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WO2025132927A1 - Compositions d'additifs de mousse de polyuréthane - Google Patents

Compositions d'additifs de mousse de polyuréthane Download PDF

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Publication number
WO2025132927A1
WO2025132927A1 PCT/EP2024/087610 EP2024087610W WO2025132927A1 WO 2025132927 A1 WO2025132927 A1 WO 2025132927A1 EP 2024087610 W EP2024087610 W EP 2024087610W WO 2025132927 A1 WO2025132927 A1 WO 2025132927A1
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WIPO (PCT)
Prior art keywords
polyols
polyurethanes
polyurethane
composition according
previous
Prior art date
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PCT/EP2024/087610
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English (en)
Inventor
Antonie-Gabriel KISS
Lijun Feng
Sebastian GISBERTZ
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Momentive Performance Materials GmbH
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Momentive Performance Materials GmbH
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Publication of WO2025132927A1 publication Critical patent/WO2025132927A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0016—Foam properties semi-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
    • C08G2110/0025—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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to polyurethane foam additive compositions, comprising one or more polyurethane foaming additives, a recycling product of a polyurethane foam, which comprises one or more polyols, and optionally one or more chemical compounds, such as in particular, (virgin) polyols, which are not obtained by the recycling of polyurethane foams, which is suitably a non-curable additive composition, a process for the manufacture of the polyurethane foam additive compositions, curable compositions comprising the polyurethane foam additive compositions and one or more polyisocyanates, polyurethanes obtained from such curable compositions, the use of the polyurethane foam additive compositions for the manufacture of polyurethane foams, a process for the manufacture of polyurethane foams using said polyurethane foam additive compositions and the use of a recycling product of a polyurethane foam comprising one or more polyols, as a functional solvent for polyurethane foaming additives.
  • Polyurethane is a thermoset material. It is impossible to recycle it as it is done with thermoplastic materials.
  • chemical processing chemolysis
  • Polyurethane foam waste is produced in order to generate recycled raw materials for polyurethane foam.
  • Different chemolysis approaches are known in the art (see e.g. Martin B. Johansen, Bjarke S. Donslund, Steffan K. Kristensen, Anders T.
  • Additives in polyurethane formation generally include certain amounts of functional solvents. These are typically small molecule glycols, such as diethylene glycol and dipropylene glycol, which are normally obtained from petrochemicals.
  • Polyol compositions comprising polyurethane foaming additives used in the manufacture of polyurethane foams are known (see e.g. US 2011/196055 A1 , US 2013/243986 A1 US 2010/152312 A1, EP 3594255A1 , US 2019/136005 A1 , US 2018/079881 A1 , US 2014/005288 and US 2020/247938 A1), but these polyol compositions do not contain any polyurethane recycling products.
  • the object underlying the invention was therefore in particular also to find a new polyurethane foam additive composition which leads to improved polyurethane foams in the manufacture of which they are used.
  • polyurethane foam additive compositions comprising a recycling product (C) from polyurethane foams, comprising one or more polyols, and one or more polyurethane foaming additives (B), which polyurethane foam additive compositions can be used directly to make polyurethane foams which are surprisingly improved in their mechanical properties.
  • the recycling product (C) from polyurethane foams containing one or more polyols can thus serve as a functional solvent for polyurethane foam additives (B) such as silicone surfactants, catalyst additives and the like, thereby replacing other conventional solvents for petrochemical-based additives and recycling polyurethane waste material.
  • This inventive approach fulfils the requirements for polyurethane foam life cycle, reduces the consumption of virgin petroleum and surprisingly improves the mechanical properties of polyurethane foams prepared by using the inventive compositions.
  • composition comprising:
  • compositions of the present invention comprise
  • composition 20 to 60 pw of a recycling product of a polyurethane foam comprising one or more polyols, with the amount of the polyurethane foaming additives (B) being at least 5 wt.-%, preferably at least 10 wt.-%, more preferably at least 20 wt.-%, based on the total weight of the composition.
  • the composition further comprises one or more chemical compounds (A), other than components (B) or (C).
  • Component (A) includes, in particular, virgin polyols, which are not obtained by the recycling of polyurethane foams.
  • Component (A) one or more chemical compounds, other than components (B) or (C).
  • Component (A) includes, in particular, so to say virgin polyols, which are not obtained by the recycling of polyurethane foams.
  • virgin polyols which are not obtained by the recycling of polyurethane foams.
  • the term of “consisting of” does not exclude the presence of any non-functional amounts of other components such as impurities.
  • components (A) When components (A) are selected from virgin polyols, which are not obtained by the recycling of polyurethane foams, components (A) include, in particular, conventional polyols and mixtures thereof used in the manufacture of polyurethanes, and polyurethane foams, in particular (see e.g. Polyurethanes Science, Technology, Markets, and Trends, Mark F. Sonnenschein, Ph.D, Wiley 2015). These polyols (A) differ in their chemical compositions from (C), the recycling product of a polyurethane foam comprising one or more polyols, in particular, in that they do not contain any additional components that result from the recycling of polyurethanes such as polyurethane foams.
  • recycling materials from polyurethanes inter alia may comprise, in particular, fillers which are still present in the recycled polyol product (C) used in the present invention.
  • the polyols (A) in particular do not contain such filler materials and are used in commercial purity grades of at least 95 wt- %.
  • polystyrene resins used as component (A) do not contain any compounds derived from polyisocyanates in particular from aromatic polyisocyanates such as toulenediamine, methylene diphenyl diamine and its derivates which are used in the manufacture of polyurethane foams, and which are usually contained in the component (C), the recycling products of one or more polyurethanes comprising one or more polyols, as will be explained in more detail below.
  • the “virgin” polyols as component (A) also often have a lower kinematic viscosity than component (C), the recycling product of a polyurethane comprising one or more polyols.
  • the kinematic viscosity of component (C) can be e.g. at least about 5-times, preferably at least about 10-times, more preferably at least about 15-times, still more preferably at least about 20-times higher than the viscosity of component (A).
  • the kinematic viscosity of component (A) is preferably in the range of about 200 to 1500 cSt (25°C), preferably about 300 to about 1000 cSt (25°C).
  • polyols (A) e.g. polyols (polyether polyols, polyester polyols, copolymer polyols also known as graft polyols) can be used.
  • the polyol (A) is a polyol having a hydroxyl number from about 10 to about 700 [see e.g. Chemistry and Technology of Polyols for Polyurethanes, by Mihail lonescu, Rapra Technology LTD. (2005)].
  • Polyols which are useful in the composition of the invention and for making a polyurethanes, particularly via the one-shot foaming procedure are any of the types presently employed in the art for the preparation of flexible slabstock foams, flexible molded foams, semi-flexible foams, and rigid foams.
  • Such polyols are typically liquids at ambient temperatures and pressures and include polyether polyols and polyester polyols having hydroxyl numbers in the range of from about 15 to about 700.
  • the hydroxyl numbers are preferably between about 20 to about 60 for flexible foams, between about 100 to about 300 for semi-flexible foams and between about 250 to about 700 for rigid foams.
  • the preferred functionality, i.e. the average number of hydroxyl groups per molecule of polyol, of the polyols is about 2 to about 4 and most preferably about 2.3 to about 3.5.
  • the preferred functionality is about 2 to about 8 and most preferably about 3 to about 5.
  • compositions of the invention include as polyol (A) for example any of the following nonlimiting classes of polyols:
  • polyether polyols derived from the reaction of polyhydroxyalkanes with one or more alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.;
  • polyether polyols derived from the reaction of high-functionality alcohols, sugar alcohols, saccharides and/or high functionality amines, if desired in admixture with low-functionality alcohols and/or amines with alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.;
  • polyether polyols derived from the reaction of phosphorus and polyphosporus acids with alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.,
  • polyether polyols derived from the reaction of polyaromatic alcohols with alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.;
  • polyether polyols derived from the reaction of ammonia and/or an amine with alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.;
  • polyester polyols derived from the reaction of a polyfunctional initiator, e.g. a diol, with a hydroxycarboxylic acid or lactone thereof, e.g. hydroxylcaproic acid or s-caprolactone;
  • a polyfunctional initiator e.g. a diol
  • a hydroxycarboxylic acid or lactone thereof e.g. hydroxylcaproic acid or s-caprolactone
  • polyoxamate polyols derived from the reaction of an oxalate ester and a diamine, e.g. hydrazine, ethylenediamine, etc. directly in a polyether polyol;
  • polyurea polyols derived from the reaction of a diisocyanate and a diamine, e.g. hydrazine, ethylenediamine, etc. directly in a polyether polyol.
  • alkylene oxide adducts of polyhydroxyalkanes are the ethylene oxide and propylene oxide adducts of aliphatic triols such as glycerol, trimethylol propane, etc.
  • the preferred class of alkylene oxide adducts are the ethylene oxide and propylene oxide adducts of ammonia, toluene diamine, sucrose, and phenol- formaldehyde-amine resins (Mannich bases).
  • Grafted or polymer polyols are used extensively in the production of flexible foams and are, along with standard polyols, one of the preferred class of polyols useful in this invention.
  • Polymer polyols are polyols that contain a stable dispersion of a polymer, for example in the polyols a) to e) above and more preferably the polyols of type a).
  • Other polymer polyols useful in this invention are polyurea polyols and polyoxamate polyols.
  • polyesterols and/or polyetherols are preferred polyols (A).
  • the average hydroxy-functionality of the polyetherols and/or polyesterols is generally from 1.9 to 8, preferably from 2.4 to 7, particularly preferably from 2.6 to 6.
  • the hydroxy-functionality of the starter molecules is assumed to calculate the average functionality.
  • the polyols (A) suitably have a hydroxyl number of generally greater than 20 mg KOH/g, preferably greater than 30 mg KOH/g, particularly preferably greater than 40 mg KOH/g.
  • 700 mg KOH/g preferably 600 mg KOH/g, particularly 500 mg KOH/g, very particularly 400 mg KOH/g, has generally been found to be an appropriate upper limit to the hydroxyl number.
  • the OH numbers indicated above relate to the totality of the polyols (A), which does not preclude individual constituents of the mixture from having higher or lower values.
  • the number-average molecular weight of the polyols (A) is preferably greater than 400 g/mol.
  • Component (A) preferably comprises polyether polyols which are produced by known methods, for example from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical by anionic polymerization using alkali metal hydroxides such as sodium or potassium hydroxide or alkali alkoxides such as sodium methoxide, sodium or potassium ethoxide or potassium isopropoxide as catalysts and with addition of at least one starter molecule comprising from 2 to 8, preferably from 3 to 8, reactive hydrogen atoms in bound form or by cationic polymerization using Lewis acids such as antimony pentachloride, boron fluoride etherate, etc., or bleaching earth as catalysts.
  • alkali metal hydroxides such as sodium or potassium hydroxide or alkali alkoxides
  • sodium methoxide sodium or potassium ethoxide or potassium isopropoxide
  • starter molecule comprising from 2 to 8, preferably from 3 to 8, reactive hydrogen atoms in bound form or by cationic
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1 ,3-propylene oxide, 1 ,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1 ,2-propylene oxide.
  • the alkylene oxides may be used individually, alternately in succession or as mixtures.
  • Possible starter molecules are alcohols such as glycerol, trimethylolpropane (TMP), pentaerythritol, sugar compounds such as sucrose, sorbitol and also amines such as methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine (TDA), naphthylamine, ethylenediamine (EDA), diethylenetriamine, 4,4'-methylenedianiline, 1 ,3-propanediamine, 1 ,6- hexanediamine, ethanolamine, diethanolamine, triethanolamine and the like.
  • TMP trimethylolpropane
  • pentaerythritol sugar compounds
  • sugar compounds such as sucrose
  • sorbitol and also amines such as methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, tol
  • condensation products of formaldehyde, phenol and diethanolamine or ethanolamine, formaldehyde, alkylphenols and diethanolamine or ethanolamine, formaldehyde, bisphenol A and diethanolamine or ethanolamine, formaldehyde, aniline and diethanolamine or ethanolamine, formaldehyde, cresol and diethanolamine or ethanolamine, formaldehyde, toluidine and diethanolamine or ethanolamine and formaldehyde, toluenediamine (TDA) and diethanolamine or ethanolamine and the like can be used as starter molecules. Preference is given to using glycerol, sucrose, sorbitol and TDA as starter molecule.
  • Such polyols are commercially available for example under the trademark Voranol® from Dow Corning such a VORANOLTM 3322 Polyol (nominal 3400 molecular weight, heteropolymer triol), and others, such as RENUVATM FF 60, VORANOLTM 3010, VORANOLTM 3010A, VORANOLTM 3011 , VORANOLTM 3022J, VORANOLTM 3322, VORANOLTM 3535,
  • VORANOLTM 4730-N VORANOLTM 8010, VORANOLTM 8010A, VORANOLTM 8010G, VORANOLTM 8022, VORANOLTM 8136, VORANOLTM 8322, VORANOLTM 8595,
  • Preferred components (A) also include glycols such as hexylene glycol, dipropylene glycol, diethylene glycol, mono propylene glycol, mono ethylene glycol, methylpentanediol, methylpropanediol, etc.
  • component (A) is selected from aliphatic polyols, i.e. non-aromatic polyols.
  • the polyurethane foaming additives (B) are conventional polyurethane foaming additives, and include products, which help in particular polyurethane foam processing at low dosage levels, typically only several weight part per hundred polyol.
  • the polyurethane foaming additives (B) include, in particular, any functional additive used in polyurethane foaming apart or different from the components which are essentially involved in the polyurethane chain growth formation reaction, that is, the polyisocyanate and the polyfunctional isocyanate-reactive components, in particular the polyol components.
  • Such functional additive for polyurethane foaming processing include e.g. chemical reaction control agents, foam cell structure control agents and foam performance control agents.
  • the polyurethane foaming additives (B) further include, for example, catalysts, such as amine catalysts and metal catalysts, surfactants, preferably silicone-based surfactants, flame or fire retardants such as chlorinated phosphate esters, chlorinated paraffins, and melamine powders; chain extenders, chain-terminators, crosslinking agents, adhesion promoters, anti-static additives, hydrolysis stabilizers, light stabilizers, such as Ultraviolet Light Absorbers (UVAs), Hindered Amine Light Stabilizers (HALS); lubricants, anti-microbial agents, processing aid additives, anti-oxidants, such hindered phenols and hindered amine stabilizers, phosphites, hydroxylamines, lactone based stabilizers; defoamers, anti-foaming agents, emission control agents (such as disclosed in WO23034354A1 included herein by reference to such document) water scavengers, molecular sieves,
  • polyurethane foaming additives (B) are selected from the group consisting of:
  • Catalysts such as amine catalysts
  • Surfactants preferably silicone-based surfactants, Metal catalysts, Flame lamination additives, Antioxidants, and Processing aid additives.
  • the polyurethane foaming additives (B) are selected from the group consisting of catalysts such amine catalysts and silicone-based surfactants.
  • Particularly preferred additives (B) include amine catalysts for the formation of polyisocyanate polyaddition products, such as amines different from the isocyanate-reactive compounds used for the polyurethane formation.
  • catalysts include alkyl amines such as bis(2- dimethylaminoethyl)ether, N , N-dimethylcyclohexylamine, N , N , N’, N’, N”- pentamethyldiethylenetriamine, N,N,N’,N’,N”-pentamethyldipropylenetriamine triethylenediamine, ethanol amines, such as 2-aminoethanol, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N- methylethanolamine, N-ethylethanolamine, diisopropylamine, bis(2-hydroxypropyl)amine, 2- [2-(dimethylamino)ethoxy]ethanol,
  • amines include alkyl amines, such as bis(2-dimethylaminoethyl)ether, N,N- dimethylaminopropylamine, N,N-dimethylcyclohexylamine, N,N,N’,N’,N”- pentamethyldiethylenetriamine, triethylenediamine, ethanol amines, such as diethanolamine, 2(2-dimethylaminoethoxy)ethanol, N-[2-(dimethylamino)ethyl]-N-methylethanolamine, dimethylethanolamine, or other amines such as 3-dimethylamino-N,N-dimethylpropionamide and N-ethylmorpholine, triethanolamine, 2-dimethylaminoethanol, N,N-
  • Such amine catalysts are commercially available, e.g. as shown in the following: 2,4,6-Tris(Dimethylaminomethyl)phenol (DABCO TMR-30; JEFFCAT TR30; RC Catalyst 6330), N,N,N’,N’-Tetramethyl-1,3-butanediamine (TMBDA), N,N-Dimethylcyclohexylamine (POLYCAT 8; JEFFCAT DMCHA), N,N-Diethylethanolamine (DEEA), N-Ethylmorpholine (JEFFCAT NEM; TOYOCAT NEM; RC Catalyst 6072), 1-azabicyclo[2.2.2]octane (QUINICLIDINE), Triethanolamine (TEA), N,N,4-Trimethyl-1-piperazineethanamine (TOYOCAT -NP), N,N’-Dimethylpiperazine (JEFFCAT DMP; RC Catalyst 6117), Dimethylethanolamine (DABCO
  • DIME 12 N-[2-(dimethylamino)ethyl]-N-methylethanolamine (DABCO T; TOYOCAT RX55), N,N,N’,N’,N”-Pentamethyldiethylenetriamine (POLYCAT 5; TOYOCAT DT; JEFFCAT PMDETA), bis(2-Dimethylaminoethyl)ether (NIAXA-99; DABCO BL-19; TOYOCAT ETS; JEFFCAT ZF-20;RC Catalyst 6433), N,N’-bis(1 ,4-dimethylpentyl)-1,4-benzenediamine (TENAMENE 4), N-[3-(dimethylamino)propyl]-N,N’,N’-trimethyl-1 ,3-propanediamine (POLYCAT 77; JEFFCAT ZR40), 4-[2-(dimethylamino)ethyl]-morpholine (DABCO T; TOYOCAT RX
  • Particularly amine catalysts are selected from: i. tertiary amino compounds having at least one further amino group, selected from primary, secondary and tertiary amino groups, ii. tertiary amino compounds having at least one active hydrogen group, such as -OH, -NH-, -NH2, and -SH groups iii. tertiary amino compounds having at least one ether group, iv. aliphatic saturated tertiary amino compounds v.
  • tertiary amino compounds selected from the group of dimethylaminopropyl urea N,N'-bis[3-(dimethylamino)propyl]urea triethylamine 1 ,2-dimethylimidazole N-(3-aminopropyl)imidazole N-(hydroxypropyl)imidazole N-(2-hydroxyethyl)imidazole tris(dimethylaminopropyl)hexahydro-1 ,3,5-triazine 1 , 1 ,3,3-tetramethylguanidine, 1 ,5,7-triaza-bicyclo[4.4.0]dec-5-ene,
  • Particular preferred amine catalysts are bis(dimethylaminoethyl)ether ((BDMAEE) BDMAEE: Niax catalyst A-99), triethylenediamine (TEDA: Niax catalyst A-100) and N,N’-Bis[3- (dimethylamino)propyl]urea (Niax Catalyst EF-700).
  • the catalyst additive is an organotin compound that is a dialkyltin salt of a carboxylic acid, including the non-limiting examples of dibutyltin diacetate, dibutyltin dilaureate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis(4-methylarnino benzoate), dibutyltindilauryl mercaptide, dibutyl tin-bis(6-methylaminocaproate), and the like, and combinations of two or more thereof.
  • organotin compound that is a dialkyltin salt of a carboxylic acid
  • trialkyltin hydroxide dialkyltin oxide, dialkyltin dialkoxide, or dialkyltin dichloride, and combinations of two or more thereof can be employed.
  • Non-limiting examples of these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin- bis(isopropoxide) dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and the like, and combinations of two or more thereof.
  • the catalyst can be an organotin catalyst such as stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, stannous oleate, or combinations of two or more thereof.
  • a further particularly preferred polyurethane foaming additives (B) includes a surfactant preferably silicone-based surfactants, more preferably a polyether functional silicone.
  • the surfactant typically supports homogenization of a blowing agent and the polyol component and regulates a cell structure of the polyurethane foam article.
  • the surfactant may include any suitable surfactant or mixtures of surfactants known in the art.
  • suitable surfactants include various silicone surfactants, salts of sulfonic acids, e.g.
  • a specific preferred, non-limiting example of a surfactant is a silicone-based surfactants such as a silicone glycol copolymer.
  • Silicone surfactants that may be used as polyurethane foaming additive (B) include, e.g. “hydrolysable” polysiloxane-polyoxyalkylene block copolymers, “non-hydrolysable” polysiloxanepolyoxyalkylene block copolymers, cyanoalkylpolysiloxanes, alkylpolysiloxanes, and polydimethylsiloxane oils.
  • the type of silicone surfactant used and the amount required depend on the type of foam produced as recognized by those skilled in the art.
  • the reaction mixture In the polyurethane foam forming process for flexible slabstock foams, the reaction mixture usually contains a level of silicone surfactant from about 0.1 to about 6 pphp, and more often from about 0.7 to about 2.5 pphp.
  • the reaction mixture For flexible molded foam the reaction mixture usually contains a level of silicone surfactant from about 0.1 to about 5 pphp, and more often from about 0.5 to about 2.5 pphp.
  • the reaction mixture For rigid foams, the reaction mixture usually contains a level of silicone surfactant from about 0.1 to about 5 pphp of silicone surfactant, and more often from about 0.5 to about 3.5 pphp. The amount used is adjusted to achieve the required foam cell structure and foam stabilization. Suitable silicone surfactants are for example described e.g.
  • a particular preferred silicone surfactant is a polyether-functional silicone surfactant, preferably comprising two polyether substituents (as described in W02016201073A1), having preferably an average molecular weight of about 500 to 10000 such as 1500 or 4000, wherein the polyether moiety comprises ethylene oxide units (EO), preferably at least 20 % EO more preferably at least 40 % EO).
  • EO ethylene oxide units
  • silicone surfactants are the polyether functional silicones described in W02023/009390 incorporated by reference here.
  • Another preferred polyurethane foaming additive (B) includes a flame lamination additive.
  • flame lamination additives are for example described in WO16164552 A1 and include, in particular, compounds for improving the bond strength in flame lamination.
  • suitable flame lamination additives include, but are not limited to, phosphorus-containing flame retardants and polyols having aromatic structural units.
  • Particularly suitable flame lamination additives include, but are not limited to, high molecular weight flame retardants such as Fyrol PNX from AKZO and Exolit OP 560 from Clariant, bisphenol A alkoxylates and commercially available_flame lamination additives such as Niax Flame Lamination Additive FLE-200LF, Niax Flame Lamination Additive FLE-500LF, etc..
  • high molecular weight flame retardants such as Fyrol PNX from AKZO and Exolit OP 560 from Clariant
  • bisphenol A alkoxylates such as Niax Flame Lamination Additive FLE-200LF, Niax Flame Lamination Additive FLE-500LF, etc.
  • the flame lamination additive may be used in the polyurethane foam-forming compositions at a concentration of from about 1 to about 10 pphp, more particularly in an amount of from about 1 to about 8 pphp and even more particularly in an amount of from about 1 to about 6 pphp, where pphp means parts per hundred parts of the total polyol used.
  • Another preferred polyurethane foaming additive (B) includes processing aids additives.
  • recycling product refers to a product which is obtained from any previously-formed polyurethane objects or materials, (such as, for example, foam technological waste, post-consumer mattresses, thermal insulation panels footwear, automotive headliners or front panels, and the like) or were otherwise not used for any intended purpose (i.e. , virgin material, such as scrap or unused commercial products and the like). That is, any pre-formed foamed polyurethane article can be used to make the “recycling product”.
  • the recyclable polyurethane articles may be in the form of conventional, slab, or molded flexible foam; rigid, semi-rigid open and closed foam; microcellular polyurethane (MCU) foam, a thermoplastic polyurethane (TPU) and any combination thereof.
  • component (C) is obtained from polyurethane foam materials.
  • component (C) the one or more recycling products of one or more polyurethanes comprising one or more polyol, is obtained from polyurethane foam materials, which are prepared from aromatic polyisocyanates, such as methylene diphenyl diisocyanate or toluene diisocyanate, and derivatives thereof, and aliphatic polyols.
  • These recycling methods generally include a mechanical step such as pulverizing or comminuting, and a chemical recycling step.
  • Various chemically recycling processes are available and include, but are not limited to, hydrogenation, pyrolysis, hydrolysis, glycolysis, alcoholysis, acidolysis, cleavage (thermal cleavage or alkaline cleavage), aminolysis, solvolysis, and any combination thereof.
  • component (C) one or more recycling products of one or more polyurethanes comprising one or more polyols, is obtained by hydrogenation, pyrolysis, hydrolysis, alcoholysis, such as glycolysis, acidolysis, cleavage (thermal cleavage or alkaline cleavage), aminolysis, solvolysis and any combination thereof, preferably (C), one or more recycling products of one or more polyurethanes comprising one or more polyols, is obtained by acidolysis, preferably component (C) is a recycling product obtained from polyurethane foam materials.
  • Components (C), i.e. one or more recycling products of one or more polyurethanes comprising one or more polyols, are also commercially available under the trademark RePoliol® from Ikano Industry, Tru. Such commercially available components (C) sold under the trademark RePoliol® are preferably used in the present invention. They are obtained at industrial scale by an acidolysis process which uses flexible polyurethane foam waste. Polymers 2021 , 13, 1736 shows in Table 3: Table 3. Typical physical properties, assessed for the Repolyol and the reference polyol.
  • 'Acid number 0.22 ⁇ 0.01 0.05 ⁇ 0.005 the physical properties of a Repoliol® (obtained by an acidolysis process) corresponding to component (C), compared to the reference commercial polyol (Voranol 3322), which corresponds to the component (A) of the present invention.
  • a first noticeable difference is the colour of the products, brown for the recycled polyol and colorless for the standard polyol.
  • the hydroxyl number which is an important parameter, indicating the total amount of isocyanate functional groups required during the foaming process, is similar for the two polyols.
  • the water content in the polyols is the same for the two polyols.
  • a typical viscosity of about 500 to about 600 cSt (determined at 25°C) is for standard polyols, while the viscosity of the recycled polyol reached 12,500 cSt (determined at 25°C) (the kinematic viscosity is measured in the present application e.g. according to ASTM D445 or ASTM D7042).
  • ASTM D445 or ASTM D7042 the viscosity of the recycled polyol reached 12,500 cSt
  • the kinematic viscosity is measured in the present application e.g. according to ASTM D445 or ASTM D7042.
  • a metering system adaptation into the production environment is suitably applied to enable the industrial use of this high viscosity material. Consequently, the recycled polyol can be considered adequate for utilization in flexible Pll formulations.
  • the kinematic viscosity of component (C), in particular, if obtained by an acidolysis process, is at least about 5-times, preferably at least about 10-times, more preferably at least about 15-times, still more preferably at least about 20-times higher than the viscosity of component (A).
  • the hydroxyl number from 35 to 650 mg KOH/g amine number: from 1 to 40 mg KOH/g acid number: from 0.1 to 20 mg KOH/g.
  • the component (C) is obtained by alcoholysis, such as glycolysis, e.g. with diethylene glycol, viscosities of the recycled polyol material can be significantly lower and can be for example in the range of about 100 to about 1000 cSt (25°C), and the hydroxyl numbers can be significantly higher and can be more than 650 mg KOH/g and for example up to 900 mg KOH/g.
  • the component (C), the one or more recycling products of one or more polyurethanes comprising one or more polyols is obtained from polyurethane foam materials, which are prepared from aromatic polyisocyanates, such as methylene diphenyl diisocyanate (MDI ) (including the isomers (4,4'-MDI, 2,4'-MDI, and 2,2'-MDI) and mixtures thereof, and also PMDI (“polymeric methylenediphenyldiisocyanate”)) or toluene diisocyanate (TDI), and derivatives thereof, and aliphatic polyols, in particular, polyether polyols, such as polyalkyleneoxide polyols, which are usually made via a polymerization reaction involving an initiator (such as a polyalcohol or amine) and alkylene oxides such as polyether polyols made from ethylene oxide (EO), or propylene oxide (PO), or a combination of EO and PO.
  • the component (C), the one or more recycling products of one or more polyurethanes comprising one or more polyols is characterized accordingly by the presence of aromatic compounds derived from the aromatic polyisocyanates, such as as methylene diphenyl diisocyanate or toluene diisocyanate, and derivatives thereof, which have been used in the manufacture of said polyurethanes which were recycled.
  • aromatic compounds derived from the aromatic polyisocyanates such as as methylene diphenyl diisocyanate or toluene diisocyanate, and derivatives thereof, which have been used in the manufacture of said polyurethanes which were recycled.
  • the component (C), the one or more recycling products of one or more polyurethanes comprising one or more polyols is normally characterized by the presence of (visible) signals in the 1 H-NMR spectrum at a chemical shift of about 6 to about 8 ppm which is commonly assigned to the presence of aromatic compounds which originates from the aromatic polyisocyanates which have been used in the manufacture of the polyurethanes which were recycled.
  • the one or more recycling products of one or more polyurethanes comprising one or more polyols usually contain chemical compounds comprising functional groups which are selected from urethane (or carbamate) groups and urea groups, and which derive from the polyurethanes which were recycled. Also, the presence of such compounds having these functional groups such as urethane compounds is easily detectable e.g. by NMR spectroscopy. Any of these characteristics of the component (C) therefore unambiguously distinguish component (C) from so called virgin polyols which are not obtained from the recycling of polyurethanes and which are commonly used for the manufacture of polyurethanes and which can be also used in particular as component (A) of the present composition.
  • component (C) the one or more recycling products of one or more polyurethanes comprising one or more polyols, and a virgin polyol, which can be used in particular as component (A).
  • inventive compositions are usually used in the form of polyurethane foaming additive compositions, that essentially consist of the polyurethane foaming additives (B) and the recycling products of one or more polyurethanes comprising one or more polyols (C) and optionally of the one or more chemical compounds (A), other than components (B) or (C).
  • Component (A) includes in particular so to say virgin polyols, which are not obtained by the recycling of polyurethanes.
  • inventive compositions usually do not contain the isocyanate-functional compounds which are used in the polyurethane foam manufacture process. They thus normally represent a non-curable additive composition, which preferably comprises (preferably consist of):
  • (C) one or more recycling products of one or more polyurethanes comprising one or more polyols, preferably wherein the weight ratio of (C) to (A) is greater than 0 and less than 5/95, more preferably less than 3/97, still more preferably less than 1/100 and most preferably less than 1/1000.
  • inventive compositions are typically obtained by a process which comprises the step of forming a mixture of (B) and (C), and optionally (A) by mixing said components (B) and (C) and optionally (A) in any suitable order with suitable mixers adapted, in particular, to the viscosity of the components used.
  • the present invention also relates to curable compositions comprising the inventive (normally non-curable) compositions and one or more polyisocyanates (D) and to polyurethanes that are obtainable by curing said curable compositions, in particular polyurethane foams.
  • inventive (normally non-curable) compositions and one or more polyisocyanates (D)
  • polyurethanes that are obtainable by curing said curable compositions, in particular polyurethane foams.
  • the manufacture of such polyurethane foams is well-known in the art and such foams are obtained by reacting one or more polyisocyanates and one or more compounds having at least two reactive hydrogen atoms in particular polyols in the presence of blowing agents and other additives.
  • a survey of the preparation of polyurethanes is given e.g. in Kunststoff-Handbuch, volume VII, "Polyurethane", 3rd edition, 1993, by Dr G. Oertel (Carl Hanser Verlag).
  • the polyisocyanates (D) that are useful in the polyurethane foam formation process of this invention are organic compounds that contain at least two isocyanate groups and generally will be any of the known aromatic or aliphatic polyisocyanates.
  • Suitable organic polyisocyanates (D) include, for example, the hydrocarbon diisocyanates, (e.g. the alkylenediisocyanates and the arylene diisocyanates), such as methylene diphenyl diisocyanate (MDI) and 2,4- and 2,6-toluene diisocyanate (TDI), as well as known triisocyanates and polymethylene poly(phenylene isocyanates) also known as polymeric or crude MDI.
  • the hydrocarbon diisocyanates e.g. the alkylenediisocyanates and the arylene diisocyanates
  • MDI methylene diphenyl diisocyanate
  • TDI 2,4- and 2,6-toluene diiso
  • the preferred isocyanates generally are, e.g., mixtures of 2,4-tolulene diisocyanate and 2,6-tolulene diisocyanate (TDI) in proportions by weight of about 80% and about 20% respectively and also about 65% and about 35% respectively based on the total weight of the composition of TDI; mixtures of TDI and polymeric MDI, preferably in the proportion by weight of about 80% TDI and about 20% of crude polymeric MDI to about 50% TDI and about 50% crude polymeric MDI based on the total weight of the composition; and all polyisocyanates of the MDI type.
  • the preferred isocyanates are, e.g., polyisocyanates of the MDI type and preferably crude polymeric MDI.
  • the Isocyanate Index is: for flexible TDI foams, typically between 85 and 120; for molded TDI foams, normally between 90 and 105; for molded MDI foams, most often between 70 and 90; and for rigid MDI foams, generally between 90 and 130.
  • Some examples of polyisocyanurate rigid foams are produced at indices as high as 250-400.
  • water In the production of flexible slabstock foams, water generally can be used in concentrations of, e.g., between 2 to 6.5 parts per hundred parts (pphp) of polyol blend, and more often between 3.5 to 5.5 pphp of polyol blend.
  • Water levels for TDI molded foams normally range, e.g., from 3 to 4.5 pphp of polyol blend.
  • the water level for example, is more normally between 2.5 and 5 pphp.
  • Rigid foam water levels for example, range from 0.5 to 5 pphp, and more often from 0.5 to 2 pphp of polyol blend.
  • blowing agents such as blowing agents based on volatile hydrocarbons or halogenated hydrocarbons and other non-reacting gases can also be used in the production of polyurethane foams in accordance with the present invention.
  • a significant proportion of the rigid insulation foam produced is blown with volatile hydrocarbons or halogenated hydrocarbons and the preferred blowing agents are the hydrochlorofluorocarbons (HCFC) and the volatile hydrocarbons pentane and cyclopentane.
  • HCFC hydrochlorofluorocarbons
  • the volatile hydrocarbons pentane and cyclopentane In the production of flexible slabstock foams, water is the main blowing agent; however, other blowing agents can be used as auxiliary blowing agents.
  • the preferred auxiliary blowing agents are carbon dioxide and dichloromethane (methylene chloride).
  • Other blowing agents may also be used such as, e.g., the chlorofluorocarbon (CFG) and the trichloromonofluoromethane (
  • Flexible molded foams typically do not use an inert, auxiliary blowing agent, and in any event incorporate less auxiliary blowing agents than slabstock foams.
  • carbon dioxide in some molded technology.
  • MDI molded foams in Asia and in some developing countries use methylene chloride, CFC-11 and other blowing agents.
  • the quantity of blowing agent varies according to the desired foam density and foam hardness as recognized by those skilled in the art.
  • the amount of hydrocarbon-type blowing agent varies from, e.g., a trace amount up to about 50 parts per hundred parts of polyol blend (pphp) and CO2 varies from, e.g., about 1 to about 10 pphp of polyol blend.
  • Crosslinkers also may be used in the production of polyurethane foams.
  • Crosslinkers are typically small molecules; usually less than 350 molecular weight, which contain active hydrogens for reaction with the isocyanate.
  • the functionality of a crosslinker is greater than 3 and preferably between 3 and 5.
  • the amount of crosslinker used can vary between about 0.1 pphp and about 20 pphp based on polyol blend and the amount used is adjusted to achieve the required foam stabilization or foam hardness.
  • Examples of crosslinkers include glycerine, diethanolamine, triethanolamine and tetrahydroxyethylethylenediamine.
  • Flexible slabstock foams are usually produced by mixing the reactants generally at an ambient temperature of between about 20° C and about 40° C.
  • the conveyor on which the foam rises and cures is essentially at ambient temperature, which temperature can vary significantly depending on the geographical area where the foam is made and the time of year.
  • Flexible molded foams usually are produced by mixing the reactants at temperatures between about 20° C and about 30° C, and more often between about 20° C and about 25° C. The mixed starting materials are fed into a mold typically by pouring.
  • the mold preferably is heated to a temperature between about 20° C and about 70° C, and more often between about 40° C and about 65° C Sprayed rigid foam starting materials are mixed and sprayed at ambient temperature. Molded rigid foam starting materials are mixed at a temperature in the range of about 20° C to about 35° C.
  • the preferred process used for the production of flexible slabstock foams, molded foams, and rigid foams in accordance with the present invention is the “one- shot” process where the starting materials are mixed and reacted in one step.
  • the inventive polyurethane foaming additive compositions serve to add the respective functional additives (B) to the curable polyurethane forming compositions, comprising one or more polyisocyanate compounds (D) and one or more or polyol components (E) used to prepare the polyurethane. That is, the components (C) and optionally (A) serve as functional solvents or carriers for the respective polyurethane foaming additives. That is, while components (C) and optionally (A) have polyol functionality they are not used as the polyol component (E) that provides sufficient polyol functionality to react with polyisocyanates (D) to form the polyurethane foams.
  • This polyol component (E) might be selected among components (A), but if components (A) are used in the inventive polyurethane foaming additive compositions, their amounts are much lower than those of the polyol component (E).
  • the amount of the inventive polyurethane foaming additive compositions added to the curable polyurethane forming compositions, comprising the polyisocyanate compound (D) and a polyol component (E) used to prepare the polyurethane foams is suitably in the range of about 0.001 to about 15 pphp (parts per hundred parts), preferably about 0.01 to about 10 pphp more preferably about 0.05 to about 5 pphp based on the polyol component (E).
  • a typical composition of curable polyurethane foam forming compositions thus comprises:
  • polyol component (E) for example being comprised of one or more polyols in components (A)
  • polyol component (E) for example being comprised of one or more polyols in components (A)
  • polyol component (E) for example being comprised of one or more polyols in components (A)
  • more preferably about 0.05 to about 5 pbw of the inventive polyurethane foaming additive compositions as described above about 10 to 100 pbw one or more polyisocyanate compounds (D), and optionally up to 10 pbw, preferably 0.001 to 10 pbw of one or more (additional) conventional polyurethane foaming additives (which are not added in the form of the inventive polyurethane foaming additive compositions but which might be selected from one or more of the polyurethane forming additives (B)).
  • the polyurethane forming additives (B) are added in the form of the inventive polyurethane foaming additive compositions comprising component (C), the one or more recycling products of one or more polyurethanes comprising one or more polyols, as a functional solvent or carries, surprisingly the mechanical properties of the resulting polyurethane foams are improved compared to foams where the additive is added solely in a conventional solvent carrier such as optional component (A).
  • the present invention further relates to the use of the inventive polyurethane foaming additive compositions for the manufacture of polyurethane foams as described before.
  • the recycled polyurethane foam (RPLIF) material (component (C)) was provided by the company Ikano under the trademark RePoliol®.
  • silicone copolymers used as surfactants are synthesized in laboratory. The detailed approach and structure definition were described in prior art (see US 5,145,879 and EP3307801 A1 /WO2016201073A1 ).
  • Inventive compositions Cat. E1 and Cat. E2 contained the recycling product of a polyurethane foam comprising one or more polyols, (C). Table 2. Comparison of the foaming and foam physical performances between comparative amine catalyst compositions with PPG only (Cat. R1 and R2) and inventive amine catalyst compositions with RPUF materials (Cat. E1 and E2)
  • the test results for the amine catalyst compositions are shown in Table 2.
  • the inventive amine catalyst compositions with the recycled polyurethane foam (RPLIF) materials show surprisingly better hardness and compression set, while showing the same foaming performance (blowing off time), a similar air flow and density, and the same fine cell structure. Comparing Ref. 1 & Ex. 1 , and Ref. 2 & Ex. 2, the hardness has 2.8% and 7.3% improvement, respectively, and the compression set has 14% and 20% improvement with reaching lower compression set reduction, respectively. Silicone surfactants (component (B)) with RPUF materials (component (C))
  • DPG dipropylene glycol (component (A))
  • RPLIF recycled polyurethane foam materials (component (C))
  • Silicone surfactants (component (B)) are simply blended according to the weight percentage above table.
  • silicone surfactant composition E with recycled polyurethane foam (RPLIF) materials show the similar performances in foaming processing and foam physical properties as with silicone surfactant composition R. Similar to Table 2 for the catalyst case, hardness and compression set with the RPUF-containing silicone composition (Inventive Ex. 3 and 4) is surprisingly improved compared to the comparative samples Ref. 3 and 4.
  • the recycled polyurethane foam (RPLIF) material surprisingly is an economical and sustainable solution to replace petroleum-derived functional solvents such as low molecular weight glycol materials in additives.
  • Preferred embodiments of the invention :
  • composition comprising:
  • composition according to embodiment 1 further comprising:
  • (A) one or more chemical compounds, other than components (B) or (C), in particular, polyols, which are not obtained by the recycling of polyurethanes.
  • composition according to embodiments 1 or 2 consisting of:
  • Catalysts such as amine catalysts
  • Surfactants preferably silicone-based surfactants
  • polyurethane foaming additives (B) are selected from amine catalysts selected from the group of: i. tertiary amino compounds having at least one further amino group, selected from primary, secondary and tertiary amino groups, ii. tertiary amino compounds having at least one active hydrogen group, such as -OH, -NH-, -NH2, and -SH groups, iii. tertiary amino compounds having at least one ether group, iv. aliphatic saturated tertiary amino compounds, v. tertiary amino compounds selected from the group of dimethylaminopropyl urea
  • N-(2-hydroxyethyl)imidazole tris(dimethylaminopropyl)hexahydro-1 ,3,5-triazine
  • virgin polyols which are not obtained by the recycling of polyurethanes, such as aliphatic polyols, for example glycols, such as hexylene glycol, dipropylene glycol, diethylene glycol, mono propylene glycol, mono ethylene glycol, methylpentanediol, methylpropanediol, and the like.
  • composition according to any of the previous embodiments wherein (C), one or more recycling products of one or more polyurethanes comprising one or more polyols, is obtained by hydrogenation, pyrolysis, hydrolysis, alcoholysis, such as glycolysis, acidolysis, cleavage (thermal cleavage or alkaline cleavage), aminolysis, solvolysis and any combination thereof, preferably (C), one or more recycling products of one or more polyurethanes comprising one or more polyols, is obtained by acidolysis.
  • composition according to any of the previous embodiments, wherein the (C), one or more recycling products of one or more polyurethanes comprising one or more polyol, is obtained from polyurethane foam materials.
  • composition according to any of the previous embodiments, wherein the component (C), the one or more recycling products of one or more polyurethanes comprising one or more polyols, is characterized by the presence of signals in the 1 H-NMR spectrum at a chemical shift of about 7 to about 9 ppm.
  • composition according to any of the previous embodiments, wherein the (C), one or more recycling products of one or more polyurethanes comprising one or more polyol, is obtained by acidolysis of one or more one or more polyurethanes, preferably of polyurethane foam materials.
  • the kinematic viscosity of component (C) is at least about 5-times, preferably at least about 10-times, more preferably at least about 15-times, still more preferably at least about 20-times higher than the viscosity of component (A),
  • the kinematic viscosity of component (C) is in the range of about 2000 to 20000 cSt (25°C), preferably about 5000 to about 17500 cSt (25°C),
  • a non-curable polyol composition comprising:
  • a process for the manufacture of a composition according to any of the previous embodiments which comprises the step of forming a mixture of (B) and (C), and optionally (A) by mixing said components (B) and (C) and optionally (A) in any suitable order.
  • a curable composition comprising the compositions according to any of the previous embodiments and one or more polyisocyanates (D).
  • a process for the manufacture of polyurethane foams comprising the steps of admixing a composition according to any of the previous embodiments with one or more polyisocyanates (D) and reacting the mixture to form a polyurethane foam.

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Abstract

La présente invention concerne des compositions d'additifs de mousse de polyuréthane, comprenant un produit de recyclage d'une mousse de polyuréthane, qui comprend un ou plusieurs polyols, et facultativement un ou plusieurs composés chimiques, autres que des additifs de mousse de polyuréthane ou des produits recyclés d'une mousse de polyuréthane, qui comprennent également des polyols vierges non obtenus par le recyclage de mousses de polyuréthane, qui est de manière appropriée une composition d'additif non durcissable, un processus de fabrication des compositions d'additifs de mousse de polyuréthane, des compositions durcissables comprenant les compositions d'additifs de mousse de polyuréthane et un ou plusieurs polyisocyanates, des polyuréthanes obtenus à partir de telles compositions durcissables, l'utilisation des compositions d'additifs de mousse de polyuréthane pour la fabrication de mousses de polyuréthane, un processus de fabrication de mousses de polyuréthane utilisant lesdites compositions d'additifs de mousse de polyuréthane et l'utilisation d'un produit de recyclage d'une mousse de polyuréthane comprenant un ou plusieurs polyols, en tant que solvant fonctionnel pour des additifs de mousse de polyuréthane.
PCT/EP2024/087610 2023-12-22 2024-12-19 Compositions d'additifs de mousse de polyuréthane Pending WO2025132927A1 (fr)

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