WO2014133986A1 - Prémélanges de mousse de polyuréthane contenant des agents gonflants oléfiniques halogénés et mousses fabriquées à partir de ceux-ci - Google Patents

Prémélanges de mousse de polyuréthane contenant des agents gonflants oléfiniques halogénés et mousses fabriquées à partir de ceux-ci Download PDF

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Publication number
WO2014133986A1
WO2014133986A1 PCT/US2014/018142 US2014018142W WO2014133986A1 WO 2014133986 A1 WO2014133986 A1 WO 2014133986A1 US 2014018142 W US2014018142 W US 2014018142W WO 2014133986 A1 WO2014133986 A1 WO 2014133986A1
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Prior art keywords
bismuth
polyol premix
catalyst
polyol
catalysts
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PCT/US2014/018142
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English (en)
Inventor
Bin Yu
David J. Williams
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Honeywell International Inc.
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Priority claimed from US14/187,633 external-priority patent/US20140171525A1/en
Application filed by Honeywell International Inc. filed Critical Honeywell International Inc.
Publication of WO2014133986A1 publication Critical patent/WO2014133986A1/fr

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    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0057—Use of organic additives containing antimony, arsenic, or bismuth
    • 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
    • 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
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

Definitions

  • the present invention pertains to polyurethane and polyisocyanurate foams, to foamable compositions, blowing agents and catalyst systems and methods for the preparation thereof.
  • Certain rigid to semi-rigid polyurethane or polyisocyanurate foams have utility in a wide variety of insulation applications including roofing systems, building panels, building envelope insulation, spray applied foams, one and two component froth foams, insulation for refrigerators and freezers, and so called integral skin for applications such as steering wheels and other automotive or aerospace cabin parts, shoe soles, and amusement park restraints.
  • Important to the large-scale commercial acceptance of rigid polyurethane foams is their ability to provide a good balance of properties.
  • many rigid polyurethane and polyisocyanurate foams are known to provide outstanding thermal insulation, excellent fire resistance properties, and superior structural properties at reasonably low densities.
  • Integral skin foams are generally known to produce a tough durable outer skin and a cellular, cushioning core.
  • Blowing agents that have heretofor been used include certain compounds within the general category of compounds including hydrocarbons, fluorocarbons, chlorocarbons,
  • the foam industry has historically used liquid blowing agents that include certain fluorocarbons because of their ease of use and ability to produce foams with superior mechanical and thermal insulation properties. These certain fluorocarbons not only act as blowing agents by virtue of their volatility, but also are encapsulated or entrained in the closed cell structure of the rigid foam and are the major contributor to the low thermal conductivity properties of the rigid urethane foams. These fluorocarbon-based blowing agents also produce a foam having a favorable k-factor.
  • the k-factor is the rate of transfer of heat energy by conduction through one square foot of one-inch thick homogenous material in one hour where there is a difference of one degree Fahrenheit perpendicularly across the two surfaces of the material. Since the utility of closed-cell polyurethane-type foams is based, in part, on their thermal insulation properties, it would be advantageous to identify materials that produce lower k-factor foams.
  • Preferred blowing agents also have low global warmthing potential.
  • hydrohaloolefins including certain hydrofluoroolefins of which trans- 1,3, 3, 3- tetrafluoropropene (1234ze(E)) and l,l,l,4,4,4hexafluorobut-2-ene (1336mzzm(Z)) are of particular interest and hydrochlorofluoroolefins of which l-chloro-3,3,3-trifluoropropene (1233zd) (including both cis and trans isomers and combinations thereof) is of particular interest.
  • Processes for the manufacture of trans-l,3,3,3-tetrafluoropropene are disclosed in U.S. patents 7,230,146 and 7, 189,884.
  • Processes for the manufacture of trans-l-chloro-3,3,3-trifluoropropene are disclosed in U.S. patents 6,844,475 and 6,403,847.
  • the foam formulation is pre-blended into two components.
  • the polyisocyanate and optionally isocyanate compatible raw materials comprising but not limited to certain blowing agents and non-reactive surfactants, comprise the first component, commonly referred to as the "A" component.
  • a polyol or mixture of polyols, one or more surfactant, one or more catalyst, one or more blowing agent, and other optional components including but not limited to flame retardants, colorants, compatibilizers, and solubilizers typically comprise the second component, commonly referred to as the "B" component.
  • polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix for small preparations and, preferably, machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like.
  • other ingredients such as fire retardants, colorants, auxiliary blowing agents, and other polyols can be added to the mixing head or reaction site. Most conveniently, however, they are all incorporated into one B component.
  • foam premix formulations having relatively high concentrations of water tend to not achieve acceptable results in storage stability, in the final foam and/or in the foam processing when certain metal catalysts are utilized.
  • this unexpected problem can be overcome by careful selection of the metal-based catalyst(s), including complexes and/or blends of metal catalyst(s) and amine catalyst(s) to produce highly advantageous and unexpected results, as described further hereinafter.
  • Applicants have found that in certain embodiments a substantial advantage can be achieved in foams, foamable compositions, foam premixes, and associated methods and systems, by the selection of a catalyst system which includes a bismuth-based catalyst.
  • Applicants have surprisingly, and unexpectedly, found that effective amounts of such catalysts result in faster or improved front-end catalytic reactivity, as compared to formulations lacking such a catalyst.
  • such reactivity is measured as decreased cream time of the formulation.
  • the improved cream time demonstrated herein is equated with a faster front-end activity of the compositions herein.
  • blowing agents, foamable compositions, pre-mixes and foams which utilize the bismuth-based catalysts provided herein, either alone or in combination with an amine catalyst and/or additional non- amine catalysts, can improve the foam formation time and/or also extend the shelf life of polyol premixes containing hydrohaloolefins and can improve the quality of the foams produced therefrom.
  • hydrohaloolefins generally, C3 and C4 hydrohaloolefins more preferably, and even more preferably but not limited to 1234ze(E), and/or 1233zd(E), and/or 1336mzzm(Z), and even more preferably with 1233zd(E).
  • Applicants have found that good quality foams can be produced according to the present invention even if the polyol blend has been aged several weeks or months.
  • the present invention relates to foamable compositions and foam premixes including a hydrohaloolefin blowing agent, one or more polyols, one or more surfactants, and a catalyst system comprising a bismuth-based catalyst.
  • a catalyst system comprising a bismuth-based catalyst.
  • Such catalysts system may also include additional amine or non-amine catalysts. In certain aspects, it includes at least one aromatic amine.
  • this invention relates to rigid to semi-rigid, polyurethane and polyisocyanurate foams and methods for their preparation, which are characterized by a fine uniform cell structure and little or no foam collapse.
  • the foams are preferably produced with an organic polyisocyanate and a polyol premix composition which comprises a combination of a blowing agent, which is preferably a hydrohaloolefin, a polyol, a silicone surfactant, and a catalyst system which one or more of the bismuth-based catalysts are included.
  • a blowing agent which is preferably a hydrohaloolefin
  • a polyol preferably a hydrohaloolefin
  • a polyol preferably a silicone surfactant
  • a catalyst system which one or more of the bismuth-based catalysts are included.
  • Such catalyst systems may also include one or more additional amine catalysts and/or additional non-amine catalysts, which may be provided in a minor proportion based on all the catalysts in the system.
  • Figure 1 illustrates comparative cream times of various metal catalysts tested.
  • Figure 2 illustrates a comparative of foam premix stability with various bismuth based catalysts.
  • the present invention in certain aspects, provides polyol premix compositions which comprise a combination of a blowing agent, one or more polyols, one or more silicone surfactants, and a catalyst system including a bismuth-based catalyst.
  • Applicants have surprisingly, and unexpectedly, found that such catalysts, when present in effective amounts, cause the composition to exhibit faster front-end catalytic reactivity. Such reactivity is also surprisingly and unexpectedly maintained as the premix is aged.
  • the compositions of the present invention provide a storage stable premix that is exhibits improved front-end reactivity.
  • the present invention provides polyol premix compositions which comprise a combination of a blowing agent, one or more polyols, one or more silicone surfactants, and a catalyst system.
  • the blowing agent comprises one or more hydrohaloolefins, and optionally a hydrocarbon, fluorocarbon, chlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, halogenated hydrocarbon, ether, ester, alcohol, aldehyde, ketone, organic acid, gas generating material, water or combinations thereof.
  • the catalyst system includes a bismuth-based catalyst system. Such catalysts may be used alone or in combination with other metal and/or amine catalysts. In certain aspects, the catalyst system also includes at least one aromatic amine catalyst.
  • the invention also provides a method of preparing a polyurethane or polyisocyanurate foam comprising reacting an organic polyisocyanate with the polyol premix composition.
  • the blowing agent component comprises a hydrohaloolefin, preferably comprising at least one or a combination of 1234ze(E), 1233zd(E), and isomer blends thereof , and/or 1336mzzm(Z), and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluorochlorocarbon, halogenated hydrocarbon, ether, fluorinated ether, ester, alcohol, aldehyde, ketone, organic acid, gas generating material, water or combinations thereof.
  • a hydrohaloolefin preferably comprising at least one or a combination of 1234ze(E), 1233zd(E), and isomer blends thereof , and/or 1336mzzm(Z)
  • the hydrohaloolefin preferably comprises at least one halooalkene such as a fluoroalkene or chlorofluoroalkene containing from 3 to 4 carbon atoms and at least one carbon- carbon double bond.
  • Preferred hydrohaloolefins non-exclusively include trifluoropropenes, tetrafluoropropenes such as (1234), pentafluoropropenes such as (1225), chlorotrifloropropenes such as (1233), chlorodifluoropropenes, chlorotrifluoropropenes, chlorotetrafluoropropenes, hexafluorobutenes (1336) and combinations of these.
  • the compounds of the present invention are the tetrafluoropropene, pentafluoropropene, and chlorotrifloropropene compounds in which the unsaturated terminal carbon has not more than one F or CI substituent. Included are 1,3,3, 3-tetrafluoropropene (1234ze); 1,1,3,3-tetrafluoropropene; 1,2,3,3,3- pentafluoropropene (1225ye), 1,1,1-trifluoropropene; 1,2,3,3,3-pentafluoropropene, 1,1 , 1,3,3- pentafluoropropene (1225zc) and 1,1,2,3,3-pentafluoropropene (1225yc); (Z)- 1,1 , 1,2,3- pentafluoropropene (1225yez); l-chloro-3,3,3-trifluoropropene (1233zd), 1 ,1 ,1 ,4,4,4- hexa
  • Preferred hydrohaloolefins have a Global Wanning Potential (GWP) of not greater than 150, more preferably not greater than 100 and even more preferably not greater than 75.
  • GWP Global Wanning Potential
  • ODP Ozone Depletion Potential
  • Preferred hydrohaloolefins also preferably have an Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not greater than 0.02 and even more preferably about zero.
  • ODP Ozone Depletion Potential
  • Preferred optional co-blowing agents non-exclusively include water, organic acids that produce CO 2 and/or CO hydrocarbons; ethers, halogenated ethers; esters, alcohols, aldehydes, ketones, pentafluorobutane; pentafluoropropane; hexafluoropropane; heptafluoropropane; trans- 1 ,2 dichloroethylene; methylal, methyl formate; 1 -chloro- 1 ,2,2,2-tetrafluoroethane ( 124); 1, 1- dichloro-l-fluoroethane (141b); 1 ,1,1,2-tetrafluoroethane (134a); 1 ,1,2,2-tetrafluoroethane ( 134); l-chloro 1,1-difluoroethane (142b); 1 ,1, 1 ,3,3-pentafluorobutane (365mfc); 1 , 1, 1, 1, 1, 1,
  • the co-blowing agent(s) include one or a combination of water and/or normal pentane, isopentane or
  • blowing agent component is preferably present in the polyol premix composition in an amount of from about 1 wt.% to about 30 wt.%, preferably from about 3 wt.% to about 30 wt.%, and more preferably from about 5 wt.% to about 25 wt.%, by weight of the polyol premix composition.
  • the hydrohaloolefin component is preferably present in the blowing agent component in an amount of from about 5 wt.% to about 99 wt.%, preferably from about 7 wt.% to about 98 wt.%, and more preferably from about 10 wt.% to about 95 wt.%, by weight of the blowing agent components; and the optional blowing agent is preferably present in the blowing agent component in an amount of from about 95 wt.% to about 1 wt.%, preferably from about 93 wt.% to about 20 wt.%, and more preferably from about 90 wt.% to about 30 wt.%, by weight of the blowing agent components.
  • the polyol component which includes mixtures of polyols, can be any polyol or polyol mixture which reacts in a known fashion with an isocyanate in preparing a polyurethane or polyisocyanurate foam.
  • Useful polyols comprise one or more of a sucrose containing polyol; Mannich polyol; a glucose containing polyol; a sorbitol containing polyol; a methylglucoside containing polyol; an aromatic polyester polyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol; graft copolymers of polyether polyols with a vinyl polymer; a copolymer of a polyether polyol with a polyurea; one or more of (a) condensed with one or more of (b), wherein (a) is selected from glycerine, ethylene glycol, diethylene glycol, trimethylolpropane, ethylene diamine, pentaery
  • composition in an amount of from about 60 wt.% to about 95 wt.%, preferably from about 65 wt.% to about 95 wt.%, and more preferably from about 65 wt.%> to about 80 wt.%>, by weight of the polyol premix composition.
  • the polyol premix composition preferably also contains a silicone surfactant.
  • the silicone surfactant is preferably used to emulsify the polyol preblend mixture, as well as to control the size of the bubbles of the foam so that a foam of a desired cell structure is obtained.
  • a foam with small bubbles or cells therein of uniform size is desired since it has the most desirable physical properties such as compressive strength and thermal conductivity. Also, it is critical to have a foam with stable cells which do not collapse prior to forming or during foam rise.
  • Silicone surfactants for use in the preparation of polyurethane or polyisocyanurate foams are available under a number of trade names known to those skilled in this art. Such materials have been found to be applicable over a wide range of formulations allowing uniform cell formation and maximum gas entrapment to achieve very low density foam structures.
  • the preferred silicone surfactant comprises a polysiloxane polyoxyalkylene block co-polymer.
  • silicone surfactants useful for this invention are Momentive's L-5130, L-5180, L- 5340, L-5440, L-6100, L-6900, L-6980 and L-6988; Air Products DC-193, DC-197, DC-5582 , DC-5357 and DC-5598; and B-8404, B-8407, B-8409 and B-8462 from Evonik Industries AG of Essen, Germany. Others are disclosed in U.S. patents 2,834,748; 2,917,480; 2,846,458 and 4,147,847.
  • the silicone surfactant component is usually present in the polyol premix
  • composition in an amount of from about 0.5 wt.% to about 5.0 wt.%, preferably from about 1.0 wt.% to about 4.0 wt.%, and more preferably from about 1.5 wt.% to about 3.0 wt.%, by weight of the polyol premix composition.
  • the polyol premix composition may optionally contain a non-silicone surfactant, such as a non-silicone, non-ionic surfactant.
  • a non-silicone surfactant such as a non-silicone, non-ionic surfactant.
  • Such may include oxyethylated alkylphenols,
  • non-silicone non-ionic surfactants are Dabco LK-221 or LK-443 which is commercially available from Air Products Corporation, and VORASURFTM 504 from DOW.
  • a non-silicone, non-ionic surfactant used it is usually present in the polyol premix composition in an amount of from about 0.25 wt.% to about 3.0 wt.%, preferably from about 0.5 wt.% to about 2.5 wt.%, more preferably from about 0.75 wt.% to about 2.5 wt. %, and even more preferably from about 0.75 wt.% to about 2.0 wt. %, by weight of the polyol premix composition.
  • the catalyst systems include at least one bismuth-based catalyst. Applicants have surprisingly, and unexpectedly, found that effective amounts of such catalysts result in faster or improved front-end catalytic reactivity, as compared to formulations lacking such a catalyst. As noted herein, the front-end catalytic activity, while not limited thereto, is measured by improved or decreased cream time. As used herein, the "effective amount" of the catalysts may include any amount wherein an improvement of cream time is measurable or detectable, as compared to formulations lacking the catalysts.
  • such catalysts are provided in an amount sufficient to provide a composition exhibiting a cream time of about or less than 10 seconds, in certain preferred aspects of about or less than 8 seconds, in further preferred aspects of about or less than 6 seconds, and in certain preferred aspects of about or less than 5 seconds. In further aspects, such catalysts are provided in an amount sufficient to provide an improved front-end reactivity or cream time of at least 10%, of at least 20%, of at least 30%, relative to compositions lacking the catalysts of the present invention or having a non-bismuth based metal catalyst or any other metal catalyst.
  • cream time means a measure of the beginning of the foam reaction between isocyanates and polyols. It is usually characterized by a change in the liquids color as it begins to rise. That is, it is measured from the mixing of all foam forming
  • compositions of the present invention provide a storage stable premix that is exhibits improved front-end reactivity.
  • bismuth-based catalyst or “bismuth-based metal catalyst,” particularly those that exhibit improved front-end reactivity or cream time, refers to salts, complexes or compositions of the metal bismuth with any organic group.
  • it may be represented by the formula Bi - (R) 3 , wherein each R may be independently selected from the group consisting of comprises a hydrogen, a halide, a hydroxide, a sulfate, a carbonate, a cyanate, a thiocyanate, an isocyanate, a isothiocyanate, a carboxylate, an oxalate, or a nitrate.
  • each R may independently include a substituted or unsubstituted alkyl, heteroalkyl, aryl, or heteroaryl group, including, but not limited to, substituted or unsubstituted alkanes, substituted or unsubstituted alkenes, substituted or unsubstituted alkynes, ketones, aldehydes, esters, ethers, alcohols, alcoholates, phenolates, glycolates, thiolates, carbonates, carboxylates, octoates, hexanoates, amides, amines, imides, imines, sulfides, sulfoxides, phosphates, or combinations thereof, where in certain embodiments, where applicable, such moieties contain between 1-20 carbon atoms, or between 1-10 carbon atoms, and may be optionally substituted at one or more positions.
  • Bi - (R) 3 may form one or a derivative of a bismuth carboxylate, a bismuth octoate, bismuth hexanoate, bismuth 2-ethylhexanoate, a bismuth acetylacetonate, bismuth ethoxide, bismuth propoxide, bismuth butoxide, bismuth isopropoxide, or bismuth butoxide.
  • organic bismuth -based catalysts of the present invention particularly those exhibiting improved front-end reactivity or cream time, include, but are not limited to, those identified by the tradenames Dabco MB20 by Air Products, K- Kat XC C227 by King Industries, Bicat 8210, Bicat 8106, Bicat 8 by Shepherd, Pucat 25 by Nihon agaku Sangyo, U600H by Nitto asei, and Tromax Bismuth 24 by Troy Chemical.
  • Any bismuth-based catalysts of the present invention may be present in the polyol premix composition in an amount of from about 0.001 wt.% to about 5.0 wt.%, 0.01 wt.% to about 4.0 wt.%, preferably from about 0.1 wt.% to about 3.5 wt.%, and more preferably from about 0.2 wt.% to about 3.5 wt. %, by weight of the polyol premix composition. While these are usual amounts, the quantity of the foregoing catalyst can vary widely, and the appropriate amount can be easily be determined by those skilled in the art. Such amounts may be the amounts provided by each individual catalyst provided to the mixture, but in certain preferred aspects total weight of the bismuth-based metal catalysts of the present invention are within these ranges.
  • the catalyst system may include an additional non-amine catalyst and/or amine catalysts.
  • the amine catalysts may include any one or more compounds containing an amino group and exhibiting the catalytic activity provided herein. Such compounds may be liner or branched or cyclic non-aromatic or aromatic in nature.
  • Useful, non-limiting, amines include primary amines, secondary amines or tertiary amines, such as those provided above.
  • Useful tertiary amine catalysts non-exclusively include N,N,N',N",N"- pentamethyldiethyltriamine, N,N-dicyclohexylmethylamine; ⁇ , ⁇ -ethyldiisopropylamine; N- methyldicyclohexylamine (Polycat 12); ⁇ , ⁇ -dimethylcyclohexylamine (Polycat 8);
  • BDMA benzyldimethylamine
  • BDMA benzyldimethylamine
  • N-methyl-N- isopropylbenzylamine N-methyl-N-cyclopentylbenzylamine
  • N-isopropyl-N-sec-butyl- trifluoroethylamine N,N-diethyl-( a -phenylethyl)amine, N,N,N-tri-n-propylamine
  • N,N,N',N',N",N"-pentamethyldiethylenetriamine N,N,N',N',N",N"- pentaethyldiethylenetriamine, N,N,N',N',N",N"-pentamethyldipropylenetriamine, tris-2,4,6- (dimethylaminomethyl)-phenol (DABCO* TMR-30), or combinations thereof.
  • Useful secondary amine catalysts non-exclusively include dicyclohexylamine; t-butylisopropylamine ; di-t- butylamine; cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine; di-( a - trifluoromethylethyl)amine; di-( a -phenylethyl)amine; or combinations thereof.
  • Useful primary amine catalysts non-exclusively include: tnphenylmethylamine and 1, 1-diethyl-n-propylamine.
  • Other useful amines include morpholines, imidazoles, ether containing compounds, and the like. These include: dimo holinodiethylether, N-ethylmorpholine, N-methylmorpholine, bis(dimethylaminoethyl) ether, imidizole, 1,2 Dimethylimidazole (Toyocat DM 70 and
  • DABCO ® 2040 n-methylimidazole, 1 ,2-dimethylimidazole, dimorpholinodimethylether, 2,2- dimo holinodiethylether (DMDEE), bis(diethylaminoethyl) ether, bis(dimethylaminopropyl) ether.
  • the catalyst may be provided in any amount to achieve the function of the instant invention without affecting the foam forming or storage stability of the composition, as characterized herein.
  • the amine catalyst may be provided in amounts less than or greater than the non-amine catalyst.
  • each R may be independently selected from the group consisting of comprises a hydrogen, a halide, a hydroxide, a sulfate, a carbonate, a cyanate, a thiocyanate, an isocyanate, a isothiocyanate, a carboxylate, an oxalate, or a nitrate.
  • each R may independently include a substituted or unsubstituted alkyl, heteroalkyl, aryl, or heteroaryl group, including, but not limited to, substituted or unsubstituted alkanes, substituted or unsubstituted alkenes, substituted or unsubstituted alkynes, ketones, aldehydes, esters, ethers, alcohols, alcoholates, phenolates, glycolates, thiolates, carbonates, carboxylates, octoates, hexanoates, amides, amines, imides, imines, sulfides, sulfoxides, phosphates, or combinations thereof, where in certain embodiments, where applicable, such moieties contain between 1-20 carbon atoms, or between 1-10 carbon atoms, and may be optionally substituted at one or more positions.
  • At least one R forms an aryl or heteroaryl aromatic ring structure, such as, but not limited to a benzene ring, or derivative thereof, which may be optionally substituted with one or a combination of any of the foregoing substitutent groups defined by R above.
  • R includes one or more of a benzene, aniline, toluene, phenyl, benzidine, benzophenone, imidazole, aminoimidazole, pyridine, or combinations thereof, each of which may be optionally substituted with one or a combination of the foregoing substitutent groups defined by R above.
  • non-limiting aromatic amines of the present invention include aniline, fluoroaniline, chloroaniline, bromoaniline, nitroaniline, aminotoluene, fluoroaminotoluene, chloroaminotoluene, bromoaminotoluene, nitroaminotoluene, diaminobenzene,
  • fluorodiaminobenzene chlorodiaminobenzene, bromodiaminobenzene, nitrodiaminobenzene, diaminotoluene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine,
  • aromatic amines may also include those under the tradenames ETHACURE® 100 and ETHACURE® 300.
  • R' comprises a heteroaryl ring moiety having at least one of N, O, or S, and from 2-20 carbon atoms, in certain aspects from 2-10 carbon atoms, and in further aspects from 2-6 carbon atoms.
  • R' may include an aminoimidazole or aminopyridine.
  • the R' heteroaryl ring may be optionally substituted at one or more positions around the ring by a substituent group, such as those defined by R above.
  • the catalyst system of the present invention may also includes at least one non-amine catalyst.
  • the non-amine catalysts are inorgano- or organo-metallic compounds.
  • Useful inorgano- or organo-metallic compounds include, but are not limited to, organic salts, Lewis acid halides, or the like, of any metal, including, but not limited to, transition metals, post-transition metals, rare earth metals (e.g. lanthanides), metalloids, alkali metals, alkaline earth metals, or the like.
  • the metals may include, but are not limited to, bismuth, lead, tin, zinc, chromium, cobalt, copper, iron, manganese, magnesium, potassium, sodium, titanium, mercury, antimony, uranium, cadmium, thorium, aluminum, nickel, cerium, molybdenum, vanadium, zirconium, or combinations thereof.
  • Non-exclusive examples of such inorgano- or organo-metallic catalysts include, but are not limited to, bismuth 2- ethylhexanote, bismuth nitrate, lead 2-ethylhexoate, lead benzoate, lead naphthanate, ferric chloride, antimony trichloride, antimony glycolate, tin salts of carboxylic acids, dialkyl tin salts of carboxylic acids, sodium acetate, potassium octoate, potassium 2-ethylhexoate, potassium salts of carboxylic acids, zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts, alkali metal carboxylic acid salts, sodium N-(2-hydroxy-5-nonylphenol)methyl-N- methylglycinate, tin (II) 2-ethylhexanoate, dibutyltin dilaurate, or combinations thereof.
  • the catalysts are present in the polyol premix composition in an amount of from about 0.001 wt.% to about 5.0 wt.%, 0.01 wt.% to about 4.0 wt.%, preferably from about 0.1 wt.% to about 3.5 wt.%, and more preferably from about 0.2 wt.% to about 3.5 wt. %, by weight of the polyol premix composition. While these are usual amounts, the quantity amount of the foregoing catalyst can vary widely, and the appropriate amount can be easily be determined by those skilled in the art.
  • the non-amine catalyst is a quaternary ammonium carboxylate.
  • Useful quaternary ammonium carboxylates include, but are not limited to: (2-hydroxypropyl)trimethylammonium 2-ethylhexanoate (TMR ® sold by Air Products and Chemicals) and (2-hydroxypropyl)trimethylammonium formate (TMR-2 ® sold by Air Products and Chemicals).
  • These quaternary ammonium carboxylate catalysts are usually present in the polyol premix composition in an amount of from about 0.25 wt.% to about 3.0 wt.%, preferably from about 0.3 wt.% to about 2.5 wt.%, and more preferably from about 0.35 wt.% to about 2.0 wt. %, by weight of the polyol premix composition. While these are usual amounts, the quantity amount of catalyst can vary widely, and the appropriate amount can be easily be determined by those skilled in the art.
  • metal catalysts are nonreactive with halogenated olefins that are adaptable for use as blowing agents and therefore appear to produce a relatively stable system, and that with a judicious selection of a metal catalyst surprisingly effective and stable compositions, systems and methods can be obtained.
  • polyurethane or polyisocyanurate foams using the compositions described herein may follow any of the methods well known in the art can be employed, see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and technology, 1962, John Wiley and Sons, New York, N.Y. or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, N.Y. or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, OH.
  • polyurethane or polyisocyanurate foams are prepared by combining an isocyanate, the polyol premix
  • foams can be rigid, flexible, or semi-rigid, and can have a closed cell structure, an open cell structure or a mixture of open and closed cells.
  • the foam formulation is pre-blended into two components.
  • the isocyanate and optionally other isocyanate compatible raw materials including but not limited to blowing agents and certain silicone surfactants, comprise the first component, commonly referred to as the "A” component.
  • the polyol mixture composition, including surfactant, catalysts, blowing agents, and optional other ingredients comprise the second component, commonly referred to as the "B" component.
  • the "B" component may not contain all the above listed components, for example some formulations omit the flame retardant if flame retardancy is not a required foam properly.
  • polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix for small preparations and, preferably, machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like.
  • other ingredients such as fire retardants, colorants, auxiliary blowing agents, water, and even other polyols can be added as a stream to the mix head or reaction site. Most conveniently, however, they are all incorporated into one B component as described above.
  • a foamable composition suitable for forming a polyurethane or polyisocyanurate foam may be formed by reacting an organic polyisocyanate and the polyol premix composition described above. Any organic polyisocyanate can be employed in polyurethane or
  • polyisocyanurate foam synthesis inclusive of aliphatic and aromatic polyisocyanates.
  • Suitable organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates which are well known in the field of polyurethane chemistry. These are described in, for example, U.S. patents 4,868,224; 3,401 ,190; 3,454,606; 3,277,138; 3,492,330; 3,001,973; 3,394,164; 3,124.605; and 3,201,372.
  • Preferred as a class are the aromatic polyisocyanates.
  • R is a polyvalent organic radical which is either aliphatic, aralkyl, aromatic or mixtures thereof, and z is an integer which corresponds to the valence of R and is at least two.
  • organic polyisocyanates contemplated herein includes, for example, the aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate and the like; the aromatic triisocyanates such as 4,4',4"- triphenylmethane triisocyanate, 2,4,6-toluene triisocyanates; the aromatic tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'5,5-'tetraisocyanate, and the like; arylalkyl polyisocyanates such as xylylene diisocyanate; aliphatic polyisocyanate such as hexamethylene-l ,6-d
  • organic polyisocyanates include polymethylene polyphenylisocyanate, hydrogenated methylene diphenylisocyanate, m- phenylene diisocyanate, naphthylene-l,5-diisocyanate, l-methoxyphenylene-2,4-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'- biphenyl diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate;
  • Typical aliphatic polyisocyanates are alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, isophorene diisocyanate, 4, 4'- methylenebis(cyclohexyl is
  • Preferred polyisocyanates are the polymethylene polyphenyl isocyanates, Particularly the mixtures containing from about 30 to about 85 percent by weight of methylenebis(phenyl isocyanate) with the remainder of the mixture comprising the polymethylene polyphenyl polyisocyanates of functionality higher than 2.
  • These polyisocyanates are prepared by conventional methods known in the art.
  • the polyisocyanate and the polyol are employed in amounts which will yield an NCO/OH stoichiometric ratio in a range of from about 0.9 to about 5.0.
  • the NCO/OH equivalent ratio is, preferably, about 1.0 or more and about 3.0 or less, with the ideal range being from about 1.1 to about 2.5.
  • trimerization catalysts are used for the purpose of converting the blends in conjunction with excess A component to polyisocyanurate- polyurethane foams.
  • the trimerization catalysts employed can be any catalyst known to one skilled in the art, including, but not limited to, glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates, and alkali metal carboxylic acid salts and mixtures of the various types of catalysts.
  • Preferred species within the classes are sodium acetate, potassium octoate, and sodium N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.
  • Optional flame retardants can also be incorporated, preferably in amount of not more than about 20 percent by weight of the reactants.
  • Optional flame retardants include tris(2- chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, tris(l,3-dichloropropyl)phosphate, tri(2-chloroisopropyl)phosphate, tricresyl phosphate, tri(2,2- dichloroisopropyl)phosphate, diethyl N,N-bis(2-hydroxyethyl) aminomethylphosphonate, dimethyl methylphosphonate, tri(2,3-dibromopropyl)phosphate, tri( 1 ,3- dichloropropyl)phosphate, and tetra-kis-(2-chloroethyl)ethylene diphosphate, triethylphosphate, N-Methylol dimethylphosphonopro
  • Other optional ingredients can include from 0 to about 7 percent water, which chemically reacts with the isocyanate to produce carbon dioxide.
  • This carbon dioxide acts as an auxiliary blowing agent.
  • Formic acid is also used to produce carbon dioxide by reacting with the isocyanate and is optionally added to the
  • Bcomponent In addition to the previously described ingredients, other ingredients such as, dyes, fillers, pigments and the like can be included in the preparation of the foams. Dispersing agents and cell stabilizers can be incorporated into the present blends.
  • Conventional fillers for use herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fibers, carbon black and silica.
  • the filler, if used, is normally present in an amount by weight ranging from about 5 parts to 100 parts per 100 parts of polyol.
  • a pigment which can be used herein can be any conventional pigment such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, iron blue siennas, molybdate oranges and organic pigments such as para reds, benzidine yellow, toluidine red, toners and phthalocyanines.
  • the polyurethane or polyisocyanurate foams produced can vary in density from about 0.5 pounds per cubic foot to about 60 pounds per cubic foot, preferably from about 1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to 6.0 pounds per cubic foot.
  • the density obtained is a function of how much of the blowing agent or blowing agent mixture disclosed in this invention plus the amount of auxiliary blowing agent, such as water or other co- blowing agents is present in the A and / or B components, or alternatively added at the time the foam is prepared.
  • These foams can be rigid, flexible, or semi-rigid foams, and can have a closed cell structure, an open cell structure or a mixture of open and closed cells. These foams are used in a variety of well known applications, including but not limited to thermal insulation, cushioning, flotation, packaging, adhesives, void filling, crafts and decorative, and shock absorption.
  • a resin with a formulation in Table 1 was prepared.
  • Various metal catalysts including bismuth, cobalt, tin, zinc, manganese, titanium, zirconium, iron, were tested in the polyol preblend.
  • the polyol blend 50°F was then reacted with equal amount of isocyanate Lupranate M20 at 70°F.
  • the cream time was recorded and was based on the interval of time between mixing together the polyol and diisocyante and the change in the color of the liquid as the mixture begins to rise.
  • Bismuth catalysts also display good stability in well-designed resin system.
  • Toyocat DM70 as the gelling catalysts which is not a front- end catalyst
  • Dabco K15 as the trimer catalyst which is good for back-end cure
  • the initial reactivity of such resin system was measured by reacting the freshly prepared resin at 50°F with equal amount of isocyanate Lupranate M20 at 70°F.
  • the aged reactivity was measured similarly, e.g. by reacting the resin (50°F) which has been aged at room temperature for a predetermined time, with Lupranate M20 at 70°F.
  • Example 2 is repeated using Dabco MB20, Bicat 8, and Bicat 8210.
  • the initial reactivity of such resin system is measured by reacting the freshly prepared resin at 50°F with equal amount of isocyanate Lupranate M20 at 70°F.
  • the aged reactivity is measured similarly, by reacting the resin (50°F) which is aged at room temperature for a predetermined time, with Lupranate M20 at 70°F.
  • Applicants also discovered that the front-end reactivity can be further improved by using an additive, Ethacure 100, without affecting the stability of the system, even though this additive is a primary amine. That is, in the following experiments Toyocat DM70 was used as the gelling catalyst, which is not a front-end catalyst, and Dabco K15 as the trimer catalyst which is good for back-end cure. These were provided with the additive Ethacure 100, a primary aromatic amine, and the bismuth catalyst Pucat 25. (Table 3).
  • the cream time was 5 seconds when the resin containing a catalyst package of Toyocat DM 70, Dabco K15 and Pucat 25, reacted with equal amount of isocyanate Lupranate M20 at 70°F .
  • the cream time decreased when Ethacure 100 was used in the resin system. Meanwhile the resin system maintained its reactivity after aging. Meanwhile, when the tin catalyst Dabco 120 was used instead of the strong front-end bismuth catalyst, the cream time is much longer, as shown in formulation D and E.
  • the bismuth-based catalysts exhibited stability and faster cream time when used with the aromatic amine.
  • Example 4 was repeated using each of the bismuth catalysts U 600H, Bicat 8106, K kcatXC C227, Dabco MB20, and Bicat 8. Consistent with the foregoing, the cream time is accelerated and within commercially tolerable levels, when reacted with equal amounts of isocyanate Lupranate M20 at 70°F. The cream time is also accelerated and the composition stable when Ethacure 100 is used in the resin system.
  • Strong front-end reactivity can be achieved by using different amine catalysts, different metal catalysts (other than bismuth) along with the bismuth catalysts. That is, in the following experiments strong front-end bismuth catalyst Bicat 8210 was used along with trimer catalyst Dabco K15 and a gelling amine catalyst Toyocat DM 70 (lower dose compared with those in Example 4) were used. Zinc-based catalyst blend K-KAT XK 617, which is not a front-end metal catalyst, is also used. Short cream time can be obtained with such a catalyst package. This cream time can be further improved by addition the aromatic amine Ethacure 100 or a weak amine catalyst DMDEE.
  • Example 6 is repeated using the bismuth-based catalysts Dabco MB20, k Kat XC C227, Bicat 8106, Bicat 8, Pucat 25, and U600H.
  • the strong front-end reactivity is similarly achieved using different amine catalysts and different metal catalysts (other than bismuth) along with the bismuth catalysts. That is, these bismuth catalysts are each used along with trimer catalyst Dabco K15 and a gelling amine catalyst Toyocat DM 70 (lower dose compared with those in Example 4) is used.
  • Zinc-based catalyst blend K-KAT XK 617 which is not a front-end metal catalyst, is also used. Short cream time is obtained with such a catalyst package. This cream time is further improved by addition the aromatic amine Ethacure 100 or a weak amine catalyst DMDEE.

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Abstract

L'invention concerne des compositions de prémélange de polyols et des mousses formées à partir de celles-ci, qui comprennent une combinaison d'un agent gonflant hydrohalogénooléfinique, d'un polyol, d'un tensioactif siliconé et d'un système catalytique qui inclut un catalyseur métallique à base de bismuth. Ces catalyseurs peuvent être utilisés seuls ou en combinaison avec un catalyseur de type amine et/ou d'autres catalyseurs qui ne sont pas de type amine.
PCT/US2014/018142 2013-02-26 2014-02-25 Prémélanges de mousse de polyuréthane contenant des agents gonflants oléfiniques halogénés et mousses fabriquées à partir de ceux-ci WO2014133986A1 (fr)

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US14/187,633 US20140171525A1 (en) 2011-02-21 2014-02-24 Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same

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WO2018022405A1 (fr) * 2016-07-25 2018-02-01 Covestro Llc Compositions formant des mousses de polyuréthane, procédés de fabrication de mousses de faible densité à l'aide de telles compositions et mousses formées à partir de celles-ci
CN109294218A (zh) * 2018-09-28 2019-02-01 上海东大聚氨酯有限公司 组合聚醚、聚氨酯泡沫原料组合物、源自其的聚氨酯泡沫及其制备方法和应用
EP3638707A4 (fr) * 2017-06-13 2021-01-20 Honeywell International Inc. Formulation de mousse perfectionnée
EP3679108A4 (fr) * 2017-09-05 2021-05-19 Huntsman Petrochemical LLC Système catalyseur destiné à des prémélanges de polyols contenant des agents d'expansion d'hydrohalooléfine
US11236192B2 (en) 2015-09-30 2022-02-01 Sekisui Chemical Co., Ltd. Flame-retardant rigid polyurethane foam
US11767394B2 (en) 2021-12-09 2023-09-26 Covestro Llc HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production
US11767407B1 (en) 2022-04-21 2023-09-26 Covestro Llc HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production
US11905707B2 (en) 2021-06-29 2024-02-20 Covestro Llc Foam wall structures and methods for their manufacture

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WO2012170912A2 (fr) * 2011-06-08 2012-12-13 Honeywell International Inc. Prémélanges de mousse de polyuréthane contenant des agents gonflants d'oléfine halogénés et des mousses fabriquées à partir de ceux-ci

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
US11236192B2 (en) 2015-09-30 2022-02-01 Sekisui Chemical Co., Ltd. Flame-retardant rigid polyurethane foam
WO2018022405A1 (fr) * 2016-07-25 2018-02-01 Covestro Llc Compositions formant des mousses de polyuréthane, procédés de fabrication de mousses de faible densité à l'aide de telles compositions et mousses formées à partir de celles-ci
EP3638707A4 (fr) * 2017-06-13 2021-01-20 Honeywell International Inc. Formulation de mousse perfectionnée
EP3679108A4 (fr) * 2017-09-05 2021-05-19 Huntsman Petrochemical LLC Système catalyseur destiné à des prémélanges de polyols contenant des agents d'expansion d'hydrohalooléfine
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CN109294218A (zh) * 2018-09-28 2019-02-01 上海东大聚氨酯有限公司 组合聚醚、聚氨酯泡沫原料组合物、源自其的聚氨酯泡沫及其制备方法和应用
US11905707B2 (en) 2021-06-29 2024-02-20 Covestro Llc Foam wall structures and methods for their manufacture
US11767394B2 (en) 2021-12-09 2023-09-26 Covestro Llc HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production
US11767407B1 (en) 2022-04-21 2023-09-26 Covestro Llc HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production

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