WO2025132927A1

WO2025132927A1 - Polyurethane foaming additive compositions

Info

Publication number: WO2025132927A1
Application number: PCT/EP2024/087610
Authority: WO
Inventors: Antonie-Gabriel KISS; Lijun Feng; Sebastian GISBERTZ
Original assignee: Momentive Performance Materials GmbH
Current assignee: Momentive Performance Materials GmbH
Priority date: 2023-12-22
Filing date: 2024-12-19
Publication date: 2025-06-26
Anticipated expiration: 2026-06-22

Abstract

The present invention relates to polyurethane foam additive compositions, comprising a recycling product of a polyurethane foam, which comprises one or more polyols, and optionally one or more chemical compounds, other than polyurethane foam additives or recycled products of a polyurethane foam, which also includes virgin polyols 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.

Description

POLYURETHANE FOAMING ADDITIVE COMPOSITIONS

FIELD OF THE INVENTION

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.

BACKGROUND OF THE INVENTION

Polyurethane is a thermoset material. It is impossible to recycle it as it is done with thermoplastic materials. To build a life cycle for polyurethane materials and products, chemical processing (chemolysis) is applied to polyurethane foam waste 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. Lindhardt, and Troels Skrydstrup: tert-Amyl Alcohol-Mediated Deconstruction of Polyurethane for Polyol and Aniline Recovery, ACS Sustainable Chemistry & Engineering 2022 10 (34), 11191-11202; and Maja Grdadolnik, Blaz Zdovc, Ana Drincic, Ozgun Can Onder, Petra Utrosa, Susana Garcia Ramos, Enrique Dominguez Ramos, David Pahovnik, and Ema Zagar: Chemical Recycling of Flexible Polyurethane Foams by Aminolysis to Recover High-Quality Polyols; ACS Sustainable Chemistry & Engineering 2023 11 (29), 10864-10873). An efficient approach is the combination of an acidolysis step and a dispersion step with the radical reaction with a polyether (see e.g. US20190359788A1 , US2021017354A1 or US 2023/0250254 A1). US2019/0359788A1 , US2021017354A1 and US 2023/0250254 A1 disclose a polyol mixture, which comprises polyurethane foaming additives resulting from the recycling product of polyurethane foams. The polyol compositions are obtained by a process wherein in a first step the polyurethane waste is reacted with a reaction mixture containing a dicarboxylic acid or dicarboxylic acid derivative and a polyetherol at temperatures of from 170° C. to 210° C. to form a dispersion; and in a second step, the dispersion obtained is reacted again with a shortchain diol and/or a short-chain triol at temperatures of from 180° C. to 230° C. to give the isocyanate-reactive polyol dispersion. There is, however, no disclosure of mixtures of the recycled polyol composition and polyurethane foaming additives, formed by a separate step of admixture thereof. Rather the recycled polyols contain unknown amounts of certain components such as calcium carbonate, SAN, PIPA and PUD due to the fact that the polyol has been obtained from recycling materials which have been subjected to little presorting. In the foaming examples the polyol compositions are used without the addition of polyurethane foaming additives.

Additives in polyurethane formation, such as silicone surfactant and amine catalysts, 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. Also the use of recyling polyols in polyurethane forming compositions comprising a polyol and a polyisocyanate component has been suggested (see e.g. EP 4282892A1 and EP 4282890 A1), but there is no disclosure of any specific composition comprising such recycling polyols in these prior art documents nor any pointer to the use of these recycling polyols as a functional solvent for polyurethane foaming additive compositions leaving alone that any beneficial effects could be achieved in the polyurethane foams in the manufacture of which said polyurethane foaming additive compositions are used.

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.

SUMMARY OF THE INVENTION

Addressing the sustainability challenges by improving the life cycle for polyurethane foams, the present invention proposes 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. DETAILED DESCRIPTION OF THE INVENTION

(In the present application “pw” means “parts by weight”).

In accordance with the present invention a composition is provided comprising:

(B) 5 to 95 pw one or more polyurethane foaming additives, and

(C) 5 to 95 pw of one or more recycling products of one or more polyurethanes comprising one or more polyols, wherein the amount of the polyurethane foaming additives (B) is at least 5 wt.-%, preferably at least 10 wt.-%, more preferably at least 20 wt.-%, based on the total weight of the composition. Preferably the compositions of the present invention, comprise

(B) 10 to 90 pw one or more polyurethane foaming additives, and

(C) 10 to 90 pw of one or more recycling products of one or more polyurethanes comprising one or more polyols, more preferably

(B) 15 to 85 pw one or more polyurethane foaming additives, and

(C) 15 to 85 pw of one or more recycling products of one or more polyurethanes comprising one or more polyols, still more preferably

(B) 20 to 80 pw one or more polyurethane foaming additives, and

(C) 20 to 80 pw of one or more recycling products of one or more polyurethanes comprising one or more polyols, still more preferably

(B) 30 to 80 pw one or more polyurethane foaming additives, and

(C) 20 to 70 pw of one or more recycling products of one or more polyurethanes comprising one or more polyols, and still more preferably

(B) 40 to 80 pw one or more polyurethane foaming additives, and

(C) 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. In an embodiment of the invention 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.

In an embodiment of the invention the composition is consisting of:

(B) 5 to 95 pw one or more polyurethane foaming additives,

(C) 5 to 95 pw of one or more recycling products of one or more polyurethanes comprising one or more polyols, and optionally

(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. Here the term of “consisting of” does not exclude the presence of any non-functional amounts of other components such as impurities.

The components (A) to (C) used in the accordance with the present invention are explained in more detail in the following.

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. As described in US 2019/0359788 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- %. Furthermore “virgin” polyols 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).

As the polyols (A) e.g. polyols (polyether polyols, polyester polyols, copolymer polyols also known as graft polyols) can be used. Typically, 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. For flexible 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. For rigid foams, the preferred functionality is about 2 to about 8 and most preferably about 3 to about 5.

The compositions of the invention include as polyol (A) for example any of the following nonlimiting classes of polyols:

(a) polyether polyols derived from the reaction of polyhydroxyalkanes with one or more alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.;

(b) 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.;

(c) polyether polyols derived from the reaction of phosphorus and polyphosporus acids with alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.,

(d) polyether polyols derived from the reaction of polyaromatic alcohols with alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.;

(e) polyether polyols derived from the reaction of ring-opening polymerization of tetrahydrofurane;

(f) polyether polyols derived from the reaction of ammonia and/or an amine with alkylene oxides, e.g. ethylene oxide, propylene oxide, etc.;

(g) 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;

(h) polyoxamate polyols derived from the reaction of an oxalate ester and a diamine, e.g. hydrazine, ethylenediamine, etc. directly in a polyether polyol;

(i) polyurea polyols derived from the reaction of a diisocyanate and a diamine, e.g. hydrazine, ethylenediamine, etc. directly in a polyether polyol.

For flexible foams, preferred types of alkylene oxide adducts of polyhydroxyalkanes are the ethylene oxide and propylene oxide adducts of aliphatic triols such as glycerol, trimethylol propane, etc. For rigid foams, 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.

Preference is given to using polyesterols and/or polyetherols as 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. In the case of polyetherols, 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. 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. Furthermore, 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 VORANOL™ 3322 Polyol (nominal 3400 molecular weight, heteropolymer triol), and others, such as RENUVA™ FF 60, VORANOL™ 3010, VORANOL™ 3010A, VORANOL™ 3011 , VORANOL™ 3022J, VORANOL™ 3322, VORANOL™ 3535,

VORANOL™ 4730-N, VORANOL™ 8010, VORANOL™ 8010A, VORANOL™ 8010G, VORANOL™ 8022, VORANOL™ 8136, VORANOL™ 8322, VORANOL™ 8595,

VORANOL™ WK 3138, VORANOL™ WL 4010, VORANOL™ 3136, DWJ 4001.01 DEV, VORALUX™ HF 505, VORALUX™ HN 395, VORANOL™ 4150, VORANOL™ 6150, SPECFLEX™ 334-028, VORALUX™ HK 643, VORALUX™ HT 760, VORALUX™ HT 762, VORALUX™ HT 767, VORALUX™ HT 1080, VORANOL™ 8150, VORANOL™ WK 3140, VORANOL™ WK 8140, VORANOL ™ WL 4099.

Preferred components (A) also include glycols such as hexylene glycol, dipropylene glycol, diethylene glycol, mono propylene glycol, mono ethylene glycol, methylpentanediol, methylpropanediol, etc.

Most preferably component (A) is selected from aliphatic polyols, i.e. non-aromatic polyols.

(B) Polyurethane foaming additives

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, fumed silicas, fillers such as calcium carbonate, microcellulose, thixotropic agents, silicones, colorants or pigments such as titanium dioxide (white), iron (III) oxide (red), chromium (III) oxides (green), carbon (black), color pastes, inert diluents, and combinations thereof (see e.g. The polyurethanes book, Editors David Randall and Steve Lee, John Willey & Sons, LTD, 2002; Szycher's Handbook of Polyurethanes, 2nd edition, 2013, chapter 18 in particular, each included herein by reference to such documents).

Preferably the 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.

More preferably the the polyurethane foaming additives (B) are selected from the group consisting of catalysts such amine catalysts and silicone-based surfactants.

The catalyst may include any suitable catalysts or mixtures of catalysts known in the art as catalysts in polyurethane formation. Examples of suitable catalysts include, but are not limited to, gelation catalysts, e.g. amine catalysts such as tertiary amines; blowing catalysts, e.g. bis(dimethylaminoethyl)ether; and metal catalysts, e.g. tin (e.g. stannous octoate), bismuth, or lead compounds etc. as described in more detail below.

Amine catalysts

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. For example such 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, 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, 3- dimethylamino-N,N-dimethylpropionamide, N,N’-dimorpholinodiethyl ether, N,N’- dimethylpiperazine, N-methylmorpholine, N-ethylmorpholine, 2-{[2- (dimethylamino)ethyl]methylamino}ethanol, 3,3'-iminobis(N,N-dimethylpropylamine), 3- (dimethylamino)-l-propylamine, 3-(diethylamino)-1-propanol, 1-(3-hydroxypropyl)pyrrolidine, 1-(2-hydroxypropyl)pyrrolidine, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperidine, 1- (3-hydroxypropyl)piperidine, 1-(2-hydroxypropyl)piperidine, 1-(3-aminopropyl)pyrrolidine, 1-(2- aminoethyl)pyrrolidine, 1-(3-aminopropyl)piperidine, 1-(2-aminoethyl)piperidine, 1-(1- pyrolidineyl)-2-propanamine, 1-(piperidin-1-yl)propan 2-amine, N-methoxyethylmorpholine, N- methylimidazole, 1-(3-aminopropyl) imidazole, 2-[2-[2-(dimethylamino)ethoxy]ethyl- methylamino]ethanol, N-methyl dicyclohexylamine, 3-{[3-

(dimethylamino)propyl]methylamino}propanol, tris (dimethyl aminopropyl)amine, 2-{[3- (dimethylamino)propyl]methylamino}ethanol, N,N,N’,N’-tetramethyl-hexamethylene diamine, N,N,N’,N’-tetramethylethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,3,5- tris(dimethylaminopropyl)- hexahydrotriazine, N,N-dimethylbenzylamine, 1 ,8 diaza bicyclo 5,4,0 undecene 7, N-methyl-N’-(2-dimethylamino) ethyl-piperazine, N,N'-bis[3- (dimethylamino)propyl]urea, N-[3-(dimethylamino)propyl]urea. N,N,N',N'-tetrakis(2- hydroxypropyl)ethylenediamine, and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine. Preferred 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- dimethylaminopropylamine, diethanolamine, trimethylamine, triethylenediamine, bis(2- dimethylaminoethyl)ether.

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 DMEA; JEFFCAT DMEA), N-Methylmorpholine (JEFFCAT NNM; RC Catalyst 101), N,N-Dimethylaminopropylamine (DMAPA; TOYOCAT RH2), N,N,N’,N’-Tetramethylethylenediamine (TMEDA; TOYOCAT-TE; JEFFCAT TMEDA), 1,3- bis(dimethylamino)propane, N,N,N’,N’-Tetramethylhexamethylenediamine (TMHDA; TOYOCAT-MR), Diethanolamine DABCO DEOA-LF; DEOA LFG; DEA), Dimethyldodecylamine (DM-12D, N,N-dimethylhexadecylamine (DM-16D; DABCO B-16), Triethylamine (ACCLIRE C (Allied), N,N-Diisopropylethanolamine (DIEA), Ethanolamine (Monoethanolamine) EA (MEA), Triethylenediamine (TEDA; NIAXA-100, DABCO Crystal; RC Catalyst 105; JEFFCAT TD-100; TOYOCAT TEDA; RC Catalyst 104), 4-butyl-morpholine (NBM), 2(2-Dimethylaminoethoxy)ethanol (PAK-LOC V; JEFFCAT ZR-70), 1,2-

Dimethylimidazole (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 XDM), N- cyclohexyldiethanolamine (DECA), N-Hydroxyethyl-N’-methylpiperazine (TOYOCAT-HP), N- (3-Dimethylaminopropyl)formamide, 1 ,3-bis(dimethylamino)-2-propanol (UC-2 (Sipene)), 2,2’- dimorpholinodiethylether (JEFFCAT DMDEE), 1 ,8-diazabicyclo[5.4.0]undec-7-ene (POLYCAT DBU; RC Catalyst 6180), Tetramethylimino-bis(propylamine) (POLYCAT 15; JEFFCAT ZR- 50B), N-Methyldicyclohexylamine (POLYCAT 12), 4-(2-methoxyethyl)-morpholine (JEFFCAT MM), N,N,N'-tris(2-hydroxypropyl)ethylenediamine (EFFCAT DPA), 1 ,3,5-tris[3- (dimethylamino)propyl]hexahydro-s-triazine (POLYCAT 41 ; JEFFCAT TR41 ; TOYOCAT TRC; RC Catalyst 6099), 3-Dimethylamino-N,N-Dimethylpropionamide (DDPA; NIAX A4; NIAX C- 191), N,N-dimethyl-(4-methyl-1-piperazinyl)-ethanamine (JEFFCAT TAP; RC Catalyst 6076), Tris(3-Dimethylamino)propylamine (POLYCAT 9; JEFFCAT Z80), ethanamine, 2,2’-[methylene bis(oxy)]bis[N,N-dimethyl- (CI-710), 4-(2-aminopropyl)morpholine (MAEM), 1-[bis(3- dimethylaminopropyl)amino]-2-propanol (JEFFCAT ZR-50), N,N,N’,N’-2-pentamethyl-1 ,2- propanediamine (PMT), N-Cocomorpholine (DABCO NCM; JEFFCAT NCM), N-Methyl,N- (N’,N’-2-Dimethylaminopropyl)ethanolamine (POLYCAT 17), 2-(2-(2-dimethylamino ethoxy)- ethylmethylamino)-amino (JEFFCAT ZF-10).

Further mention can be made of the amine catalysts disclosed in WO 2021/177946, the catalyst compositions disclosed in WO 2021/177944, the entire content of which is included herewith by reference to such documents.

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,

2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane,

N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine),

4-ethyl-2,2-dimethyl-1-oxa-4-aza-2-silacyclohexane,

N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine) (bis(2-dimethylaminoethyl)ether), and triethylenediamine (1 ,4-diazabicyclo[2.2.2]octane); vi. any of the above amine catalysts blocked with an organic acid, and vii. mixtures of the above amine catalysts.

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).

Metal catalysts

Apart from amine catalysts suitable catalysts include metal catalysts such as: strong metal bases compounds such as alkali and alkaline earth metal hydroxides, alkoxides, phenoxides, and the like, acidic metal salts of strong acids such as ferric chloride, stannous chloride, antimony trichloride, bismuth nitrate and chloride, and the like; chelates of various metals such as those which can be obtained from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone- 2-carboxylate, acetylacetoneimine, bis-acetylacetone alkylenediimines, salicylaldehydeimine, and the like, with various metals such as Be, Mg, Zn, Cd, Pb, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, Ni, or metal ion compounds such as MoO2⁺⁺, UO2⁺⁺, and the like; alcoholates and phenolates of various metals such as Ti(OR)4, Sn(OR)4, Sn(OR)2, AI(OR)3, and the like, wherein R is an organic group such as alkyl or aryl of from 1 to about 12 carbon atoms, and reaction products of alcoholates with carboxylic acids, beta-diketones, and 2-(N,N-dialkylamino) alkanols, such as well known chelates of titanium obtained by this or equivalent procedures; salts of organic acids with a variety of metals such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Bi, and Cu, including, for example, sodium acetate, potassium laurate, calcium hexanoate, stannous acetate, stannous octoate, stannous oleate, lead octoate, metallic driers such as manganese and cobalt naphthenate, and the like; organometallic derivatives of tetravalent tin, tri valent and pentavalent As, Sb, and Bi, and metal carbonyls of iron and cobalt; and combinations of two or more thereof.

In one embodiment, 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.

Similarly, in another embodiment there may be used 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.

In one embodiment, the catalyst can be an organotin catalyst such as stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, stannous oleate, or combinations of two or more thereof.

Surfactants

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. Non-limiting examples of suitable surfactants include various silicone surfactants, salts of sulfonic acids, e.g. alkali metal and/or ammonium salts of oleic acid, stearic acid, dodecylbenzene- or dinaphthylmethanedisulfonic acid, and ricinoleic acid, foam stabilizers such as siloxaneoxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkyl-phenols, oxyethylated fatty alcohols, paraffin oils, castor oil, castor oil esters, and ricinoleic acid esters, and cell regulators, such as paraffins, fatty alcohols, and dimethylpolysiloxanes. 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. 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. 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. 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. in US 5,489,617, US 8,044,109, US 5,145,879, EP3307801A1/W02016201073A1) WO16164552 A1 ,_W016201073 A1 , EP1753799B1 , US9587068B2, W02023/009390 and Dipak D. Pukale et al.: “Review on Silicone Surfactants: Silicone-based Gemini Surfactants, Physicochemical Properties and Applications”, Tenside Surf. Det. 56 (2019) 4 all incorporated by reference here. They are commercially available for example under the trademark NIAX® of Momentive Performance Materials such as NIAX® L-895, L-894, L-882, L-850, L-820, or L-800.

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).

Further preferred silicone surfactants are the polyether functional silicones described in W02023/009390 incorporated by reference here.

Flame lamination additive

Another preferred polyurethane foaming additive (B) includes a flame lamination additive. Such flame lamination additives are for example described in WO16164552 A1 and include, in particular, compounds for improving the bond strength in flame lamination. Examples of 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..

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.

Antioxidants

Another preferred polyurethane foaming additive (B) includes antioxidants such as those described already above. They retard the thermal oxidation of polyurethanes by stopping the chain-breaking reactions initiated by oxygen, oxygen free radicals. Antioxidants in synergistic mixtures with phosphites or phosphines are particularly effective. A comprehensive list of possible antioxidants to be used in polyurethane foams is disclosed for example in W02019/110726 (see in particular the “Background of the invention”) the disclosure of which is incorporated herein by reference to such document. Further suitable antioxidants are described in Szycher's Handbook of Polyurethanes, 2nd edition, 2013, see chapter 18 in particular).

Processing aids additives

Another preferred polyurethane foaming additive (B) includes processing aids additives.

Processing aids additives include for example products stabilizing foaming process, preventing foam splitting, and unifying foaming performance along foaming rising direction, such as Geocell GM-280, GM-225, Niax GM-206, and GM-210, and other products improving foaming processing capability, such as lubricants, including (014-018) fatty alcohols, dicarboxylic acid esters, fatty acid esters, fatty acids, fatty acid soaps, and fatty acid amines, and mold-release agents.

The most preferred polyurethane foaming additives (B) are silicone surfactants and amine catalysts, which are two of the most important additives for producing polyurethane foams.

(C) Recycling product of a polyurethane foam

The term “one or more recycling products of one or more polyurethanes comprising one or more polyols” (in the following sometimes simply referred to as “recycling product” as used herein, 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. Preferably component (C) is obtained from polyurethane foam materials. Preferably 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.

In an embodiment of the invention 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. Usually these recycling products of the polyurethanes comprising one or more polyols (C), are used as such, that is, they are not subjected to a further step of isolation or purification step of the polyols contained therein after the polyurethanes have been subjected to a chemical recycling processes as described before.

Such processes are known in the art and are described for example in the following references: Kiss, G.; Rusu, G.; Bandur, G.; Hulka, I.; Romecki, D.; Peter, F. Advances in Low-Density Flexible Polyurethane Foams by Optimized Incorporation of High Amount of Recycled Polyol. Polymers 2021 , 13, 1736. https://doi.org/10.3390/polym13111736 and references cited therein; Kiss G, Rusu G, Peter F, Tanase I, Bandur G. Recovery of Flexible Polyurethane Foam Waste for Efficient Reuse in Industrial Formulations. Polymers (Basel). 2020 Jul 10; 12(7): 1533. doi: 10.3390/polym12071533. PMID: 32664336; PMCID: PMC7407941 and references cited therein; ACS Sustainable Chem. Eng. 2023, 11 , 10864-10873 (Maja Grdadolnik et al., “Chemical Recycling of Flexible Polyurethane Foams by Aminolysis to Recover High-Quality Polyols” https://doi.org/10.1021/acssuschemeng.3c02311) and references cited therein; Soltysihski, M., Piszczek, K., Romecki, D., Narozniak, S., Tomaszewska, J., & Skorczewska, K. (2021) Conversion of polyurethane technological foam waste and post-consumer polyurethane mattresses into polyols - industrial applications. Polimery, 63(3), 234-238. https://doi.Org/10.14314/polimery.2018.3.8 and references cited therein; Martin B. Johansen, Bjarke S. Donslund, Steffan K. Kristensen, Anders T. Lindhardt, and Troels Skrydstrup: tert-Amyl Alcohol-Mediated Deconstruction of Polyurethane for Polyol and Aniline Recovery, ACS Sustainable Chemistry & Engineering 2022 10 (34), 11191-11202 and references cited therein; US2019/0359788A1 and US2021017354A1 and references cited therein - the contents of all of these references are incorporated to the present application by reference to them.

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, Poland. 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.

Characteristic Repolyol Reference Polyol

Color Brown Colorless

Water content (%) 0.05 ± 0.02 0.05 ± 0.02

Viscosity (cSt) 12,500 ± 110 550 ± 8.7

Hydroxyl number (mg KOH/g) 46.00 ± 1.02 48.00 ± 1.11

'Acid number (mg KOH/g) ’ 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. As explained therein 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. The main difference is the viscosity. 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). While processing a material with such high viscosity is difficult in the industrial application, people skilled in the art are familiar with polyols with even higher viscosities. Hence, 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.

Thus, in a preferred embodiment the kinematic viscosity of component (C), in particular, if obtained by an acidolysis process, is higher than the viscosity of component (A).

Preferably 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).

Preferably the kinematic viscosity of component (C), in particular, if obtained by an acidolysis process, is in the range of about 2000 to 20000 cSt (25°C), preferably about 5000 to about 17500 cSt (25°C), still more preferably about 8000 to about 15000 cSt (25°C).

Preferably 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. However, if 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.

As explained above the component (C), i.e. one or more recycling products of one or more polyurethanes comprising one or more polyol, are not single polyol components but generally comprise further components, which are derived from the recycled polyurethanes, such as pigments, fillers such as calcium carbonate, acrylonitrile/styrene copolymers, polymer polyols on e.g. acrylonitrile/styrene copolymers, PUD polyols on polyurea dispersions (polyurea dispersions) and PIPA polyols on polyurethane dispersions (polyisocyanate polyaddition), melamines, surfactants, and particles such as sand particles, wood particles, cellulose fiber particles, textile fiber particles etc., flame retardants.

Preferably 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.

Usually 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.

Accordingly, 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 ¹H-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.

Furthermore component (C), 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.

A skilled person in the art can therefore easily distinguish between 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).

The 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.

Accordingly, the 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):

(A) one or more chemical compounds, other than components (B) or (C), including virgin polyols, which are not obtained by the recycling of polyurethane foams,

(B) one or more polyurethane forming additives, and

(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.

The 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. 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. For flexible and semi-flexible foams, 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. For rigid foams, the preferred isocyanates are, e.g., polyisocyanates of the MDI type and preferably crude polymeric MDI.

The amount of polyisocyanate included in the foam formulations used relative to the amount of other materials in the formulations is described in terms of “Isocyanate Index”. “Isocyanate Index” means the actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate required to react with all the active hydrogen in the reaction mixture multiplied by one hundred (100) [see e.g. Oertel, Polyurethane Handbook, ibid.]. The Isocyanate Indices in the reaction mixtures used in the process of this invention generally are between 60 and 140. More usually, 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 often is used as a reactive blowing agent in both flexible and rigid foams. 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. For MDI molded foam, 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. Physical 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. In the production of flexible slabstock foams, water is the main blowing agent; however, other blowing agents can be used as auxiliary blowing agents. For flexible slabstock foams, 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 (CFC-11).

Flexible molded foams typically do not use an inert, auxiliary blowing agent, and in any event incorporate less auxiliary blowing agents than slabstock foams. However, there is a great interest in the use of 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. When used, 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.

Temperatures useful for the production of polyurethanes vary depending on the type of foam and specific process used for production as well understood by those skilled in the art. 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).

For example, 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:

100 pbw (parts by weight) polyol component (E) (for example being comprised of one or more polyols in components (A)), about 0.001 to about 15, preferably about 0.01 to about 10, 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)).

As described above, if 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 present invention further relates to the use of components (C), that is, one or more recycling products of one or more polyurethanes comprising one or more polyols, as a functional solvent for the polyurethane foaming additives (B). The present invention further relates to a process for the manufacture of polyurethane foams, comprising the steps of admixing the inventive polyurethane foaming additive composition with one or more polyisocyanates (D), a polyol component (E) (for example being comprised of one or more polyols in components (A)) and optionally 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)) and reacting the mixture to form a polyurethane foam, and the polyurethan foams, obtainable by this process.

While the scope of the present invention is defined by the appended claims, the following examples illustrate certain aspects of the invention and, more particularly, describe methods for evaluation. The examples are presented for illustrative purposes and are not to be construed as limitations on the present invention.

EXAMPLES

(All percentages are weight percentages (wt.-%), all parts are weight parts (pw)).

Component (C):

The recycled polyurethane foam (RPLIF) material (component (C)) was provided by the company Ikano under the trademark RePoliol®.

Components (B);

The 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 ).

Amine catalysts BDMAEE and TEDA, and dipropylene glycol are purchased as normal commercial grades, typically purchased from Sigma-Aldrich for laboratory scale.

Amine catalyst (component (BD composition with RPUF materials (component (CD

Table 1 - Amine catalysts compositions

BDMAEE (N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine) (Bis(2- dimethylaminoethyl)ether)): Niax catalyst A-99,

TEDA (triethylenediamine (1,4-diazabicyclo[2.2.2]octane)): Niax catalyst A-100

DPG: dipropylene glycol

RPUF: recycled polyurethane foam materials

The amine catalysts shown in Table 1 are blended with the RPUF (component (C)) and DPG (component (A)) according to the weight percentages given in above Table 1. 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))

Table 3 - Silicone surfactant compositions

Silicone copolymer (component (B)): same as Silicone D described EP3307801 B1 (Silicone polyether surfactant with two polyether substituents - 4000 MW polyether containing 40% EO, and 1500 MW polyether containing 40% EO)

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.

Table 4. Comparison of the foaming and foam physical performances between silicone surfactants with DPG and with RPLIF

As shown in Table 4, the silicone surfactant composition E with recycled polyurethane foam (RPLIF) materials (component (C)) 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.

Therefore, 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:

1. A composition, comprising:

(B) 5 to 95 pw one or more polyurethane foaming additives, and

(C) 5 to 95 pw of one or more recycling products of one or more polyurethanes comprising one or more polyols, wherein the amount of the polyurethane foaming additives (B) is at least 5 wt.-%, preferably at least 10 wt.-%, more preferably at least 20 wt.-%, based on the total weight of the composition.

2. A 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.

3. A composition according to embodiments 1 or 2, consisting of:

(B) 5 to 95 pw one or more polyurethane foaming additives,

(C) 5 to 95 pw of one or more recycling products of one or more polyurethanes comprising one or more polyols, and

(A) 0 to 90 pw one or more chemical compounds, other than components (B) or (C) as defined before.

4. A composition according to any of the previous embodiments, wherein the 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.

5. A composition according to any of the previous embodiments, wherein the polyurethane foaming additives (B) are selected from the group consisting of catalysts, such as amine catalysts, and silicone-based surfactants.

6. A composition according to any of the previous embodiments, wherein the 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,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,

2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane, N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine), 4-ethyl-2,2-dimethyl-1-oxa-4-aza-2-silacyclohexane, N,N,N',N'-tetramethyl-2,2'-oxybis(ethylamine) (bis(2-dimethylaminoethyl)ether), and triethylenediamine (1 ,4-diazabicyclo[2.2.2]octane); vi. any of the above amine catalysts blocked with an organic acid, and vii. mixtures of the above amine catalysts.

7. A composition according to any of the previous embodiments, wherein (A), the one or more chemical compounds, other than components (B) or (C) are selected from the group consisting of 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.

8. A 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.

9. A composition according to the previous embodiments, wherein (C), the one or more recycling products of one or more polyurethanes comprising one or more polyols, obtained, has not been subjected to a step of isolation or purification of the polyols contained therein, after the polyurethanes were subjected to the cleavage or recycling process.

10. A composition according to any of the previous embodiments, which does not contain isocyanate-functional compounds. 11. A composition according to any of the previous embodiments, which is a non-curable additive composition.

12. A 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.

13. A composition according to any of the previous embodiments, wherein the (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.

14. A 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 aromatic compounds derived from aromatic polyisocyanates used in the manufacture of said polyurethanes.

15. A 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 ¹H-NMR spectrum at a chemical shift of about 7 to about 9 ppm.

16. A 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.

17. A composition according to any of the previous embodiments 2 to 16, wherein the kinematic viscosity (determined at 25°) of the components (C), preferably obtained by acidolysis, and (A) satisfy one or more of the following requirements:

(i) 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),

(ii) 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),

(iii) The kinematic viscosity of component (A) is in the range of about 200 to 1500 cSt (25°C), preferably about 300 to about 1000 cSt (25°C).

18. A non-curable polyol composition, comprising:

(A) one or more chemical compounds, other than components (B) or (C) such as polyols, which are not obtained by the recycling of polyurethane foams,

(B) one or more polyurethane forming additives, and (C) one or more recycling products of one or more polyurethanes comprising one or more polyols, 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.

19. 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.

20. A curable composition comprising the compositions according to any of the previous embodiments and one or more polyisocyanates (D).

21. Polyurethanes obtainable by curing the composition according to the previous embodiment.

22. Use of the compositions according to any of the previous embodiments for the manufacture of polyurethane foams.

23. Use of a (C), one or more recycling products of one or more polyurethanes comprising one or more polyols, as a functional solvent for polyurethane foaming additives (B).

24. 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.

25. Polyurethan foams, obtainable by the process of embodiment 24.

Claims

1. A composition, comprising:

(B) 5 to 95 parts by weight one or more polyurethane foaming additives, and

(C) 5 to 95 parts by weight of one or more recycling products of one or more polyurethanes comprising one or more polyols, wherein the amount of the polyurethane foaming additives (B) is at least 5 wt.-%, preferably at least 10 wt.-%, more preferably at least 20 wt.-%, based on the total weight of the composition.

2. A composition according to claim 1 , further comprising:

3. A composition according to claims 1 , consisting of:

(B) 5 to 95 parts by weight one or more polyurethane foaming additives,

(C) 5 to 95 parts by weight of one or more recycling products of one or more polyurethanes comprising one or more polyols, and

(A) 0 to 90 parts by weight one or more chemical compounds, other than components (B) or (C) as defined before.

4. A composition according to any of the previous claims, wherein the 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.

5. A composition according to any of the previous claims, wherein the polyurethane foaming additives (B) are selected from the group consisting of catalysts, such as amine catalysts, and silicone-based surfactants.

6. A composition according to any of the previous claims, wherein the 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,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,

7. A composition according to any of the previous claims, wherein (A), the one or more chemical compounds, other than components (B) or (C) are selected from the group consisting of 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.

8. A composition according to any of the previous claims, 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.

9. A composition according to the previous claim, wherein (C), the one or more recycling products of one or more polyurethanes comprising one or more polyols, obtained, is not subjected to a step of isolation or purification of the polyols contained therein.

10. A composition according to any of the previous claims, which does not contain isocyanate-functional compounds.

11. A composition according to any of the previous claims, which is a non-curable additive composition.

12. A composition according to any of the previous claims, wherein the (C), one or more recycling products of one or more polyurethanes comprising one or more polyol, is obtained from polyurethane foam materials.

13. A composition according to any of the previous claims, wherein the (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 or toluene diisocyanate, and derivatives thereof, and aliphatic polyols.

14. A composition according to any of the previous claims, 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 aromatic compounds derived from aromatic polyisocyanates, such as methylene diphenyl diisocyanate or toluene diisocyanate, and derivatives thereof, used in the manufacture of said polyurethanes.

15. A composition according to any of the previous claims, 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 ¹H-NMR spectrum at a chemical shift of about 6 to about 8 ppm.

16. A composition according to any of the previous claims, 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.

17. A composition according to any of the previous claims 2 to 16, wherein the kinematic viscosity (determined at 25°) of the components (C), preferably obtained by acidolysis, and (A) satisfy one or more of the following requirements:

18. A non-curable polyol composition, comprising:

19. A process for the manufacture of a composition according to any of the previous claims 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.

20. A curable composition comprising the compositions according to any of the previous claims and one or more polyisocyanates (D).

21. Polyurethanes obtainable by curing the composition according to the previous claim.

22. Use of the compositions according to any of the previous claims for the manufacture of polyurethane foams.

24. A process for the manufacture of polyurethane foams, comprising the steps of admixing a composition according to any of the previous claims with one or more polyisocyanates

(D) and reacting the mixture to form a polyurethane foam.

25. Polyurethan foams, obtainable by the process of claim 24.