[go: up one dir, main page]

WO2024258458A1 - Compositions de formation de mousse de polyuréthane contenant des oléfines halogénées, mousses associées et leurs procédés de production - Google Patents

Compositions de formation de mousse de polyuréthane contenant des oléfines halogénées, mousses associées et leurs procédés de production Download PDF

Info

Publication number
WO2024258458A1
WO2024258458A1 PCT/US2024/016141 US2024016141W WO2024258458A1 WO 2024258458 A1 WO2024258458 A1 WO 2024258458A1 US 2024016141 W US2024016141 W US 2024016141W WO 2024258458 A1 WO2024258458 A1 WO 2024258458A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
polyurethane foam
forming composition
polyether polyol
monol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/016141
Other languages
English (en)
Inventor
Brandon W. Parks
Rick L. Adkins
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro LLC
Original Assignee
Covestro LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro LLC filed Critical Covestro LLC
Publication of WO2024258458A1 publication Critical patent/WO2024258458A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5033—Polyethers having heteroatoms other than oxygen having nitrogen containing carbocyclic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • 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
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • 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
    • C08G18/4829—Polyethers containing 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
    • 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
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having 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
    • C08G18/70—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
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2330/00—Thermal insulation material

Definitions

  • This specification pertains generally to halogenated olefin-containing polyurethane foamforming compositions, and polyurethane foams produced therefrom.
  • Rigid polyurethane foams are used in numerous applications. They are produced by reacting a polyisocyanate and an isocyanate-reactive compound, usually a polyol, in the presence of a blowing agent.
  • a polyisocyanate usually a polyol
  • an isocyanate-reactive compound usually a polyol
  • One use of such foams is as a thermal insulation medium in the construction of refrigerated storage devices, including refrigerated appliances and tractor trailers.
  • the thermal insulating properties of closed-cell rigid foams are dependent upon a number of factors, including the average cell size and the thermal conductivity of the contents of the cells.
  • the thermal conductivity of the contents of the cells depends upon the blowing agent(s) used. Fluorocarbons have historically often been used because of their low thermal conductivity.
  • fluorocarbons including chlorofluorocarbons (“CFCs”), hydrofluorocarbons (“HFCs”) and hydrochlorofluorocarbons (“HCFCs”), are greenhouse gases that have been phased out of use.
  • CFCs chlorofluorocarbons
  • HFCs hydrofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • Halogenated olefins such as HCFOs, are environmentally-friendlier alternatives for such fluorocarbons, but they can be costly.
  • K- factor thermal conductivity
  • the thickness of the refrigerator wall or door could be reduced while achieving similar insulation properties, thus allowing for increased internal storage space.
  • this specification relates to polyurethane foam-forming compositions.
  • These polyurethane foam-forming compositions comprise a polyol blend, a blowing agent composition, and a polyisocyanate.
  • the polyol blend has a weighted average functionality of 3 to 6 and a weighted average hydroxyl number of 300 to 500 mg KOH/g.
  • the blowing agent composition comprises (1) a physical blowing agent and (2) a carbon dioxide-generating chemical blowing agent, in which the physical blowing agent comprises a halogenated olefin that is present (i) in an amount of 1% to 30% by weight, based on total weight of the polyurethane foam-forming composition except for the weight of the polyisocyanate, and (ii) in an amount of at least 80% by weight, based on total weight of physical blowing agent in the blowing agent composition.
  • the physical blowing agent composition and the carbon dioxide generating chemical blowing agent are present in a relative ratio, by weight, of at least 5:1.
  • the polyisocyanate comprises a urethane-modified polyisocyanate having a NCO group content of 25 to 35% by weight, based on the total weight of the urethane-modified polyisocyanate, and comprises a reaction product of components comprising: (1) a polymethylene polyphenyl polyisocyanate; and (2) a monol.
  • the polyisocyanate is present in an amount sufficient to provide an isocyanate index of 0.90 to 1.50 [0007] In other respects, this specification relates to methods of producing a polyurethane foam.
  • the methods comprise reacting, at an isocyanate index of 0.90 to 1.50, a polyurethane foam-forming composition comprising a polyol blend, a blowing agent composition, and a polyisocyanate.
  • a polyurethane foam-forming composition comprising a polyol blend, a blowing agent composition, and a polyisocyanate.
  • the polyol blend has a weighted average functionality of 3 to 6 and a weighted average hydroxyl number of 300 to 500 mg KOH/g.
  • the blowing agent composition comprises (1) a physical blowing agent and (2) a carbon dioxide-generating chemical blowing agent, in which the physical blowing agent comprises a halogenated olefin that is present (i) in an amount of 1% to 30% by weight, based on total weight of the polyurethane foam-forming composition except for the weight of the polyisocyanate, and (ii) in an amount of at least 80% by weight, based on total weight of physical blowing agent in the blowing agent composition.
  • the physical blowing agent composition and the carbon dioxide generating chemical blowing agent are present in a relative ratio, by weight, of at least 5:1.
  • the polyisocyanate comprises a urethane-modified polyisocyanate having a NCO group content of 25 to 35% by weight, based on the total weight of the urethane-modified polyisocyanate, and comprises a reaction product of components comprising: (1) a polymethylene polyphenyl polyisocyanate; and (2) a monol.
  • any numerical range recited in this specification includes all sub-ranges of the same numerical precision subsumed within the recited range.
  • a range of " 1.0 to 10.0" is intended to include all sub-ranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6.
  • Any maximum numerical limitation recited in this specification is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein.
  • the term “functionality” refers to the average number of reactive hydroxyl groups, -OH, present per molecule of the -OH functional material that is being described.
  • the hydroxyl groups react with isocyanate groups, -NCO, that are attached to the isocyanate compound.
  • hydroxyl number and “OH number” refer to the number of reactive hydroxyl groups available for reaction, and is expressed as the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of the polyol (ASTM D4274-16).
  • Equivalent weight refers to the weight of a compound divided by its valence.
  • polyurethane foam-forming composition useful in the production of rigid polyurethane foams.
  • a rigid foam is characterized as having a ratio of compressive strength to tensile strength of at least 0.5:1, elongation of less than 10%, as well as a low recovery rate from distortion and a low elastic limit, as described in in "Polyurethanes: Chemistry and Technology, Part II Technology," J. H. Saunders & K. C. Frisch, Interscience Publishers, 1964, page 239.
  • the polyurethane foams of this specification are the reaction product of a polyurethane- foam forming composition that includes a polyisocyanate.
  • polyisocyanate encompasses diisocyanates, as well as isocyanates of greater functionality than 2.0.
  • the polyisocyanate comprises a urethane-modified polyisocyanate.
  • the urethane-modified polyisocyanates employed in the polyurethane foam-forming compositions of this specification comprise the reaction product of components comprising: (1) a polymethylene polyphenyl polyisocyanate ('pMDI"), and (2) a monol.
  • 'pMDI polymethylene polyphenyl polyisocyanate
  • the term "monol” means one or more isocyanate-reactive compounds containing an average isocyanate-reactive group functionality of no more than 1.2, such as 0.8 to 1.2.Further, the urethane-modified polyisocyanate described herein is not a polyisocyanate prepolymer.
  • a "polyisocyanate prepolymer” refers to a polyisocyanate that is a the reaction product of a polyisocyanate and one or more isocyanate-reactive compounds containing an average isocyanate reactive group functionality of greater than 1.2.
  • the polyurethane foam-forming compositions of this specification may comprise a polyisocyanate prepolymer in addition to the urethane-modified polyisocyanate described herein.
  • pMDI is a mixture of diphenylmethane diisocyanate ("MDI") and one or more homologues thereof in which the isocyanate functionality of the homologue(s) is more than 2.
  • the pMDI has an average isocyanate functionality of 2.1 to 3.2, such as 2.5 to 3.2, or, in some cases 2.6 to 3.2 or 2.8 to 3.2.
  • the general formula of pMDI can be represented by the general structure: in which n is an integer having a value of 0 or more.
  • the pMDI comprises: i) up to 60% by weight of a first polymethylene polyphenyl polyisocyanate having a general formula (I), based on 100% by weight of the polymethylene polyphenyl polyisocyanate,
  • n is an integer having a value or 1 or more.
  • the pMDI has an NCO content of 25 to 35% by weight, 29 to 34% by weight, or 29.0 to 32.0% by weight, based on the total weight of the urethane-modified polyisocyanate.
  • the pMDI has a viscosity at 25°C (measured according to EN ISO 3219, October 1994) of 100 to 750 mPa-s, such as 100 to 600 mPa-s, or 150 to 450 mPa-s.
  • the urethane-modified polyisocyanates present in the polyurethane foamforming compositions of this specification comprise the reaction product of components comprising the pMDI and a monol.
  • the monol comprises a compound represented by the structure:
  • any one or more of R 1 , R 2 and R 3 may also represent any of the aforementioned groups that further contain functional groups that do not react with an isocyanate group.
  • Examples of compounds represented by the foregoing structure include primary alcohols, secondary alcohols, tertiary alcohols, or a combination of any two or more thereof, as well as aromatic monols, aliphatic monols, cycloaliphatic monols, or a combination of any two or more thereof, each of which may be saturated or unsaturated, cyclic, linear or branched.
  • Such alcohols may contain 1 to 56, 1 to 36, 1 to 26, 10 to 15, or 12 to 15 carbon atoms.
  • Suitable monols include, without limitation, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2- hydroxypentane, 3-hydroxypentane, the isomeric primary and secondary methylbutyl alcohols, n-hexanol, n-heptanol, n-octanol, n-nonanol, 2-ethylhexanol, primary and secondary trimethylhexanols, cyclohexanol, alkyl substituted cyclohexanols, cyclopentanol, cyclohexylmethanol, phenol, alkyl substituted phenols (such as nonylphenol), benzyl alcohol, n-decanol, n-undecanol, n-dodecanol, n- tridecanol, n-t
  • the monol may include a fluorinated monol, specific examples of which include, without limitation, 2,2,2-trifluoroethanol,
  • the monol may include higher equivalent weight oligomers or polymers that are derived from such monomeric monols.
  • the monol may comprise a polyether monol having an equivalent weight of, for example, at least 850, such as at least 1000, at least 1100 or at least 1200 and up to 10,000, such as up to 7000 or up to 4500.
  • polyether monol refers to compounds of the above specified equivalent weight range which have a theoretical functionality of 1.0 to 1.2.
  • Such polyether monols can prepared by condensing an alkylene oxide with a monol initiator.
  • Suitable alkylene oxides include, for example, ethylene oxide, propylene oxide, butylene oxide, amylene oxide, hexylene oxide, aralkylene oxides, such as styrene oxide, and halogenated alkylene oxides, such as trichlorobutylene oxide, as well as combinations of any two or more thereof.
  • Suitable monol initiators include any of the monols described above. In addition to the monofunctional compounds, the initiator may also include a relatively small amount of a di- or higher functional compounds, such as ethylene glycol, propylene glycol, glycerol, and the like.
  • such di- or higher functional compounds are present in an amount of no more than 10% by weight, no more than 5% by weight, or no more than 1% by weight, based on the total weight of initiator used to prepare the polyether monol.
  • monol initiator is present in an amount of at least 90% by weight, at least 95% by weight, or at least 99% by weight, based on total weight of the initiator used to prepare the polyether monol.
  • the alkoxylation may be performed by a suitable method such as, for example, by base catalysis utilizing strong bases such as sodium hydroxide, potassium hydroxide, sodium methoxide, or potassium methoxide, among others.
  • suitable catalysts include diethylzinc, combinations of metal naphthenates and tertiary amines, and the like.
  • the catalyst includes a double metal cyanide (DMC) complex catalysts such as, for example, hexacyanocobaltate.
  • DMC double metal cyanide
  • the isocyanate-reactive compounds reacted with pMDI to produce the urethane-modified polyisocyanates employed in the polyurethane foam-forming compositions of this specification may also include a relatively small amount of compounds that have an isocyanate-reactive functionality of greater than 1, such as diols and higher-functional polyols, provided however, that such higher functionality compounds are not employed in an amount sufficient to result in an average isocyanate-reactive group functionality of greater than 1.2 for the compounds reacted with the pMDI.
  • such di- and/or higher-functional compounds may be present in an amount of up to 10% by weight, such as up to 5% by weight or up to 1% by weight, based on the total weight of isocyanate-reactive compounds reacted with pMDI to produce the urethane-modified polyisocyanate.
  • the monol is characterized by having a relatively high hydrocarbon content.
  • the monol has an hydrocarbon content of at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, or, in some cases at least 95% by weight, based on the total weight of the monol.
  • the monol has a hydrocarbon content of less than 100% by weight, such as no more than 99.99% by weight, no more 99.9% by weight, no more than 99.5% by weight, or no more than 99% by weight, based on the total weight of the monol.
  • hydrocarbon content refers to the total weight of all carbon and hydrogen atoms present in a molecule.
  • hydrocarbon content refers to the total weight of all carbon and hydrogen atoms present in the polyether monol and not just the weight of the carbons atoms and hydrogen atoms present in the monol used as a starter to produce the polyether monol.
  • the pMDI and the monol are reacted together in relative amounts such that 5 to 5000, such as 7 to 4500, NCO equivalents are present for each OH equivalent that is present.
  • Any suitable reaction temperature may be employed, such as a temperature of 20°C to 100°C or 40°C to 80°C.
  • the polyisocyanate is present in an amount sufficient to provide an isocyanate index of 0.90 to 1.50, such as 1.20 to 1.50.
  • the foregoing urethane-modified polyisocyanate is essentially the sole polyisocyanate present in the polyurethane foam-forming composition. Therefore, in these implementation, the urethane-modified polyisocyanate is present in the polyurethane foam-forming composition in an amount sufficient to provide an isocyanate index of 0.90 to 1.50, such as 1.20 to 1.50.
  • the polyurethane foam-forming compositions described in this specification also comprise a polyol blend.
  • the polyol blend has a weighted average functionality of 3 to 6, 3 to 5, 3.5 to 4.5, or 3.8 to 4.2, and/or a weighted average hydroxyl number of 300 to 500 mg KOH/g, such as 350 to 450 mg KOH/g.
  • the polyol blend is present in the polyurethane foam-forming composition in an amount of at least 50% by weight, such as 50 to 90% by weight or 60 to 80% by weight, based on the total weight of the polyurethane foam-forming composition except for the weight of polyisocyanate that is present.
  • the polyol blend comprises an amine-initiated polyether polyol.
  • amine-initiated polyether polyol refers to a polyether polyol that is the reaction product of an H-functional starter comprising an amine, such as aliphatic amines and/or aromatic amines, and alkylene oxide.
  • the amine starter comprises an aromatic amine.
  • aromatic amine-initiated polyether polyol refers to a polyether polyol that is the reaction product of an H-functional starter comprising an aromatic amine, such as toluenediamine (“TDA”), with alkylene oxide.
  • the amine H-fimctional starter used to prepare the amine-initiated polyether polyol is not an alkanolamine and, as a result, in some of these cases, the amine-initiated polyether polyol is distinct from the alkanolamine-initiated polyether polyol described below.
  • the amine employed has an amine functionality of at least 2, such as 2 to 3.
  • suitable (cyclo)aliphatic amine starters include, without limitation, 1,2-ethylenediamine, 1,3 -propylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, pentane diamine, isophorone diamine, 1,10-decanediamine and diaminocyclohexylmethane, pentamethylenediamine, and combinations of any two or more thereof.
  • aromatic amines which can be used include crude TDA obtained by the nitration of toluene followed by reduction; 2,3-TDA, 3,4-TDA, 2,4-TDA, 2,6-TDA or mixtures thereof; aniline; 4,4'-methylene dianiline; methylene-bridged polyphenyl polyamines composed of isomers of methylene dianilines and triamines or polyamines of higher molecular weight prepared by reacting aniline with formaldehyde by methods known in the art.
  • a mixture composed of 2,3- TDA and 3,4-TDA (commonly referred to as "o-TDA") is used.
  • H-functional starters may also be used to prepare the amine-initiated polyether polyol.
  • H-functional starters include, for example, water, propylene glycol, glycerin, ethylene glycol, ethanol amines, diethylene glycol, or a mixture of any two or more thereof.
  • amine in some cases aromatic amine, is the predominant or essentially sole H-functional starter used to produce the amine-initiated polyether polyol.
  • amine in some cases aromatic amine, is present in an amount of more than 50% by weight, such as at least 80% by weight, at least 90% by weight, or even 100% by weight, based on the total weight of H-functional starter used to produce the amine-initiated polyether polyol.
  • alkylene oxides may be used to produce the amine-initiated polyether polyol, such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide and mixtures thereof.
  • the alkylene oxides may be added individually, sequentially one after the other to form blocks or in a mixture to form a heteric polyether.
  • the amine-initiated polyether polyols may have primary or secondary hydroxyl end groups.
  • propylene oxide is the primary or essentially sole alkylene oxide used to prepare the amine-initiated polyether polyol.
  • propylene oxide is used in an amount of more than 50% by weight, such as at least 80% by weight, at least 90% by weight, or even 100% by weight, based on the total weight of alkylene oxide used to prepare the amine-initiated polyether polyol.
  • ethylene oxide is employed in a relatively small amount.
  • ethylene oxide is used in an amount of no more than 10% by weight, no more than 5% by weight, no more than 1% by weight, or, in some cases, 0% by weight, based on the total weight of alkylene oxide used to prepare the amine-initiated polyether polyol.
  • the amine-initiated polyether polyol has an OH number of 200 to 600 mg KOH/g and a functionality of at least 2.5. In some implementations, the amine-initiated polyether polyol has an OH number of 300 to 500 mg KOH/g, such as 380 to 420 mg KOH/g and an average functionality of 3.5 to 4.5, 3.8 to 4.2 or 4.0.
  • the amine-initiated polyether polyol in some implementations, has a content of -C2H4O- units of less than 10% by weight, such as less than 5% by weight, less than 2% by weight, or, in some cases, 0% by weight, based on total weight of the amine- initiated polyether polyol.
  • the amine-initiated, such as aromatic amine-initiated, polyether polyol is present in an amount of at least 30% by weight, based on the total weight of the polyol blend. More specifically, in some implementations, the amine-initiated, such as aromatic amine-initiated, polyether polyol is present in an amount of 30 to 80% by weight, such as 30 to 60% by weight, or, in some cases, 40 to 60% by weight or 40 to 50% by weight, based on the total weight of the polyol blend. [0039] Moreover, in some cases, the polyol blend also includes a saccharide-initiated polyether polyol.
  • saccharide-initiated polyether polyol refers to a polyether polyol that is the reaction product of an H-functional starter comprising saccharide, such as sucrose, with alkylene oxide.
  • suitable alkylene oxides include those mentioned earlier with respect to the amine-initiated polyether polyol.
  • suitable saccharide initiators are sucrose, sorbitol, maltitol, etc. as well as other mono-saccharides, di-saccharides, tri-saccharides and polysaccharides.
  • Other initiator compounds are often used in combination with the saccharide initiator to prepare the saccharide initiated polyether polyol.
  • Saccharides can be co-initiated with for example, compounds such as water, propylene glycol, glycerin, ethylene glycol, ethanol amines, diethylene glycol, or a mixture of any two or more thereof, however, in some cases, little or no amine initiator is used to prepare the saccharide-initiated polyether polyol.
  • compounds such as water, propylene glycol, glycerin, ethylene glycol, ethanol amines, diethylene glycol, or a mixture of any two or more thereof, however, in some cases, little or no amine initiator is used to prepare the saccharide-initiated polyether polyol.
  • compounds such as water, propylene glycol, glycerin, ethylene glycol, ethanol amines, diethylene glycol, or a mixture of any two or more thereof, however, in some cases, little or no amine initiator is used to prepare the saccharide-initiated polyether polyol.
  • saccharide is the predominant H-functional starter used to produce the saccharide-initiated polyether polyol. This means that, in these implementations, saccharide is present in an amount of more than 50% by weight, such as at least 70% by weight or at least 80% by weight, based on the total weight of H-functional starter used to produce the saccharide-initiated polyether polyol.
  • propylene oxide is the primary or essentially sole alkylene oxide used to prepare the saccharide-initiated polyether polyol.
  • propylene oxide is used in an amount of more than 50% by weight, such as at least 60% by weight, or at least 70% by weight, based on the total weight of alkylene oxide used to prepare the saccharide-initiated polyether polyol.
  • ethylene oxide is employed in a relatively small amount.
  • ethylene oxide is present in an amount of no more than 50% by weight, such as no more than 40% by weight, or, in some cases, no more than 30% by weight, based on the total weight of alkylene oxide used to prepare that saccharide-initiated polyether polyol.
  • the saccharide-initiated polyether polyol has an OH number of
  • the saccharide-initiated polyether polyol has a content of -C2H4O- units of less than 50% by weight, such as less than 40% by weight, or no more than 30% by weight, based on total weight of the saccharaide-initiated polyether polyol.
  • the saccharide-initiated polyether polyol is present in an amount of at least 30% by weight, based on the total weight of the polyol blend. More specifically, in some cases, the saccharide-initiated polyol is present in an amount of 30 to 60% by weight, such as 30 to 50% by weight, or, in some cases, 35 to 45% by weight, based on the total weight of the polyol blend.
  • the polyol blend may include an aliphatic triol-initiated polyether polyol.
  • aliphatic-triol-initiated polyether polyol refers to a polyether polyol that is the reaction product of an H-functional starter comprising an aliphatic triol, such as glycerin, with alkylene oxide.
  • suitable alkylene oxides include alkylene oxides include those mentioned earlier with respect to the amine-initiated polyether polyol.
  • Other initiator compounds may be used in combination with the aliphatic triol initiator to prepare the aliphatic triol-initiated polyether polyol.
  • Aliphatic triols can be co-initiated with for example, compounds such as water, propylene glycol, sucrose, ethylene glycol, diethylene glycol, or a mixture of any two or more thereof, however, in some cases, little or no amine initiator and no saccharide initiator is used to prepare the aliphatic triol-initiated polyether polyol. As will be appreciated, it is possible to use a wide variety of individual initiator compounds in combination with aliphatic triol initiator.
  • aliphatic triol is the predominant H-functional starter used to produce the aliphatic triol-initiated polyether polyol. This means that, in these implementations, aliphatic triol is present in an amount of more than 50% by weight, such as at least 70% by weight or at least 80% by weight, based on the total weight of H-functional starter used to produce the aliphatic triol-initiated polyether polyol.
  • propylene oxide is the primary or essentially sole alkylene oxide used to prepare the aliphatic triol-initiated polyether polyol. This means that, in these implementations, propylene oxide is used in an amount of more than 50% by weight, such as at least 60% by weight, or at least 70% by weight, based on the total weight of alkylene oxide used to prepare the aliphatic triol-initiated polyether polyol. In some implementations, ethylene oxide is employed in a relatively small amount.
  • ethylene oxide is present in an amount of no more than 50% by weight, such as no more than 40% by weight, or, in some cases, no more than 30% by weight, based on the total weight of alkylene oxide used to prepare that aliphatic triol-initiated polyether polyol.
  • the aliphatic triol-initiated polyether polyol has a content of -C2H4O- units of less than 50% by weight, such as less than 40% by weight, or no more than 30% by weight, based on total weight of the aliphatic triol-initiated polyether polyol.
  • the aliphatic triol-initiated polyether polyol is present in an amount of at least 30% by weight, based on the total weight of the polyol blend. More specifically, in some cases, the aliphatic triol-initiated polyol is present in an amount of 30 to 60% by weight, such as 30 to 50% by weight, or, in some cases, 35 to 45% by weight, based on the total weight of the polyol blend.
  • the polyol blend may comprise an alkanolamine-initiated polyether polyol.
  • alkanolamine-initiated polyether polyol refers to a polyether polyol prepared by reacting at least one alkylene oxide with one or more suitable initiator compounds in the presence of a suitable catalyst, in which the initiator compounds comprise one or more alkanolamines.
  • Suitable catalysts including basic catalysts (such as sodium or potassium hydroxide or tertiary amines such as methyl imidazole) and DMC catalysts.
  • each of the recited polyether polyols, including the "alkanolamine-initiated polyether polyol” and the "aliphatic amine- initiated polyether polyol" are different from each other.
  • alkanolamine refers to compounds represented by the formula: NHz— Z— OH in which Z represents a divalent radical which is a straight chain or branched chain alkylene radical having 2 to 6 carbon atoms, a cycloalkylene radical having 4 to 6 carbon atoms or a dialkylene ether radical having 4 to 6 carbon atoms.
  • the dialkylene ether radical may be represented by the formula:
  • alkanolamines that may be used in the preparation of the alkanolamine-initiated polyether polyol include monoethanolamine, l-amino-2-propanol, 2-amino-l- propanol, 3-amino-l-propanol, l-(2-aminoethoxy) ethanol, l-amino-2-butanol, 2-amino-3-butanol, 2- amino-2-methylpropanol, 5-amino pentanol, 3-amino-2, 2-dimethyl propanol, 4-aminocyclohexanol, as well as mixtures of any two or more thereof.
  • alkanolamine is the predominant H-functional starter used to produce the alkanolamine-initiated polyether polyol. This means that, in these implementations, alkanolamine is present in an amount of more than 50% by weight, such as at least 70% by weight or at least 80% by weight, based on the total weight of H-functional starter used to produce the alkanolamine-initiated polyether polyol.
  • propylene oxide is the primary or essentially sole alkylene oxide used to prepare the alkanolamine-initiated polyether polyol. This means that, in these implementations, propylene oxide is used in an amount of more than 50% by weight, such as at least 60% by weight, or at least 70% by weight, based on the total weight of alkylene oxide used to prepare the alkanolamine-initiated polyether polyol. In some implementations, ethylene oxide is employed in a relatively small amount.
  • ethylene oxide is present in an amount of no more than 50% by weight, such as no more than 40% by weight, or, in some cases, no more than 30% by weight, based on the total weight of alkylene oxide used to prepare that alkanolamine-initiated polyether polyol.
  • the alkanolamine-initiated polyether polyol has an OH number of at least 500 mg KOH/g, such as 500 to 900 mg KOH/g, 600 to 800 mg KOH/g, or, in some cases, 680 to 720 mg KOH/g, and a functionality of 2.5 to 4, such as 2.5 to 3.5.
  • the polyol blend may, if desired, include other compound with isocyanate-reactive groups, such as chain extenders and/or crosslinking agents, and higher molecular weight polyether polyols and polyester polyols not described above.
  • Chain extenders and/or crosslinking agents include, for example, ethylene glycol, propylene glycol, butylene glycol, glycerol, diethylene glycol, dipropylene glycol, dibutylene glycol, trimethylolpropane, pentaerythritol, ethylene diamine, and diethyltoluenediamine.
  • Polyester polyols may be prepared from, for example, an organic dicarboxylic acid having 2 to 12 carbon atoms, such as an aliphatic dicarboxylic acid having 4 to 6 carbon atoms, and a polyvalent alcohol, such as a diol or triol having 2 to 12 carbon atoms.
  • dicarboxylic acid examples include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the polyol blend has a content of -C2H4O- units of 3 to 6%, such as 4 to 6% by weight, based on total weight of the polyurethane foam-forming composition.
  • a content of -C2H4O- units refers to the calculated weight of -C2H4O- units present in a polyol that are formed during production of the polyol itself (as opposed to -C2H4O- units that may already be present in a reactant used to prepare the polyol).
  • -C2H4O- units can result from use of ethylene oxide as an alkylene oxide and/or use of an H-functional starter containing a - C2HiZ-group in which Z represents a Zerewitinoff-active hydrogen atom (sometimes also referred to merely as "active hydrogen"), such as can be the case where Z represents a hydrogen bonded to N, O or S.
  • Z represents a Zerewitinoff-active hydrogen atom
  • -C2H4Z- units may result, for example, from use of diethylene glycol as a hydroxyl-containing material.
  • a polyol blend has a content of- C2H4O- units of 3 to 6% by weight, based on total weight of the polyurethane foam-forming composition
  • 3 to 6% by weight of the polyurethane foam-forming composition, based on total weight of the polyurethane foam-forming composition is -C2H4O- units formed during production of the polyol(s) that are used, as calculated based on the weight of materials used to make the polyols.
  • the polyurethane foam-forming compositions of this specification further comprises a physical blowing agent composition comprising a halogenated olefin.
  • the halogenated olefin comprises a hydrofluoroolefin ("HFO"), a hydrochlorofluoroolefms ("HCFOs”), or a combination thereof.
  • HFO hydrofluoroolefin
  • HCFOs hydrochlorofluoroolefms
  • Suitable such halogenated olefms include, without limitation, l,l,l,4,4,4-hexafluoro-2-butene (cis and/or trans isomers), l-chloro-3,3,3- trifluoropropene (HCFO-1233zd, E and/or Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), HCFO1223, l,2-dichloro-l,2-difluoroethene (E and/or Z isomers), 3,3-dichloro-3-fluoropropene, 2- chloro-l,l,
  • the halogenated olefin is present in an amount of 1 to 30% by weight, such as 5 to 30% by weight, 10 to 30% by weight or 15 to 25% by weight or 18 to 22% by weight, based on the total weight of the polyurethane foam-forming composition except for the weight of the polyisocyanate.
  • the isocyanate-reactive composition may include one or more other physical blowing agents, such as other halogenated blowing agents, such as CFCs, HCFCs, and HFCs, and/or hydrocarbon blowing agents, such as butane, n-pentane, cyclopentane, hexane, and/or isopentane (i.e. 2- methylbutane).
  • other physical blowing agents such as other halogenated blowing agents, such as CFCs, HCFCs, and HFCs
  • hydrocarbon blowing agents such as butane, n-pentane, cyclopentane, hexane, and/or isopentane (i.e. 2- methylbutane).
  • the isocyanate-reactive composition is substantially or, in some cases, completely free, of such other physical blowing agents.
  • the halogenated olefin such as HCFO
  • the halogenated olefin is present in amount of at least 80% by weight, such as at least 90% by weight, at least 95% by weight, at least 99% by weight or, in some cases 100% by weight, based on the total weight of the physical blowing agent in the blowing agent composition.
  • the polyurethane foam-forming compositions of this specification include a carbon dioxide generating chemical blowing agent, such as water and/or a formate-blocked amine, is also included.
  • a carbon dioxide generating chemical blowing agent such as water
  • the carbon dioxide generating chemical blowing agent such as water
  • the carbon dioxide generating chemical blowing agent is utilized in an amount of 0.5 to 5.0% by weight, such as 1 to 3% by weight, or 1.0 to 2.0% by weight, or 1.2 to 1.8% by weight, based on the total weight of the polyurethane foam-forming composition except for the weight of the polyisocyanate.
  • the physical blowing agent composition and the carbon dioxide generating chemical blowing agent are present in a relative ratio, by weight, of at least 5:1, such as 5:1 to 50:1, 5:1 to 20:1 or, in some cases, 10:1 to 15:1.
  • the polyurethane foam-forming composition also typically comprises a surfactant.
  • Suitable surfactant include, for example, organosilicon compounds, such as polysiloxane-polyalkyene- block copolymers, such as a polyether-modified polysiloxane.
  • Other possible surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkylsulfonic esters, or alkylarylsulfonic acids.
  • Such surfactants are employed in amounts sufficient to stabilize the foaming reaction mixture against collapse and the formation of large and uneven cells.
  • surfactant is utilized in an amount of 0.2 to 5.0% by weight, such as 1 to 3% by weight, based on the total weight of the polyurethane foam-forming composition except for the weight of the polyisocyanate.
  • the polyurethane foam-forming compositions of this specification also typically comprise a catalyst, such as a tertiary amine, tertiary phosphine, a metal chelate, an acid metal salt, a strong base, a metal alcoholate and/or phenolate, a metal salt of an organic acid, or a combination thereof.
  • a catalyst such as a tertiary amine, tertiary phosphine, a metal chelate, an acid metal salt, a strong base, a metal alcoholate and/or phenolate, a metal salt of an organic acid, or a combination thereof.
  • the catalyst comprises an organotin catalyst and/or tertiary amine catalyst.
  • a combination of at least one “blowing” catalyst, which strongly promotes the reaction of an isocyanate group with a water molecule to form carbon dioxide, and either at least one “gelling” catalyst, which strongly promotes the reaction of an alcohol group with an isocyanate to form the urethane, or at least one trimerization catalyst, may be used.
  • tertiary amine catalysts include: pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N',N"-tris(3- dimethylaminopropyl-)hexahydrotriazine, tetramethylethylenediamine, tetraethylene diamine, benzyldimethylamine or a combination thereof.
  • the tertiary amine catalyst includes pentamethyldiethylenetriamine, N,N',N"-dimethylaminopropyl-hexahydrotriazine, N,N- dimethylcyclohexylamine, or a combination thereof.
  • Additional materials which may optionally be included in the foam-forming compositions of the present invention include: pigments, colorants, fillers, antioxidants, flame retardants, and stabilizers.
  • Exemplary flame retardants useful in the foam-forming composition of the present invention include, but are not limited to, reactive bromine based compounds known to be used in polyurethane chemistry and chlorinated phosphate esters, including but not limited to, tri(2-chloroethyl)phosphate (TECP), tri(l,3-dichloro-2-propyl)phosphate, tri(l-chloro-2-propyl)phosphate (TCPP) and dimethyl propyl phosphate (DMPP).
  • TCP tri(2-chloroethyl)phosphate
  • TCPP tri(l,3-dichloro-2-propyl)phosphate
  • DMPP dimethyl propyl phosphate
  • This specification is also directed to processes for producing rigid polyurethane foams.
  • a polyisocyanate is reacted with an isocyanate-reactive composition comprising the polyol blend.
  • the isocyanate functional component and the polyol blend are mixed at an isocyanate index of 0.90 to 1.50, such as 1.20 to 1.50.
  • the polyol blend is reacted with an polyisocyanate in the presence of the blowing agent composition, the catalyst composition, a surfactant and any other optional ingredients.
  • the rigid foams may be prepared by blending all of the polyurethane foam-forming composition components, except for the polyisocyanate, together in a phase stable mixture, and then mixing this mixture in the proper ratio with the polyisocyanate.
  • one or more of the components, such as the surfactant may be combined with the polyisocyanate prior to mixing it with the polyol blend.
  • Other possible implementations would include adding one or more of the components as a separate stream, together with the polyol blend and polyisocyanate.
  • phase stable means that the composition does not visibly separate when stored for 7 days at about 70°F (or 21°C).
  • component A polyisocyanate
  • component B isocyanate-reactive composition which typically includes the polyol blend, blowing agent, water, catalyst and surfactant
  • the components may be mixed in the proper ratio at a temperature of 5 to 50°C, such as 15 to 35°C, injected or poured into a mold having the temperature controlled to within a range of 20 to 70°C, such as 35 to 60°C. The mixture then expands to fill the cavity with the rigid polyurethane foam.
  • the rigid polyurethane foams may also be prepared by the so-called "quasi prepolymer" method. In this method, a portion of the polyol component is reacted in the absence of the urethane-forming catalysts with the polyisocyanate component in proportion so as to provide 10% to 35% of free isocyanate groups in the reaction product based on the prepolymer. To prepare foam, the remaining portion of the polyol is added and the components are allowed to react together in the presence of the blowing agent and other appropriate additives such as the catalysts, and surfactants. Other additives may be added to either the isocyanate prepolymer or remaining polyol or both prior to the mixing of the components, whereby at the end of the reaction, rigid foam is provided.
  • the rigid foam can be prepared in a batch or continuous process by the one- shot or quasi-prepolymer methods using any well-known foaming apparatus.
  • the rigid foam may be produced in the form of slab stock, moldings, cavity fillings, sprayed foam, frothed foam or laminates with other materials such as hardboard, plasterboard, plastics, paper or metal as facer substrates.
  • the object is to retain the blowing agent in the cells to maintain a low thermal conductivity of the insulating material, i.e., the rigid foam.
  • the rigid foams produced according to implementations of this specification have a closed-cell content of more than 80 percent, more than 85 percent, or more than 88 percent, as measured according to ASTM D6226-15.
  • the thermal conductivity of foams produced according to various implementations of the present specification indicates that the foams have acceptable insulating properties, i.e., the foams have athermal conductivity measured at 35°F (2°C) of less than 0.126 BTU-in/h-ft 2 -°F and measured at 75°F (24°C) of less than 0.140 BTU-in/h-ft 2 -°F for foam from the core of 2-inch thick panels, as measured according to ASTM C518-15.
  • This specification also relates to the use of the rigid foams described herein for thermal insulation. That is, the rigid foams of the present specification may find use as an insulating material in refrigeration apparatuses. These rigid foams can be used, for example, as an intermediate layer in composite elements or for filling hollow spaces of refrigerators and freezers, or refrigerated trailers. These foams may also find use in the construction industry or for thermal insulation of long-distance heating pipes and containers.
  • the present invention also provides a composite article comprising rigid foam as disclosed herein sandwiched between one or more facer substrates.
  • the facer substrate may be plastic (such a polypropylene resin reinforced with continuous bi-directional glass fibers or a fiberglass reinforced polyester copolymer), paper, wood, or metal.
  • the composite article may be a refrigeration apparatus such as a refrigerator, freezer, or cooler with an exterior metal shell and interior plastic liner.
  • the refrigeration apparatus may be a trailer, and the composite article may include the foams produced according to the present invention in sandwich composites for trailer floors or sidewalls.
  • Polyol 2 A sucrose/glycerine/propylene glycol/water initiated polyether polyol (100% propylene oxide) having an OH number of 410 mg KOH/g and an average functionality of 4.28;
  • Polyol 3 A sucrose/glycerine initiated polyether polyol (100% propylene oxide) having an OH number of 470 mg KOH/g and an average functionality of 4.66;
  • Polyol 5 An ethylenediamine initiated polyether polyol (100% propylene oxide) having an OH number of 60 mg KOH/g and an average functionality of 3.71;
  • Polyol 6 A sucrose/propylene glycol/water initiated polyether polyol (100% propylene oxide) having an OH number of 470 mg KOH/g and an average functionality of 5.24;
  • Polyol 7 A sucrose/water initiated polyether polyol (100% propylene oxide) having an OH number of 380 mg KOH/g and an average functionality of 5.81;
  • Polyol 8 A monoethanolamine initiated polyether polyol (100% propylene oxide) having an OH number of 700 mg KOH/g and an average functionality of 3.0;
  • Polyol 9 A glycerine initiated polyether polyol (100% propylene oxide) having an OH number of 470 mg KOH/g and an average functionality of 3.0;
  • Polyol 10 A sucrose/water initiated polyether polyol (70% propylene oxide/30% ethylene oxide block) having an OH number of 470 mg KOH/g and an average functionality of 5.52;
  • Polyol 11 A glycerine initiated polyether polyol (100% propylene oxide) having an OH number of 112 mg KOH.g and an average functionality of 3;
  • Polyol 12 A glycerine initiated polyether polyol (100% propylene oxide) having an OH number of 240 mg KOH/g and an average functionality of 3.0;
  • Polyol 13 An aromatic polyester polyol having an OH number of 230-250 mg KOH/g and a functionality of 2 (commercially available from Stepan Company as STEPANPOL® PS-2502A);
  • Alcohol 1 a C12-C15 primary alcohol blend with a hydroxyl number 267-276, NeodolTM 25 from Shell Chemicals;
  • Alcohol 2 Tridecafluoro- 1 -octanol, Capstone 62TM Alcohol commercially available from Chemours;
  • Surfactant 1 silicone surfactant with a hydroxyl number of 54 mg KOH/g, VorasurfTM DC 5357 from Dow;
  • Surfactant 2 a polyorganosiloxane polyether copolymer believed to have a hydroxyl number of 105 mg KOH/g, available as Tegostab® B-8465 from Evonik;
  • Surfactant 3 non-hydrolyzable silicone surfactant with a hydroxyl number of 66 mg KOH/g, NiaxTM L- 5440 from Momentive;
  • Surfactant 4 silicone surfactant with a hydroxyl number of 110 mg KOH/g, available as Tegostab® IB- 8499 from Evonik;
  • Catalyst 1 N,N,N',N”,N”-pentamethyldiethylenetriamine, PolycatTM 5 from Evonik;
  • Catalyst 2 a solution of potassium-octoate in diethylene glycol, Dabco® K-15 from Evonik;
  • Catalyst 3 N,N-Dimethylcyclohexylamine, PolycatTM 8 from Evonik;
  • Catalyst 4 N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine, PolycatTM 41 from Evonik;
  • Catalyst 5 (2-Hydroxypropyl)trimethylammonium formate, Dabco® TMR-2 from Evonik;
  • Catalyst 6 2,2'-dimorpholinodiethylether, JEFFCAT® DMDEE from Huntsman;
  • Catalyst 7 1,2-dimethylimidazole, Dabco® 2041 from Evonik;
  • Catalyst 8 N-methyhnorpholine, JEFFCAT® NMM from Huntsman;
  • Catalyst 9 N,N-Dimethylbenzylamine, Addocat® DB from Lanxess;
  • Additive 1 Tris (2-chloroisopropyl) phosphate, FyrolTM PCF from ICL Industrial Products;
  • Blowing Agent 1 cyclopentane
  • Blowing Agent 2 trans-l,l,l-trifhioro-3-chloropropene, Solstice® LBA from Honeywell International
  • Isocyanate 1 polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa s @ 25°C (MONDUR® MR from Covestro);
  • Isocyanate 2 polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.3%; viscosity 400 mPa s @ 25°C (MONDUR® 44V40 from Covestro);
  • Isocyanate 3 Prepared by adding Isocyanate 1 (3000g) to a 5-L 3-neck flask with stirring under nitrogen, heating Isocyanate 1 to 60°C, adding Alcohol 1 (180g) dropwise, maintaining the solution temperature at 60°C, and continuing heating for 1 hour to give Isocyanate 3 with an isocyanate content of 27.1% and 413 mPa.s@25°C viscosity;
  • Isocyanate 4 Prepared by adding Isocyanate 1 (3000g) to a 5-L 3-neck flask with stirring under nitrogen, heating Isocyanate 1 60°C, adding Alcohol 2 (240g) dropwise, maintaining the solution temperature at 60°C, and continuing heating for 1 hour to give Isocyanate 4 with an isocyanate content of 26.8% and 358 mPa.s@25°C viscosity;
  • Isocyanate 5 Prepared by adding Isocyanate 1 (3000g) to a 5-L 3-neck flask with stirring under nitrogen, heating Isocyanate 1 to 60°C, adding Alcohol 1 (75g) dropwise, maintaining the solution temperature at 60°C, and continuing heating for 1 hour to give Isocyanate 5 with an isocyanate content of 29.5% and 261 mPa.s@25°C viscosity; and
  • Isocyanate 6 Prepared by adding Isocyanate 1 (3000g) to a 5-L 3-neck flask with stirring under nitrogen, heating Isocyanate 1 to 60°C, adding Alcohol 2 (90g) dropwise, maintaining the solution temperature at 60°C, and continuing heating for 1 hour to give Isocyanate 6 with an isocyanate content of 30.2% and 266 mPa.s@25°C viscosity.
  • a master batch was prepared by mixing the polyols, catalysts, surfactant, water and blowing agents in the amounts indicated in Table 1.
  • Foams were prepared by mixing the masterbatch with the Isocyanate in an amount sufficient to provide the isocyanate index listed in Table 1 and pouring the mixture into an 83 ounce paper cup. The cream time, gel time, tack-free time and free rise density (“FRD”) were recorded.
  • Foam panels were also prepared by hand using an air-powered mixer (-3000 rpm) and utilizing a temperature controlled mold (120°F; dimensions of 25" x 13" x 2"). The isocyanate-reactive composition and isocyanate temperatures were maintained at 25°C and all samples were demolded after 3 minutes. Minimum fill was determined by slightly overfilling the mold cavity and then removing the excess foam such that the foam weight contained in the 25" x 13" x 2" volume could be measured. After determining the minimum fill value, foam panels were prepared to obtain a desired density approximately 8-12% over the minimum fill density. Results are in Table 1.
  • Results in Table 1 represent the average results of three replicate experiments. Examples 2-3, 5-6 and 8, 10-11, 13, 15, and 17 are inventive examples and Examples 1, 4, 7, 9, 12, 14, and 16 are comparative examples. Table 1

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions de formation de mousse de polyuréthane qui comprennent un mélange de polyols, une composition d'agent d'expansion et un polyisocyanate. Le mélange de polyols a une fonctionnalité moyenne pondérée de 3 à 6 et un indice d'hydroxyle moyen pondéré de 300 à 500 mg KOH/g. La composition d'agent d'expansion comprend un agent d'expansion physique et un agent d'expansion chimique générant du dioxyde de carbone, l'agent d'expansion physique comprenant une oléfine halogénée qui est présente (i) en une quantité de 1% à 30% en poids, sur la base du poids total de la composition de formation de mousse de polyuréthane à l'exception du poids du polyisocyanate, et (ii) en une quantité d'au moins 80% en poids, sur la base du poids total d'agent d'expansion physique dans la composition d'agent d'expansion. La composition d'agent d'expansion physique et l'agent d'expansion chimique générant du dioxyde de carbone sont présents dans un rapport relatif, en poids, d'au moins 5:1. Le polyisocyanate comprend un polyisocyanate modifié par uréthane ayant une teneur en groupe NCO de 25 à 35% en poids, sur la base du poids total du polyisocyanate modifié par uréthane, et comprend un produit de réaction de composants comprenant un polyisocyanate de polyméthylène polyphényle et un monol.
PCT/US2024/016141 2023-06-16 2024-02-16 Compositions de formation de mousse de polyuréthane contenant des oléfines halogénées, mousses associées et leurs procédés de production Pending WO2024258458A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363508557P 2023-06-16 2023-06-16
US63/508,557 2023-06-16

Publications (1)

Publication Number Publication Date
WO2024258458A1 true WO2024258458A1 (fr) 2024-12-19

Family

ID=90458425

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2024/016141 Pending WO2024258458A1 (fr) 2023-06-16 2024-02-16 Compositions de formation de mousse de polyuréthane contenant des oléfines halogénées, mousses associées et leurs procédés de production

Country Status (1)

Country Link
WO (1) WO2024258458A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4843054A (en) 1987-02-26 1989-06-27 Arco Chemical Technology, Inc. Preparation of filterable double metal cyanide complex catalyst for propylene oxide polymerization
US5158922A (en) 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
US5470813A (en) 1993-11-23 1995-11-28 Arco Chemical Technology, L.P. Double metal cyanide complex catalysts
WO1996037540A1 (fr) * 1995-05-23 1996-11-28 Minnesota Mining And Manufacturing Company Composition expansible contenant un agent gonflant perfluorochimique insature
EP0581191B1 (fr) * 1992-07-27 1997-05-21 Takeda Chemical Industries, Ltd. Production et utilisation de mousse de polyuréthane rigide à cellules ouvertes
US20190389996A1 (en) * 2017-01-31 2019-12-26 Basf Se Hfo containing pu formulation
JP2022142752A (ja) * 2021-03-16 2022-09-30 日本パフテム株式会社 ウレタン樹脂組成物、ウレタン樹脂発泡体、ウレタン樹脂組成物の原料組成物及びウレタン樹脂組成物の原料キット

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4843054A (en) 1987-02-26 1989-06-27 Arco Chemical Technology, Inc. Preparation of filterable double metal cyanide complex catalyst for propylene oxide polymerization
US5158922A (en) 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
EP0581191B1 (fr) * 1992-07-27 1997-05-21 Takeda Chemical Industries, Ltd. Production et utilisation de mousse de polyuréthane rigide à cellules ouvertes
US5470813A (en) 1993-11-23 1995-11-28 Arco Chemical Technology, L.P. Double metal cyanide complex catalysts
WO1996037540A1 (fr) * 1995-05-23 1996-11-28 Minnesota Mining And Manufacturing Company Composition expansible contenant un agent gonflant perfluorochimique insature
US20190389996A1 (en) * 2017-01-31 2019-12-26 Basf Se Hfo containing pu formulation
JP2022142752A (ja) * 2021-03-16 2022-09-30 日本パフテム株式会社 ウレタン樹脂組成物、ウレタン樹脂発泡体、ウレタン樹脂組成物の原料組成物及びウレタン樹脂組成物の原料キット

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. H. SAUNDERSK. C. FRISCH: "Polyurethanes: Chemistry and Technology, Part II Technology", 1964, INTERSCIENCE PUBLISHERS, pages: 239

Similar Documents

Publication Publication Date Title
US11505670B2 (en) Polyurethane foams co-blown with a mixture of a hydrocarbon and a halogenated olefin
US10640600B2 (en) Rigid polyurethane foams suitable for use as panel insulation
US10851196B2 (en) Rigid polyurethane foams suitable for use as panel insulation
US10752725B2 (en) Rigid polyurethane foams suitable for use as panel insulation
US12134676B2 (en) Rigid polyurethane foams suitable for use as panel insulation
US11161931B2 (en) Polyol blends and their use in producing PUR-PIR foam-forming compositions
US11053340B2 (en) HCFO-containing isocyanate-reactive compositions, related foam-forming compositions and PUR-PIR foams
US12312465B2 (en) HFCO-containing isocyanate-reactive compositions, polyurethane foams formed therefrom, and composite articles that include such foams
US20170158801A1 (en) Rigid polyurethane foams suitable for wall insulation
US20120022179A1 (en) Process for producing rigid polyurethane foams
US11767394B2 (en) HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production
CN110461897A (zh) 多元醇组分及其用于制备硬质聚氨酯泡沫的用途
US20220403096A1 (en) Hcfo-containing isocyanate-reactive compositions, related foam-forming compositions and polyurethane foams
US11767407B1 (en) HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production
US20240400744A1 (en) Polyol blends that include an isopropylidenediphenol-based polyether polyol, related compositions and foams
US11753516B2 (en) HFO-containing compositions and methods of producing foams
US11827735B1 (en) HFO-containing isocyanate-reactive compositions, related foam-forming compositions and flame retardant PUR-PIR foams
WO2024258458A1 (fr) Compositions de formation de mousse de polyuréthane contenant des oléfines halogénées, mousses associées et leurs procédés de production
WO2025101305A1 (fr) Compositions formant une mousse de polyuréthane contenant une hcfo, mousses associées et leurs procédés de production

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24713817

Country of ref document: EP

Kind code of ref document: A1