramides, polysiloxanes, polybutadienes, and polyacetones. Particularly preferred isocyanate-reactive compounds contain 2 to 4 reactive amino or hydroxyl groups.
  • isocyanate-reactive compounds are generally included in the isocyanate-reactive component in an amount of from about 5 to about 80% by weight (based on total weight of isocyanate-reactive component), preferably from about 5 to about 60% by weight, most preferably from about 10 to about 50% by weight.
  • Suitable hydroxyl-containing polyethers are known and commercially available.
  • Such polyether polyols can be prepared, for example, by the polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin, optionally in the presence of BF 3 , or by chemical addition of such epoxides, optionally as mixtures or successively, to starting components containing reactive hydrogen atoms, such as water, alcohols, or amines.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin
  • starting components include ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3-, or 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol, 4,4′-dihydroxydiphenylpropane, aniline, 2,4- or 2,6-diaminotoluene, ammonia, ethanolamine, triethanolamine, or ethylene diamine.
  • Sucrose polyethers may also be used. Polyethers that contain predominantly primary hydroxyl groups (up to about 90% by weight, based on all of the hydroxyl groups in the polyether) are preferred.
  • Polyethers modified by vinyl polymers of the kind obtained, for example, by the polymerization of styrene and acrylonitrile in the presence of polyethers are also suitable, as are polybutadienes containing hydroxyl groups.
  • Particularly preferred polyethers include polyoxyalkylene polyether polyols, such as polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, and polytetramethylene diol.
  • Hydroxyl-containing polyesters are also suitable for use in the isocyanate-reactive component.
  • Suitable hydroxyl-containing polyesters include reaction products of polyhydric alcohols (preferably diols), optionally with the addition of trihydric alcohols, and polybasic (preferably dibasic) carboxylic acids.
  • polyhydric alcohols preferably diols
  • polybasic preferably dibasic carboxylic acids.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof may be used for preparing the polyesters.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic, or heterocyclic and may be substituted, e.g., by halogen atoms, and/or unsaturated.
  • Suitable polycarboxylic acids include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, maleic acid, maleic acid anhydride, fumaric acid, dimeric and trimeric fatty acids, dimethyl terephthalic, and terephthalic acid bis-glycol esters.
  • Suitable polyhydric alcohols include ethylene glycol, 1,2- and 1,3-propanediol, 1,4- and 2,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,3- and 1,4-bis(hydroxy-methyl)cyclohexane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, pentaerythritol, quinnitol, mannitol, sorbitol, methyl glycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol, and poly-butylene glycols.
  • polyesters may also contain a proportion of carboxyl end groups.
  • Polyesters of lactones, such as F-caprolactone, or of hydroxycarboxylic acids, such as co-hydroxycaproic acid may also be used.
  • Hydrolytically stable polyesters are preferably used in order to obtain the greatest benefit relative to the hydrolytic stability of the final product.
  • Preferred polyesters include polyesters obtained from adipic acid or isophthalic acid and straight chained or branched diols, as well as lactone polyesters, preferably those based on caprolactone and diols.
  • Suitable polyacetals include compounds obtained from the condensation of glycols, such as diethylene glycol, triethylene glycol, 4,4′-dihydroxydiphenylmethane, and hexanediol, with formaldehyde or by the polymerization of cyclic acetals, such as trioxane.
  • Suitable polycarbonates include those prepared by the reaction of diols, such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, or thiodiglycol, with phosgene or diaryl carbonates such as diphenyl carbonate.
  • diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, or thiodiglycol
  • phosgene or diaryl carbonates such as diphenyl carbonate.
  • Suitable polyester carbonates include those prepared by the reaction of polyester diols, with or without other diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, or thiodiglycol, with phosgene, cyclic carbonates, or diaryl carbonates such as diphenyl carbonate.
  • Suitable polyester carbonates more generally include compounds such as those disclosed in U.S. Pat. No. 4,430,484.
  • Suitable polythioethers include the condensation products obtained by the reaction of thiodiglycol, either alone or with other glycols, formaldehyde, or amino alcohols.
  • the products obtained are polythio-mixed ethers, polythioether esters, or polythioether ester amides, depending on the components used.
  • Suitable polyester amides and polyamides include, for example, the predominantly linear condensates prepared from polybasic saturated and unsaturated carboxylic acids or the anhydrides thereof and polyvalent saturated or unsaturated amino alcohols, diamines, polyamines, and mixtures thereof.
  • hydroxyl-containing compounds include polyhydroxyl compounds already containing urethane or urea groups. Products of addition of alkylene oxides to phenol-formaldehyde resins or to urea-formaldehyde resins are also suitable.
  • Polyhydroxyl compounds in which polyadducts or polycondensates or polymers are present in a finely dispersed or dissolved form may also be used according to the invention, provided that the molecular weights range from about 400 to about 10,000.
  • Polyhydroxyl compounds of this type may be obtained, for example, by carrying out polyaddition reactions (e.g., reactions between polyisocyanates and amino functional compounds) or polycondensation reactions (e.g., between formaldehyde and phenols or amines) in situ in the above-mentioned hydroxyl-containing compounds.
  • Suitable compounds may also be obtained according to U.S. Pat. Nos. 3,869,413 or 2,550,860 by mixing a previously prepared aqueous polymer dispersion with a polyhydroxyl compound and then removing water from the mixture.
  • Polyhydroxyl compounds modified with vinyl polymers such as those obtained, for example, by the polymerization of styrene and acrylonitrile in the presence of polycarbonate polyols (U.S. Pat. No. 3,637,909) are also suitable for the process of the invention.
  • Suitable isocyanate-reactive compounds containing amino groups include the so-called amine-terminated polyethers containing primary or secondary (preferably primary) aromatically or aliphatically (preferably aliphatically) bound amino groups. Compounds containing amino end groups can also be attached to the polyether chain through urethane or ester groups.
  • amine-terminated polyethers can be prepared by any of several methods known in the art. For example, amine-terminated polyethers can be prepared from polyhydroxyl polyethers (e.g., polypropylene glycol ethers) by a reaction with ammonia in the presence of Raney nickel and hydrogen.
  • Polyoxyalkylene polyamines can be prepared by a reaction of the corresponding polyol with ammonia and hydrogen in the presence of a nickel, copper, chromium catalyst.
  • Polyethers containing amino end groups may be prepared by hydrogenation of cyanoethylated polyoxypropylene ethers.
  • Relatively high molecular weight polyhydroxy-polyethers suitable for the present invention may be converted into the corresponding anthranilic acid esters by reaction with isatoic acid anhydride.
  • Relatively high molecular weight compounds containing amino end groups may also be obtained by reacting isocyanate prepolymers based on polyhydroxyl polyethers with hydroxyl-containing enamines, aldimines, or ketimines and hydrolyzing the reaction product.
  • Aminopolyethers obtained by the hydrolysis of compounds containing isocyanate end groups are also preferred amine-terminated polyethers.
  • Preferred amine-terminated polyethers are prepared by hydrolyzing an isocyanate compound having an isocyanate group content of from 0.5 to 40% by weight.
  • the most preferred polyethers are prepared by first reacting a polyether containing two to four hydroxyl groups with an excess of an aromatic polyisocyanate to form an isocyanate terminated prepolymer and then converting the isocyanate groups to amino groups by hydrolysis.
  • Amine-terminated polyethers useful in the present invention are in many cases mixtures with other isocyanate-reactive compounds having the appropriate molecular weight. These mixtures generally should contain (on a statistical average) two to four isocyanate reactive amino end groups.
  • Suitable crosslinking agents or chain extenders which may be included in the isocyanate-reactive component of the present invention generally have a molecular weight of less than 399 and a functionality of from about 2 to about 6 (preferably 2 to 4). Chain extenders generally have a functionality of about 2 and crosslinkers generally have a functionality greater than 2. Such compounds typically contain hydroxyl groups, amino groups, thiol groups, or a combination thereof, and generally contain 2 to 8 (preferably 2 to 4) isocyanate-reactive hydrogen atoms.
  • the chain extender and/or cross-linking agent is generally included in the isocyanate-reactive component in an amount of from about 1 to about 75% by weight, based on total weight of isocyanate-reactive component, preferably, from about 10 to about 65% by weight, most preferably from about 15 to about 55% by weight.
  • the preferred hydroxyl-containing chain extenders and crosslinkers include glycols and polyols, such as 1,2-ethanediol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, cyclohexane-dimethanol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, glycerol, trimethylol-propane, 1,2,6-hexanetriol, pentaerythritol, 1,2,4-butanetriol, and trimethylolethane.
  • glycols and polyols such as 1,2-ethanediol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,6-hexanediol, 1,8-octan
  • Suitable chain extenders also include hydroxyl-containing polyethers having a molecular weight of less than 399.
  • Suitable hydroxyl-containing polyethers can be prepared, for example, by the methods discussed above for the higher molecular weight hydroxy-containing polyethers except that only lower molecular weight polyethers are used.
  • Glycerol which has been propoxylated and/or ethoxylated to produce a polyol having a molecular weight of less than 399 is an example.
  • Particularly suitable polyethers include polyoxyalkylene polyether polyols, such as polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, and polytetramethylene diol having the requisite molecular weights.
  • Amine chain extenders preferably contain exclusively aromatically bound primary or secondary (preferably primary) amino groups and preferably also contain alkyl substituents.
  • aromatic diamines include 1,4-diaminobenzene, 2,4- and/or 2,6-diaminotoluene, meta-xylene diamine, 2,4′- and/or 4,4′-diamino-diphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 1-methyl-3,5-bis(methylthio)-2,4- and/or -2,6-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4- and/or -2,6-diaminobenzene, 4,6-dimethyl-2-ethyl
  • cyclo cyclo-aliphatic diamines
  • a particularly suitable (cyclo)-aliphatic diamine is 1,3-bis(aminomethyl)cyclohexane. Such diamines may, of course, also be used as mixtures.
  • Suitable tertiary amine or ammonium compounds useful in the isocyanate-reactive component of the present invention include isocyanate-reactive tertiary amine polyethers, fatty amido-amines, ammonium derivatives of fatty amido-amines and mixtures thereof.
  • Suitable catalysts include tertiary amines and metal compounds known in the art.
  • Suitable tertiary amine catalysts include triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N′,N′-tetramethylethylene diamine, pentamethyldiethylene triamine, and higher homologs, 1,4-diazabicyclo[2.2.2]octane, N-methyl-N′-(dimethylamino-ethyl)piperazine, bis(dimethylaminoalkyl)piperazines, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl) adipate, N,N,N′,N′-tetramethyl-1,3-butanediamine, N,N-dimethyl-p
  • the catalysts used may also be the known Mannich bases of secondary amines (such as dimethylamine) and aldehydes (preferably formaldehyde) or ketones (such as acetone) and phenols.
  • Suitable catalysts also include certain tertiary amines containing isocyanate reactive hydrogen atoms.
  • examples of such catalysts include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, their reaction products with alkylene oxides (such as propylene oxide and/or ethylene oxide) and secondary-tertiary amines.
  • Other suitable catalysts include organic metal compounds, especially organic tin, bismuth, and zinc compounds.
  • Suitable organic tin compounds include those containing sulfur, such as dioctyl tin mercaptide and, preferably, tin(II) salts of carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate, and tin(II) laurate, as well as tin(IV) compounds, such as dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, dibutytin maleate, and dioctyltin diacetate.
  • sulfur such as dioctyl tin mercaptide and, preferably, tin(II) salts of carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate, and
  • Suitable bismuth compounds include bismuth neodecanoate, bismuth versalate, and various bismuth carboxylates known in the art.
  • Suitable zinc compounds include zinc neodecanoate and zinc versalate.
  • Mixed metal salts containing more than one metal are also suitable catalysts.
  • the catalyst is generally included in the isocyanate-reactive component in an amount of from about 0.01 to about 7% by weight, based on total weight of isocyanate-reactive component, preferably from about 0.5 to about 6% by weight, most preferably from about 1 to about 5% by weight.
  • Suitable blowing agents for use in the preparation of polyurethane foams include water and/or readily volatile organic substances.
  • Organic blowing agents include acetone, ethyl acetate, methanol, ethanol, low-boiling hydrocarbons (such as butane, hexane, or heptane) or fluorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, or other halogen-substituted alkanes (such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloro-methane, chlorodifluoromethane, and dichlorodifluoromethane), diethyl ether, or carboxylic acids (such as lactic acid, citric acid, and malonic acid), as well as carbon dioxide generated by the hydrolysis of isocyanate groups.
  • a blowing effect may also be obtained by adding compounds which decompose at temperatures above room
  • the blowing agent is generally included in the isocyanate-reactive component in an amount of from about 0.05 to about 7% by weight, based on total weight of isocyanate-reactive component, preferably from about 0.1 to about 6% by weight, most preferably from about 0.5 to about 5% by weight.
  • additives which may optionally be included in the isocyanate-reactive component of the invention and include, for example, flame retardants, internal mold release agents, surfactants, acid scavengers, water scavengers, cell regulators, pigments, dyes, UV stabilizers, plasticizers, fungistatic or bacteriostatic substances, and fillers.
  • Suitable flame retardants include phosphonates, phosphites, and phosphates (such as dimethyl methylphosphonate, ammonium polyphosphate, and various cyclic phosphate and phosphonate esters known in the art); halogen-containing compounds known in the art (such as brominated diphenyl ether and other brominated aromatic compounds); melamine; antimony oxides (such as antimony pentoxide and antimony trioxide); zinc compounds (such as various known zinc borates); aluminum compounds (such as alumina trihydrate); and magnesium compounds (such as magnesium hydroxide).
  • phosphonates such as dimethyl methylphosphonate, ammonium polyphosphate, and various cyclic phosphate and phosphonate esters known in the art
  • halogen-containing compounds such as brominated diphenyl ether and other brominated aromatic compounds
  • melamine antimony oxides (such as antimony pentoxide and antimony trioxide)
  • zinc compounds such as various known zinc borates
  • Internal mold release agents are compounds that are added to the reactive components of the isocyanate addition reaction, usually the isocyanate-reactive component, to assist in the removal of a polyurethane product from a mold.
  • Suitable internal mold release agents for the present invention include those based at least in part on fatty acid esters (e.g., U.S. Pat. Nos. 3,726,952, 3,925,527, 4,058,492, 4,098,731, 4,201,847, 4,254,228, 4,868,224, and 4,954,537); metal and/or amine salts of carboxylic acids, amido carboxylic acids, phosphorus-containing acids, or boron-containing acids (e.g., U.S. Pat. Nos.
  • polysiloxanes e.g., U.S. Pat. No. 4,504,313
  • amidines e.g., U.S. Pat. Nos. 4,764,540, 4,789,688, and 4,847,307
  • resins prepared by the reaction of isocyanate prepolymers and a polyamine-polyamine component e.g., U.S. Pat. No. 5,198,508
  • Surfactants include emulsifiers and foam stabilizers.
  • suitable surfactants include any of several silicone surfactants known in the art (including, for example, those available commercially from Dow Corning Corporation, Union Carbide Chemical and Plastics Co., Inc., and Rhein Chemie Corporation), as well as various amine salts of fatty acids (such as diethyl-amine oleate or diethanolamine stearate) and sodium salts of ricinoleic acids.
  • Acid scavengers are compounds that control the acidity and water concentration of the compositions of the invention.
  • Preferred acid scavengers include various orthoesters (such as trimethyl orthoformate), carbodiimides (such as 2,2′,6,6′-tetraisopropyidiphenylcarbodiimide, available as STABOXAL I and STABOXAL P from Rhein Chemie Corp.), and epoxides (such as 3,4-epoxycyclohexylmethyl 3,4-epoxy-cyclohexylcarboxylate, available as ERL-4221 from Union Carbide).
  • orthoesters such as trimethyl orthoformate
  • carbodiimides such as 2,2′,6,6′-tetraisopropyidiphenylcarbodiimide, available as STABOXAL I and STABOXAL P from Rhein Chemie Corp.
  • epoxides such as 3,4-epoxycyclohexylmethyl 3,4-
  • Water scavengers are compounds that maintain a low water content in the compositions of the invention. Suitable water scavengers are described, for example, in U.S. Pat. Nos. 3,755,222 and 4,695,618. Examples of suitable water scavengers include alkali aluminosilicates (available as BAYLITH L, BAYLITH T, and BAYLITH W powders or pastes from Bayer AG, Germany) and chemically reacting water scavengers (such as ZOLDINE MS-Plus from Angus Chemical Company).
  • alkali aluminosilicates available as BAYLITH L, BAYLITH T, and BAYLITH W powders or pastes from Bayer AG, Germany
  • chemically reacting water scavengers such as ZOLDINE MS-Plus from Angus Chemical Company.
  • Known fillers and/or reinforcing substances such as barium sulfate, calcium carbonate, calcium silicate, clays, kieselguhr, whiting, mica, and especially glass fibers, liquid crystal fibers, glass flakes, glass balls, microspheres, aramide fibers, and carbon fibers, are also suitable.
  • the storage-stable isocyanate-reactive compositions of the present invention can be prepared by mixing the individual components in any order but are preferably prepared by combining the base polyols first and subsequently adding any catalyst, blowing agent, filler, etc. to the polyol mixture.
  • the isocyanate-reactive compositions of the present invention can be used for the preparation of various urethane-based products by reaction injection molding (“RIM”).
  • RIM reaction injection molding
  • polyurethane also refers to polyureas and polyurethane polyurea hybrids.
  • the isocyanate-reactive component is allowed to react with an organic polyisocyanate.
  • Suitable polyisocyanates are known in the art. Suitable polyisocyanates can be unmodified isocyanates, modified polyisocyanates, or isocyanate prepolymers.
  • Suitable organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. Examples of such isocyanates include those represented by the formula
  • n is a number from 2 to about 5 (preferably 2 to 3) and Q is an aliphatic hydrocarbon group containing 2 to about 18 (preferably 6 to 10) carbon atoms, a cycloaliphatic hydrocarbon group containing 4 to about 15 (preferably 5 to 10) carbon atoms, an araliphatic hydrocarbon group containing 8 to 15 (preferably 8 to 13) carbon atoms, or an aromatic hydro-carbon group containing 6 to about 15 (preferably 6 to 13) carbon atoms.
  • Suitable isocyanates include ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1,6- hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and -1,4-diisocyanate, and mixtures of these isomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (“isophorone diisocyanate”); 2,4- and 2,6-hexahydrotoluene diisocyanate and mixtures of these isomers; dicyclohexylmethane-4,4′-diisocyanate (“hydrogenated MDI”, or “HMDI”); 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers
  • isocyanate-containing distillation residues accumulating in the production of isocyanates on a commercial scale, optionally in solution in one or more of the polyisocyanates mentioned above. It is also possible to use mixtures of the polyisocyanates described above.
  • polyisocyanates such as 2,4- and 2,6-toluene diisocyanates and mixtures of these isomers (“TDI”); polyphenyl-polymethylene-polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation (“crude MDI”); and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, or biuret groups (“modified polyisocyanates”).
  • TDI 2,4- and 2,6-toluene diisocyanates and mixtures of these isomers
  • CAMDI polyphenyl-polymethylene-polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation
  • isocyanate prepolymers prepared by reaction of any of the above polyisocyanates with a sub-stoichiometric amount of an isocyanate-reactive compound are also possible.
  • Machines useful for conducting the RIM process of the present invention are known to those skilled in the art and are commercially available from Hennecke, Krauss-Maffei Corporation and Cannon, Inc.
  • the quantity of isocyanate component should preferably be such that the isocyanate index is from 80 to 130, preferably from 90 to 120, most preferably from 100 to 120.
  • isocyanate index is meant the quotient of the number of isocyanate groups divided by the number of isocyanate-reactive groups, multiplied by 100.
  • Molded foams prepared using the compositions of the present invention are prepared by a RIM process.
  • RIM processes generally two separate streams are intimately mixed and subsequently into a suitable mold.
  • the first stream is generally the isocyanate component and the second stream is typically the isocyanate-reactive component.
  • the catalyst, blowing agent and other additives are typically included in the isocyanate-reactive component. More than two streams may, however, be used in such processes.
  • Suitable mold materials include metals (for example, aluminum or steel) or plastics (for example, unsaturated polyester resin or epoxide resin). In the mold, the foamable reaction mixture foams to form the molded product.
  • preferred isocyanate-reactive compositions of the invention include: (1) from 0.5 to 30% by weight (more preferably from 5 to 25% by weight, most preferably from 10 to 20% by weight) of blown bio-based oil; (2) from 5 to 80% by weight (more preferably from 5 to 60% by weight) of a polyether polyol having a molecular weight of at least 400; (3) from 1 to 75% by weight (more preferably from 10 to 65% by weight) of chain extender or crosslinker; (4) from 0.05 to 7% by weight (more preferably from 0.1 to 6% by weight) of blowing agent; and (5) from 0.01 to 7% by weight (more preferably from 0.5 to 6% by weight) of catalyst, all amounts being based on the total amount of materials present in the isocyanate-reactive component.
  • Other, optional additives, if included, are generally used in an amount of from 1 to 30% by weight, based on total weight
  • the polyurethane foams produced in accordance with the present invention are rigid foams having a closed cell content of at least 90%, preferably at least 95%, most preferably approximately 100%. These rigid foams have densities of from 8 to 55 lbs/ft 3 , preferably from 15 to 55, most preferably from 25 to 45. These foams have a Shore D hardness of at least 40, preferably from 50-75.
  • the heat sag values for foams made in accordance with the present invention are at least slightly better than for foams made with the traditional polyether polyols, but generally are substantially better than the heat sag values for the traditional foams made with polyether polyols only.
  • the heat distortion temperature for foams made in accordance with the present invention are at least high, but generally higher, than those for foams made with traditional polyether polyols only.
  • the other physical properties of the foams made in accordance with the present invention are comparable to those of rigid foams produced with traditional polyether polyols only.
  • POLYOL A a polymerized soybean oil having a hydroxyl functionality of 1.8, a hydroxyl number of 51.8 and an equivalent weight of 1100 which is commercially available under the name SoyOyl P38.05 (low odor) from Urethane Soy Systems Co., Inc.
  • POLYOL B a polymerized soybean oil having a hydroxyl functionality of 3, a hydroxyl number of 174 and an equivalent weight of 322 which is commercially available under the name SoyOyl P38.GC5 from Urethane Soy Systems Co., Inc.
  • POLYOL C a polymerized soybean oil having a hydroxyl functionality of 3.4, a hydroxyl number of 65.8 and an equivalent weight of 850 which is commercially available under the name SoyOyl P56.05 from Urethane Soy Systems Co., Inc.
  • POLYOL D glycerol-started polyether of propylene oxide and ethylene oxide (83 wt. % propylene oxide and 17 wt. % ethylene oxide) having a hydroxyl number of 28 and a functionality of 3.
  • POLYOL E PE
  • Glycerol-started polyether of propylene oxide having a functionality of 3 and a hydroxyl number of 1050 (molecular weight about 160)
  • CATALYST A (CA) N,N-dimethylcyclohexylamine (available as POLYCAT 8 from Air Products & Chemicals, Inc.)
  • CATALYST B Glycol acid salt of tetraethylenediamine and 1,1-dibutyltin diacetate (available as DABCO DC-2 from Air Products & Chemicals, Inc.)
  • PU-1748 A quaternary ammonium salt of the amide of tall oil and N,N′ dimethyl-1,3-diamine propane.
  • ISOCYANATE A polymeric diphenylmethane diisocyanate having an NCO content of 31.5% by weight which is commercially available from Bayer Corporation under the name Mondur MR.
  • ISOCYANATE B (IB) modified diphenylmethane diisocyanate having an NCO content of 27% by weight which is commercially available from Bayer Corporation under the name Mondur 486.
  • IZU Izod, unnotched Determined in accordance with ASTM D 256 (reported in ft-lb/in)
  • An isocyanate-reactive component composed of the materials listed in Table 5 in the amounts indicated in parts by weight in Table 5 was prepared. The isocyanate-reactive component was then reacted with ISOCYANATE A in an amount such that the Isocyanate Index was 110 using a Cannon HE-120 RIM machine. The reaction mixture was introduced into an aluminum plaque mold. The properties of the molded article are reported in Table 6.
  • TMA analysis was also conducted on each of the plaques produced in Examples 19-30 using a Perkin Elmer TMA7 in the penetration mode.
  • the plaques were heated to temperatures of from ⁇ 50° C. to 250° C. at 5° C. per minute. Liquid nitrogen was used as the coolant and helium gas was used as the purge. The force on the probe was 500 mN.
  • Table 8 The results are this analysis are given in Table 8 below and are graphically presented in FIG. 2 (plaques from Examples 31, 35 and 39), 3 (plaques from Examples 32, 36 and 40), 4 (plaques from Examples 33, 37 and 41) and 5 (plaques from Examples 34, 38 and 42).

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US09/876,778 US20030083394A1 (en) 2001-06-07 2001-06-07 Polyurethane foams having improved heat sag and a process for their production
EP02011575A EP1264850B1 (en) 2001-06-07 2002-05-27 Polyurethane foams having improved heat sag and a process for their production
AT02011575T ATE373684T1 (de) 2001-06-07 2002-05-27 Polyurethanschäume mit verbesserten heissbiegewiderstandseigenschaften und verfahren zu ihrer herstellung
ES02011575T ES2294064T3 (es) 2001-06-07 2002-05-27 Espumas de poliuretano que presentan una deformacion termica mejorada y un procedimiento para su produccion.
DK02011575T DK1264850T3 (da) 2001-06-07 2002-05-27 Polyurethanskum med forbedret varmböjningsstyrke og en fremgangsmåde til fremstilling deraf
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CA2388585A CA2388585C (en) 2001-06-07 2002-05-31 Polyurethane foams having improved heat sag and a process for their production
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BR0202107-2A BR0202107A (pt) 2001-06-07 2002-06-05 Espumas de poliuretano que têm arqueamento pelo calor melhorado e um processo para a produção das mesmas
KR1020020031565A KR20020093586A (ko) 2001-06-07 2002-06-05 열처짐성이 개선된 폴리우레탄 포움 및 그의 제조방법
JP2002165615A JP2003026757A (ja) 2001-06-07 2002-06-06 向上したヒートサグを有するポリウレタンフォーム並びにその製造方法および成分
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CN02121817A CN1390869A (zh) 2001-06-07 2002-06-07 经改进热挠度的聚氨酯泡沫塑料及其生产方法
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CA2388585A1 (en) 2002-12-07
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ATE373684T1 (de) 2007-10-15
BR0202107A (pt) 2003-04-22
NZ519353A (en) 2003-11-28
DE60222496D1 (de) 2007-10-31
HUP0201931A2 (hu) 2003-03-28
US20030166735A1 (en) 2003-09-04
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