A polyurea-containing compound and its use in producing a polymer having improved tensile strength

Abstract

The present disclosure provides a reaction system for producing a polymer, the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: a polyol compound, a polyamine compound, or a mixture thereof; and a polyurea-containing compound represented by structure (1), wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is H or a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; Y is a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; R'' is an isocyanate-reactive group; and n is from 2 to 10.

Description

A POLYUREA-CONTAINING COMPOUND AND ITS USE IN PRODUCING A POLYMER HAVING IMPROVED TENSILE STRENGTHFIELD OF INVENTION

[0001] The present disclosure relates to a reaction system for producing a polymer, wherein the reaction system comprises inter alia a polyurea-containing compound. The reaction system comprising the polyurea-containing compound leads to improved tensile strength properties of the resultant polymer when compared to a comparative reaction system which does not comprise the polyurea-containing compound.

[0002] The present disclosure also relates to a method of preparing the reaction system, a method of producing the polymer, a polymer obtainable by the method as described herein, and the use of the polyurea-containing compound in a reaction system for producing a polymer to increase the tensile strength of the polymer.

[0003] The present disclosure promotes green chemistry and recycling of waste polyurethane material, because the polyurea-containing compound used to prepare a new polymer is obtainable from waste polyurethane material. Therefore, the recycled mass content of the new polymer is increased.BACKGROUND

[0004] Urea-modified polymers (herein referred to as "polymers") are widely used in a broad range of applications, largely because of the ability of the urea groups to modify the properties of a polymer, especially polyurethane-based polymers. Thus, polyurethane-based polymers, which incorporate urea groups, are very useful from a commercial standpoint.

[0005] A polymer, as used herein, may be formed when reacting a polyisocyanate with a polyol and / or polyamine, optionally in the presence of water. When water is present, the water reacts with the polyisocyanate to form a polyamine and carbon dioxide, and in turn the polyamine reacts with the polyisocyanate to form a urea group. The carbon dioxide is used as a blowing agent. However, the carbon dioxide released during the reaction may cause defects in the resultant polymer which may affect the properties of the polymer, and thus the water-polyisocyanate reaction to form a urea group may not be preferred.

[0006] In the case of a polyamine being used, the polyamine reacts with the polyisocyanate to form a urea group. There are two main types of polyamines used to prepare polymers. The first polyamine is a low molecular weight polyamine chain extender, such as diethyl toluene diamine (DETDA). However, some of the low molecular weight polyamines are under regulatory pressure, which affects the ease of use of such polyamines. The second polyamine is a highmolecular weight polyetheramine, such as Jeffamines available from Huntsman Corporation. However, polyetheramines are typically expensive.

[0007] Therefore, there is a need for more safe and cost-effective solutions to incorporate urea groups into polymers, especially polyurethane-based polymers.

[0008] An example of an application which needs a solution to increase the amount of urea groups in a polymer is the spray coating application. Polyurethane-based systems are widely employed in the spray coating industry, and low molecular weight polyamine chain extenders and polyetheramines are often employed to introduce the urea groups in the polyurethane. However, there is a commercial desire to replace the expensive and potentially unsafe low molecular weight polyamine chain extender and / or polyetheramines with cheaper, safer alternatives to form urea groups in the polyurethane polymer when used in spray coating.

[0009] Moreover, there is a need for a polymer which has improved tensile strength properties, so that the polymer may be used for applications where a high tensile strength is required, such as in spray coatings. Specifically, there is a need to improve the tensile strength of a polyurethane- based polymer formed from the polyamine chain extenders and polyetheramines mentioned above. Furthermore, there is a need to be able to fine tune the reaction profile when forming the polymer, such as the polyurethane-based polymer.

[0010] There is also a need to use green chemistry and encourage the recycling of waste polyurethane material. In particular, it would be a huge advancement if the above problems and needs could be addressed while increasing the amount of waste polyurethane material that is recycled.

[0011] The present disclosure addresses the problems and needs mentioned above. That is, the present disclosure provides a safe and cost-effective solution to incorporate urea groups into polymers (such as polyurethane-based polymers), which improves the tensile strength of the polymers, and which may increase the amount of waste polyurethane material that is recycled.SUMMARY

[0012] In a first aspect, there is provided reaction system for producing a polymer (such as a polyurethane-based polymer), the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: i) a polyol compound, a polyamine compound, or a mixture thereof, wherein said compounds are different from the polyurea-containing compound represented by structure (1); and ii) a polyurea-containing compound represented by structure (1):wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is H or a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; Y is a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; R" is an isocyanate-reactive group; and n is from 2 to 10.

[0013] The use of the polyurea-containing compound represented by structure (1) allows for the partial or full replacement of the polyamines currently used in the art in e.g., spray coating formulations. This may therefore save costs and avoid regulatory issues. Moreover, the use of the polyurea-containing compound represented by structure (1) leads to excellent tensile strength of the polymers, and even leads to improved tensile strength of the polymers compared to polymer systems which do not comprise the polyurea-containing compound. As a further point, the polyurea-containing compound represented by structure (1) may be obtained from recycling of waste polyurethane material, and therefore the recycled content of the polymer is increased. Furthermore, the use of the polyurea-containing compound represented by structure (1) allows for tuneable reaction profiles.

[0014] In a second aspect, there is provided method of preparing the reaction system as defined herein, comprising: i) recycling a polyurethane material by mixing the polyurethane material with an aminolysis agent having the following structure:R"-Y-NHR' wherein R', Y and R" are as defined herein, under the conditions required to obtain a slurry comprising a polyurea-containing compound represented by structure (1) as defined herein;ii) optionally isolating the polyurea-containing compound represented by structure (1); iii) providing side B as defined herein by mixing component (i) (the polyol compound, the polyamine compound, or mixture thereof) and the polyurea-containing compound represented by structure (1) obtained in step (i) or (ii); and iv) providing side A as defined herein.

[0015] Obtaining the polyurea-containing compound represented by structure (1) by recycling of a polyurethane material, and adding the polyurea-containing compound to the reaction system, increases the recycled content of the polymer produced from the reaction system. Moreover, it is beneficial to isolate the polyurea-containing compound from the slurry (also termed "recyclate") as the other components of the slurry may negatively affect the properties (such as tensile strength) of the resultant polymer.

[0016] In a third aspect, there is provided a method of producing a polymer, the method comprising the following steps: i) mixing side A with side B of the reaction system as defined herein to form a reactive mixture; and ii) curing the reactive mixture to form a polymer.

[0017] In a fourth aspect, there is provided a polymer obtainable by the method as defined herein.

[0018] In a fifth aspect, there is provided the use of a polyurea-containing compound according to structure (1) as defined herein in a reaction system for producing a polymer to increase the tensile strength of the polymer.

[0019] In a sixth aspect, there is provided a reaction system for producing a polymer, the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: i) a polyol compound, a polyamine compound, or a mixture thereof; and ii) a polyurea-containing compound obtainable by aminolysis of a polyurethane material, wherein the aminolysis comprises mixing the polyurethane material with an aminolysis agent having the following structure:R"-Y-NHR'wherein R' is H or a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; Y is a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; and R" is an isocyanate-reactive group.

[0020] The embodiments described should not be read to limit or otherwise narrow the scope of any inventive concepts otherwise provided by the present disclosure. While multiple embodiments are disclosed, other embodiments will become apparent to those skilled in the art from the following description. Accordingly, the description is to be regarded as illustrative rather than restrictive.DETAILED DESCRIPTION

[0021] There is provided a reaction system for producing a polymer, such as a polyurethane-based polymer, the reaction system comprising side A (isocyanate component) and side B (isocyanatereactive component, or sometimes called a polyol component).

[0022] The reaction system therefore comprises two components (side A and side B) which are separate and only mixed when forming a reactive mixture.

[0023] [Side A]

[0024] Side A is an isocyanate component and comprises a polyisocyanate compound. More than one type of polyisocyanate compound may be present in side A. The phrase "polyisocyanate compound" refers to a molecule which has two or more isocyanate functional groups in the molecule.

[0025] The polyisocyanate compound is not particularly limited, and any polyisocyanate compound known in the art may be used. The polyisocyanate compound may be an aliphatic polyisocyanate (including alicyclic polyisocyanates), an aromatic polyisocyanate, a prepolymer of a polyisocyanate, or a combination thereof. In one embodiment, the polyisocyanate compound is an aromatic polyisocyanate, an alkyl polyisocyanate, a cycloalkyl polyisocyanate, or a combination thereof. In one embodiment, the polyisocyanate compound is an aromatic polyisocyanate. In an embodiment, the polyisocyanate compound is an aromatic diisocyanate compound, preferably a methylene diphenyl diisocyanate (MDI)-based compound. The polyisocyanate compound may be pure MDI or may be a prepolymer thereof, i.e., a prepolymer made from MDI and a polyol.

[0026] Examples of aliphatic polyisocyanates suitable for use as the polyisocyanate compound include, but are not limited to, hexamethylene diisocyanate (HDI), tetraalkyl xylene diisocyanate, cyclohexane diisocyanate, 1,12-dodecane diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-and 1,4-cyclohexane diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl- cyclohexane (isophorone diisocyanate), 4,4'-, 2,2'- or 2,4'-dicyclohexyl-methane diisocyanate, as well as the corresponding isomer mixtures.

[0027] Examples of aromatic polyisocyanates suitable for use as the polyisocyanate compound include, but are not limited to, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'- or 2,4'- or 2,2'-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene diisocyanate (mixtures of MDI and oligomers thereof known in the art as "crude" or polymeric MDI having an isocyanate functionality of greater than 2), 2,4- or 2,6-toluene diisocyanate (TDI), dianisidine diisocyanate, bitolylene diisocyanate, naphthalene-l,4-diisocyanate and diphenylene 4,4'- diisocyanate.

[0028] Prepolymers formed from the reaction of a polyisocyanate (e.g., MDI, modified MDI and / or polymeric-MDI) with a polyol may also be suitable for use as the polyisocyanate compound. The polyol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, other polyol which may be used either individually or in combinations of two or more, or a combination thereof. In addition, the polyol may be a copolymer of one or more of a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, or other polyol.

[0029] According to an embodiment, the polyisocyanate compound may be an isocyanate-terminated prepolymer. The isocyanate-terminated prepolymer may be prepared by reaction of an excessive amount of a polyisocyanate having at least 80 weight%, or at least 85 weight%, or at least 90 weight%, or at least 95 weight%, of MDI (such as 4,4'-MDI) with a suitable difunctional polyol in order to obtain a prepolymer having a desired NCO value. Methods to prepare prepolymers have been described in the art. The relative amounts of polyisocyanate and polyol depend on their equivalent weights and on the desired NCO value and can be determined easily by those skilled in the art. The NCO value of the isocyanate-terminated prepolymer is preferably above 3%, preferably above 5%, more preferably above 8%, and more preferably above 10%. The NCO value of the isocyanate-terminated prepolymer may be from 3% to 40%, or from 5% to 30%, or from 10% to 20%.

[0030] In an embodiment, side A may comprise at least 50 weight%, or at least 75 weight%, or at least 80 weight%, or at least 85 weight%, or at least 90 weight%, or at least 95 weight%, or about 100 weight%, of the polyisocyanate compound, based upon 100 weight% of side A. In an embodiment, side A may comprise at least 50 weight%, or at least 75 weight%, or at least 80 weight%, or at least 85 weight%, or at least 90 weight%, or at least 95 weight%, or about 100 weight%, of an aromatic diisocyanate, such as MDI (preferably, 4,4'-diphenylmethanediisocyanate) or a prepolymer based upon MDI and a polyol, based upon 100 weight% of side A.

[0031] [Side B]

[0032] Side B comprises a polyol compound, a polyamine compound, or a mixture thereof, as well as a polyurea-containing compound represented by structure (1). Preferably, side B comprises a polyol compound and a polyamine compound. This results in a polyurethane-based polymer being formed when side A and side B are mixed and cured.

[0033] [Polyol compound]

[0034] The phrase "polyol compound" refers to a molecule which has two or more hydroxyl functional groups in the molecule. More than one type of polyol compound may be present in side B.

[0035] The polyol compound is not particularly limited, and any polyol compound known in the art may be used. The polyol compound may be a polyether polyol, a polyester polyol, a polyesterpolyether polyol, a polycarbonate polyol, a polycaprolactone polyol, other polyol which may be used either individually or in combinations of two or more, or combinations thereof.

[0036] Examples of polyether polyols include, but are not limited to, polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymer, polytetramethylene ether glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether polyols obtained by ring-opening co-polymerization of alkylene oxides, such as ethylene oxide and / or propylene oxide and / or butylene oxide, with isocyanate-reactive initiators having functionality from 2 to 8.

[0037] The polyether polyol may be made by the addition of alkylene oxides to initiators, which may contain from 2 to 8 active hydrogen atoms per molecule. In some embodiments, the initiators may include glycols, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, ethylenediamine, ethanolamine, diethanolamine, aniline, toluenediamines (e.g., 2,4- and 2,6- toluenediamines), polymethylene polyphenylene polyamines, N-alkylphenylene- diamines, o-chloro-aniline, p-aminoaniline, diaminonaphthalene, or a combination thereof. Suitable alkylene oxides that may be used to form the polyether polyols include ethylene oxide (EO), propylene oxide (PO), butylene oxide, or a combination thereof. In one embodiment, the polyol compound may be an ethylene oxide / propylene oxide polyether polyol, obtained by reacting ethylene oxide and propylene oxide with a suitable initiator having functionality from 2 to 8.

[0038] Examples of polyester polyols include, but are not limited to, those which may be obtained by reacting a diol and a polybasic acid. Examples of diols include ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3-methyl-l,5-pentanediol, 1,9-nonanediol and 2-methyl-l,8-octanediol. Examples of polybasic acids include phthalic acid, dimer acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid and sebacic acid.

[0039] Examples of polycarbonate polyols include, but are not limited to, aliphatic polycarbonate diols, for example those based upon alkylene glycols, ether glycols, alicyclic glycols or mixtures thereof. In some embodiments, the alkylene groups for preparing the polycarbonate polyol can comprise from 5 to 10 carbon atoms and can be a straight chain, cycloalkylene or combinations thereof. Non-limiting examples of such alkylene groups include hexylene, octylene, decylene, cyclohexylene and cyclohexyldimethylene. The polycarbonate polyols can be prepared, in non-limiting examples, by reacting the alkylene glycol with a dialkyl carbonate, such as methyl, ethyl, n-propyl or n-butyl carbonate, or diaryl carbonate, such as diphenyl or dinaphthyl carbonate, or by reacting a hydroxy-terminated alkylene diol with phosgene or bischloroformate, in a manner well known to those skilled in the art.

[0040] Examples of polycaprolactone polyols include, but are not limited to, those prepared by condensing caprolactone in the presence of an initiator such as water, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propylene glycol, polyethylene glycol, polypropylene glycol, poly(oxyethylene-oxypropylene)glycols and similar polyalkylene glycols, either blocked or capped containing up to about 40 or more alkyleneoxy units in the molecule, 3-methyl-l,5-pentanediol, cyclohexanediol, 4,4'-methylene- bis-cyclohexanol, 4,4'-isopropylidene bis-cyclohexanol, xylenediol, 2-(4- hydroxymethylphenyl)ethanol, 1,4-butanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, triisopropanolamine, erythritol, pentaerythritol and N,N,N',N'-tetrakis-(2- hydroxyethyl)ethylene diamine. The caprolactone reacted with the initiator can be caprolactone itself or a substituted caprolactone as described in US Pat. No. 3169945.

[0041] The weight-average molecular weight (as measured by gel permeation chromatography when referred to herein) of the polyol compound may be from about 500 g / mol to about 50000 g / mol, or from about 500 g / mol to about 25000 g / mol, or from about 950 g / mol to about 15000 g / mol, or from about 1000 g / mol to about 10000 g / mol, or from about 1000 g / mol to 7000 g / mol.

[0042] In one embodiment, the polyol compound may be present in side B in an amount of at least 10 weight%, or at least 15 weight%, or at least 20 weight%, or at least 25 weight%, or from 10 weight% to 70 weight%, or from 10 weight% to 60 weight%, or from 10 weight% to 50 weight%, or from 15 weight% to 45 weight%, or from 20 weight% to 40 weight%, based upon 100 weight% of side B.

[0043] [Polyamine compound]

[0044] The phrase "polyamine compound" refers to a molecule which has two or more amine functional groups in the molecule. More than one type of polyamine compound may be present in side B.

[0045] The polyamine compound is not particularly limited, and any polyamine compound known in the art may be used. The polyamine compound may be (i) a polymer terminated with an amine group and having a weight average molecular weight of 500 g / mol or above, (ii) a polyamine having a molar mass of below 500 g / mol, or (iii) a combination thereof.

[0046] In one embodiment, component (i) of side B comprises (i) a polymer terminated with an amine group and having a weight average molecular weight of 500 g / mol or above, and (ii) a polyamine having a molar mass of below 500 g / mol.

[0047] The polymer terminated with an amine group and having a weight average molecular weight of 500 g / mol or above contains at least two amine groups, i.e. has an amine functionality of two or more. In one embodiment, the polymer terminated with an amine group is a diamine. The at least two amine groups may independently be primary or secondary amine groups, and are preferably all primary amine groups. In one embodiment, the polymer part of the polymer terminated with an amine group is a polyether polymer, and may be formed from ethylene oxide and propylene oxide units. In one embodiment, the polymer part of the polymer is aliphatic. In one embodiment, the weight average molecular weight of the polymer terminated with an amine group is 750 g / mol or above, or 1000 g / mol or above, or 1500 g / mol or above, or from 500 g / mol to 10,000 g / mol, or from 1000 g / mol to 5000 g / mol, or from 1000 g / mol to 3000 g / mol. In one embodiment, the polymer terminated with an amine group has a weight average molecular weight of 1000 g / mol to 5000 g / mol and is a polymer terminated with at least two primary amine groups. In one embodiment, the polymer terminated with an amine group has a weight average molecular weight of 1000 g / mol to 5000 g / mol and is a polyether polymer terminated with two primary amine groups. Suitable polymers terminated with an amine group and having a weight average molecular weight of 500 g / mol or above are available from Huntsman Corporation under the tradename Jeffamine®, such as Jeffamine® D2000 (a 2000 molecular weight aliphatic primary amine terminated polyoxypropylene diamine).

[0048] The polyamine having a molar mass of below 500 g / mol contains at least two amine groups, i.e. has an amine functionality of two or more. In one embodiment, the polyamine having a molar mass below 500 g / mol is a diamine. In one embodiment, amine groups in the polyamine having a molar mass of below 500 g / mol are each primary or secondary amine groups. In one embodiment, the polyamine having a molar mass of below 500 g / mol is an aromatic diaminechain extender. In one embodiment, the polyamine has a molar mass below 450 g / mol, or below 400 g / mol, or below 350 g / mol. Suitable polyamines having a molar mass of below 500 g / mol include Unilink® 4200 (4,4'-methylenebis [N-sec-butylaniline], available from Dorf Ketal). The polyamine having a molar mass of below 500 g / mol is a different compound from the chain extender compound mentioned below.

[0049] In one embodiment, the polyamine compound may be present in side B in an amount of at least 10 weight%, or at least 15 weight%, or at least 20 weight%, or at least 25 weight%, or at least 30 weight%, or at least 35 weight%, or at least 40 weight%, or from 10 weight% to 70 weight%, or from 20 weight% to 60 weight%, or from 30 weight% to 60 weight%, or from 35 weight% to 55 weight%, or from 40 weight% to 50 weight%, based upon 100 weight% of side B. In one embodiment, the polyamine having a molar mass of below 500 g / mol may be present in side B in an amount of at least 5 weight%, or at least 10 weight%, or at least 15 weight%, or from 5 weight% to 40 weight%, or from 10 weight% to 30 weight%, or from 15 weight% to 25 weight%, based upon 100 weight% of side B. In one embodiment, the polymer terminated with an amine group and having a weight average molecular weight of 500 g / mol or above may be present in an amount of at least 5 weight%, or at least 10 weight%, or at least 15 weight%, or at least 20 weight%, or from 5 weight% to 50 weight%, or from 10 weight% to 40 weight%, or from 15 weight% to 40 weight%, or from 15 weight% to 35 weight%, based upon 100 weight% of side B. In one embodiment, the polyamine having a molar mass of below 500 g / mol may be present in side B in an amount of from 10 weight% to 30 weight%, and the polymer terminated with an amine group and having a weight average molecular weight of 500 g / mol or above may be present in side B in an amount of from 15 weight% to 35 weight%, based upon 100 weight% of side B.

[0050] Polymers terminated with an amine group and having a weight average molecular weight of 500 g / mol or above and polyamines having a molar mass of below 500 g / mol are often used in combination in spray coating formulations. The present inventors have found that the polyamines having a molar mass of below 500 g / mol and / or the polymers terminated with an amine group and having a weight average molecular weight of 500 g / mol or above may be replaced with the polyurea-containing compound represented by structure (1). Moreover, it has been found by the present inventors that replacing these compounds with the polyurea- containing compound represented by structure (1) increases the tensile strength of a resultant polymer, as well as potentially lowering the cost of the reaction system and increasing the recycled content of the polymer.

[0051] [Polyurea-containing compound represented by structure (1)]

[0052] The polyurea-containing compound is represented by structure (1):wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is H or a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; Y is a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; R" is an isocyanate-reactive group; and n is from 2 to 10.

[0053] As used herein, the term "substituted" refers to (at least one) substituent group on the group to which it relates, e.g. a substituted aromatic group refers to an aromatic group which contains at least one substituent group.

[0054] The substituent group can be any substituent group known in the art. Examples of the substituent group include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a silyl group, an alkoxy group, an amino group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a silyloxy group, a heterocyclic oxy group, a carbamoyl group, a carbamoyloxy group, a heterocyclic thio group, a sulfamoyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a hydrazino group, an imino group, a cyano group, a hydroxy group, a nitro group, a mercapto group, a sulfo group, a carboxy group, a hydroxamic acid group, a sulfino group, a boronate group (-B(OH)2 ), a phosphato group (- OPO(OH)2 ), a phosphono group (-PO(OH)2 ), and a sulfate group (-OSO3 H). The group selected from the substituent group may further have a substituent. In one embodiment, the substituent group contains 12 or less carbon atoms. In another embodiment, the substituentgroup is an alkyl group which contains 12 or less carbon atoms, or 10 or less carbon atoms, or 5 or less carbon atoms, or 3 or less carbon atoms.

[0055] As used herein, the term "aromatic group" refers to its usual meaning in the art. In one embodiment, the aromatic group contains 20 or less carbon atoms, or from 6 to 20 carbons atoms, or from 6 to 15 carbons atoms. Examples of aromatic groups include a phenyl group, a naphthyl group, and an alkylene diphenyl group (such as methylene diphenyl group). An example of a substituted phenyl group is a tolyl group. In one embodiment, the aromatic group is a phenyl group or a methylene diphenyl group.

[0056] As used herein, the term "aliphatic group" refers to its usual meaning in the art, namely a hydrocarbon group which is saturated or unsaturated and which is straight chained or branched, wherein the carbon to carbon chain in the hydrocarbon group may be interrupted with heteroatoms such as oxygen, nitrogen and sulfur. In one embodiment, the aliphatic group contains 20 or less carbon atoms, or from 1 to 15 carbons atoms. Examples of aliphatic groups include an alkyl group, an alkenyl groups, and an alkynyl group. In one embodiment, the aliphatic group is an alkyl group having from 1 to 20 carbon atoms. In another embodiment, the aliphatic group is a methyl group, a ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group.

[0057] As used herein, the term "alicyclic group" refers to its usual meaning in the art, namely a group which contains one or more carbon to carbon rings which may be saturated or unsaturated, but which do not have aromatic character. The carbon to carbon bonds in the ring may be interrupted with heteroatoms such as oxygen, nitrogen and sulfur. In one embodiment, the alicyclic group contains 30 or less carbon atoms, or from 5 to 20 carbons atoms. Examples of alicyclic groups include a cycloalkyl group and a cycloalkenyl groups. In one embodiment, the alicyclic group is a cycloalkyl group having from 5 to 20 carbon atoms.

[0058] As used herein, the term "polymeric group" refers to a group which has a polymeric unit, i.e., a group which has a repeating unit. The polymeric group may be derived from polymeric methylene diphenyl diisocyanate.

[0059] As used herein, the term "hydrocarbon group" refers to a chemical group containing at least carbon and hydrogen atoms, which has a backbone made from carbon atoms (also called the "main chain" herein). The hydrocarbon group may be a linear group, a branched group or a cyclic group. The main chain in the hydrocarbon group may contain carbon to carbon double bonds (i.e. unsaturated carbon to carbon bonds) and / or may contain heteroatoms (such as oxygen to form an ether group, nitrogen, or sulfur). In one embodiment, the hydrocarbon groups of R' and Y independently contain from 1-100 carbon atoms, or from 1-50 carbon atoms,or from 1-10 carbon atoms, or from 1-6 carbon atoms. In one embodiment, the hydrocarbon groups of R' and Y independently do not contain unsaturated carbon to carbon bonds. In one embodiment, the hydrocarbon groups of R' and Y independently do not contain heteroatoms. The hydrocarbon groups of R' and Y are independent of one another, and therefore may be different in the same molecule.

[0060] In one embodiment, R' is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylalkyl.

[0061] In one embodiment, R' is a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms, or from 1 to 5 carbon atoms, or from 1 to 3 carbon atoms. In one embodiment, R' may be a methyl group, an ethyl group or a propyl group.

[0062] In one embodiment, R' is a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms, or 6 to 12 carbon atoms. In one embodiment, R' is a phenyl group or a naphthyl group.

[0063] In one embodiment, R' is a substituted or unsubstituted arylalkyl group having from 6 to 20 carbon atoms, or 6 to 15 carbon atoms.

[0064] In one embodiment, R' is H, a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms or a substituted or unsubstituted arylalkyl group having from 6 to 20 carbon atoms. In one embodiment, R' is H or a substituted or unsubstituted alkyl group having from 1 to 5 carbon atoms. In one embodiment, R' is a methyl group.

[0065] In one embodiment, Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl, a polyether group, or a hydrocarbon group containing an ether functional group.

[0066] In one embodiment, Y is a substituted or unsubstituted alkyl group having 1-10 carbon atoms, or 1-6 carbon atoms, or 1-3 carbon atoms. In one embodiment, Y may be a methyl group, an ethyl group or a propyl group.

[0067] In one embodiment, Y is a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms, or 6 to 12 carbon atoms. In one embodiment, Y is a phenyl group or a naphthyl group.

[0068] In one embodiment, Y is a substituted or unsubstituted arylalkyl group having from 6 to 20 carbon atoms, or 6 to 15 carbon atoms.

[0069] In one embodiment, Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 20 carbon atoms or a substituted or unsubstituted arylalkyl group having from 6 to 20 carbon atoms.

[0070] In one embodiment, Y is a polyether group having at least two ether functional groups. In one embodiment, Y is a polymeric group having at least two ether functional groups in its backbone.

[0071] In one embodiment, X is a methylene diphenyl group, a tolyl group, a hexyl group, an isophorone group, or a polymeric group derived from methylene diphenyl diisocyanate.

[0072] In one embodiment, R" is independently -OH, -COOH, -NHR, -NH2, wherein R is an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms. In one embodiment, R" is -OH, -NHR, - NH2, wherein R is an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms. In one embodiment, R" is -OH.

[0073] In one embodiment, n is from 2 to 10, or 2 to 9, or 2 to 8, or 2 to 7, or 2 to 6, or 2 to 5, or 2 to 4, or 2 to 3, or 2.

[0074] In one embodiment, R' is H or a substituted or unsubstituted alkyl group; Y is a substituted or unsubstituted alkyl group; R" is independently -OH, -COOH, -NHR, -NH2, wherein R is a substituted or unsubstituted alkyl group; and n is 2 to 8. In one embodiment, R' is H or a substituted or unsubstituted alkyl group having from 1-5 carbon atoms; Y is a substituted or unsubstituted alkyl group having from 1-10 carbon atoms; R" is -OH; and n is 2 to 8.

[0075] In one embodiment, X is an aromatic group having 6 to 20 carbon atoms or an aliphatic group having 1 to 15 carbon atoms; R' is H or a substituted or unsubstituted alkyl group having from 1-5 carbon atoms; Y is a substituted or unsubstituted alkyl group having from 1-6 carbon atoms; R" is -OH; and n is 2 to 8.

[0076] In one embodiment, the polyurea-containing compound is represented by structure (2), or preferably structure (2a), structure (2b), structure (2c), or a combination thereof:structure (2b):structure (2c):wherein X, R', Y and R" are as defined herein.

[0077] In one embodiment, the polyurea-containing compound represented by structure (1) is obtainable by aminolysis of a polyurethane material, wherein the aminolysis comprises mixing the polyurethane material with an aminolysis agent having the following structure:R"-Y-NHR' wherein R', Y and R" are as defined herein.

[0078] Suitable aminolysis agents include alkanolamines and polyamines. The polyamines may be diamines, polyamines or polyetheramines. Suitable examples of polyamines include 1,2- ethylenediamine, 1,4-butanediamine, 1,6-diaminohexane, 1,8-diaminooctane, 1,12- diaminododecane, N,N'-dimethyl-l,6-hexanediamine, N,N'-dimethylethylenediamine, N,N'- dimethyl-l,3-propanediamine, xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- methylenebis(cyclohexylamine), isophoronediamine, diethelenetriamine, tetraethylenepentamine, triethylenetetramine, dipropylenetriamine, polyethylenimine, 2,2'- (ethylenedioxy)bis(ethylamine), poly(ethylene glycol) diamine, polypropylene glycol) bis(2- aminopropyl ether), O,O'-bis(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol, poly(tetramethylene ether glycol)-block-polypropylene glycol diamine and poly(tetramethylene ether glycol) diamine. Suitable examples of alkanolamines include 2-methylethanolamine (N-MEA), 2-ethylethanolamine (N-EEA), 2-butylethanolamine (N-BEA), 2-(isopropyl ethanolamine), amino-2-propanol, 5-amino-l-pentanol, 6-amino-l- pentanol, 10-amino-l-decanol, 3-amino-l-propanol, diglycolamine, ethanolamine (MEA), 2-(2- aminoethylamino) ethanol (2-AEAE), 4-amino-l-butanol, 2-amino-l-butanol, l-amino-2- butanol, 2-amino-3-methyl-l-butanol, 3-amino-2-methyl-l-butanol, 3-amino-l-propanol, 2- amino-2-methyl-l-propanol, 2-amino-l-propanol, methanolamine, heptaminol, 2- (ethylamino)ethanol, 3-methylamino-l-propanol, dimethanolamine, dimethylethanolamine, diethanolamine and diisopropanolamine.

[0079] In one embodiment, the aminolysis agent is an alkanolamine. In one embodiment, the aminolysis agent is 2-methylethanolamine (N-MEA).

[0080] In one embodiment, R', Y and R" in structure (1) derive from the aminolysis agent when the polyurea-containing compound is made by aminolysis of polyurethane material. In one embodiment, X in structure (1) derives from the polyisocyanate used to make the polyurethane material when the polyurea-containing compound is made by aminolysis of polyurethane material, and thus the type of polyurethane material determines the group X in structure (1).

[0081] In one embodiment, the aminolysis method comprises mixing the aminolysis agent with the polyurethane material. The polyurethane material is preferably in ground or in pellet, flake or bead form. Optionally, a catalyst is added to the mixture at this stage, such as a metal hydroxide and preferably KOH, to form an aminolysis agent / catalyst mixture. The skilled person would know a suitable quantity of catalyst to use. Optionally, the reaction is carried out under an inert atmosphere, such as Nj. The mixture is then heated up, e.g., to above 80°C, or 100°C- 200°C, or 125°C to 175°, or to about 150°C, and stirred for the required period of time for the polyurethane to break down. This time period may be from 30 mins to 10 hours, or from 1 hour to 5 hours, or from 1 hour to 3 hours, or about 2 hours. Then the aminolysis agent is removed (by e.g. distillation, for instance at between 130-160°C at 20 to 40 mbar). The obtained product (slurry) contains inter alia polyurea-containing compound represented by structure (1) and recovered polyols, diols, and surfactants. In one embodiment, the slurry may then be purified and the polyurea compound may be isolated. The isolation may be carried out by washing the slurry with a suitable solvent such as toluene, filtering off the powder, and drying the powder (e.g., at 50°C under vacuum) to obtain isolated polyurea compound.

[0082] In one embodiment, the isolated polyurea-containing compound represented by structure (1) is used in side B. In an alternative embodiment, the slurry itself, without isolation of thepolyurea-containing compound represented by structure (1), can be used in side B of the reaction system herein.

[0083] The polyurethane material is not particularly limited and any polyurethane material may be used in the method to produce the polyurea-containing compound represented by structure (1). The polyurethane material may be selected MDI-based polyurethane, a TDI-based polyurethane, HMDI-based polyurethane, IPDI-based polyurethane and H12MDI-based polyurethane. In one embodiment, the polyurethane material is MDI-based polyurethane and / or TDI-based polyurethane.

[0084] The polyurea-containing compound represented by structure (1) may also be made via a fossilbased method. This may involve mixing an aminolysis agent (e.g., N-MEA) with a suitable solvent (e.g., toluene) to form an aminolysis agent / solvent mixture, and then adding in a polyisocyanate (e.g., MDI) to the aminolysis agent / solvent mixture. The polyisocyanate may be mixed with a suitable solvent (e.g., toluene) before addition to the aminolysis agent / solvent mixture. The polyisocyanate / aminolysis agent / solvent mixture thus formed is mixed for a sufficient period of time (such as from 1 to 10 hours, or from 1 to 5 hours, or about 3 hours) at a suitable temperature (such as room temperature, or from 10 to 100°C, or from 20 to 30°C) to obtain a solution. The solution is then filtered to obtain a powder, which is then washed with a suitable solution (such as HCI solution) to obtain a solid powder. The solid powder may then be dried (e.g., under vacuum at 30°C). The solid powder is the polyurea-containing compound represented by structure (1).

[0085] In one embodiment, the polyurea-containing compound represented by structure (1) may be present in side B in an amount of at least 10 weight%, or at least 15 weight%, or at least 20 weight%, or at least 25 weight%, or from 10 weight% to 70 weight%, or from 10 weight% to 60 weight%, or from 10 weight% to 50 weight%, or from 15 weight% to 45 weight%, or from 20 weight% to 40 weight%, based upon 100 weight% of side B.

[0086] [Further components]

[0087] According to an embodiment, side B may comprise one or more chain extender compounds each having a weight-average molecular weight of less than about 500 g / mol. A chain extender compound is typically a diol compound. The chain extender compound is not particularly limited, and any chain extender compound known in the art may be used. The one or more chain extender compounds is independently selected from water, 1,6-hexanediol, 1,4- butanediol, monoethylene glycol, diethylene glycol, triethyleneglycol, tetraethyleneglycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,-3-butanediol, 1,5- pentanediol, polycaprolactone diol, 2-methyl-l,3-propanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, hydroquinone bis (2-hydroxyethyl) ether (HQEE), 1,3-Bis (2- hydroxyethyl) resorcinol (HER), ethanolamine, methyldiethanolamine and / or phenyldiethanolamine, or any combinations thereof.

[0088] According to an embodiment, side B may comprise a blowing agent. The blowing agent is not particularly limited, and any blowing agent known in the art may be used. The blowing agent may be a physical blowing agent, a chemical blowing agent, or a combination thereof. Suitable physical blowing agents may be selected from CO2, N2, isobutene, methylformate, dimethyl ether, methylene chloride, acetone, t-butanol, argon, krypton, xenon, chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluoro carbons (HCFCs), hydrofluoroolefins (HFOs), Hydrochlorofluoro olefins (HCFOs), and hydrocarbons such as pentane, isopentane and cyclopentane and mixtures thereof. Suitable chemical blowing agents may be selected from water, mono-carboxylic acid (e.g., formic acid) and polycarboxylic acid.

[0089] According to an embodiment, side B may comprise a catalyst. The catalyst is not particularly limited, and any catalyst known in the art may be used. A catalyst may be included in side B in order to improve the cure of the reaction mixture formed when sides A and B are mixed. Suitable catalysts include blocked tertiary amine catalysts (such as DABCO®8154 available from Evonik), blocked formic acid catalysts (such as JEFFCAT®ZF-54 available from Huntsman Corporation) and a tertiary amine blow catalyst (such as POLYCAT®SA 5 available from Evonik).

[0090] According to an embodiment, side B may comprise a surfactant. The surfactant is not particularly limited, and any surfactant known in the art may be used. Examples of suitable commercially available surfactants include, but are not limited to Tegostab B8494, Tegostab B8905, Tegostab B8993, Tegostab B8948, Tegostab B8017, Tegostab B8930, Tegostab B8950, Tegostab B8960, Vorasurf DC193, Vorasurf 5382, Niax L1500, Niax L1550, Niax L1542, Niax UAX 7061, Niax UAX 6897, Niax UAX 6639, Niax UAX 7061, Tegostab B8466 and Tegostab B8416.

[0091] Other additives may be present in side B, such as UV stabilizers, fire retardants and the like which are known in the art.

[0092] [Method of preparing the reaction system]

[0093] The present disclosure provides a method of preparing the reaction system as defined herein, comprising: i) recycling a polyurethane material by mixing the polyurethane material with an aminolysis agent having the following structure:R"-Y-NHR' wherein R', Y and R" are as defined herein,under the conditions required to obtain a slurry comprising a polyurea-containing compound represented by structure (1) as defined herein; ii) optionally isolating the polyurea-containing compound represented by structure (1); iii) providing side B as defined herein by mixing component (i) (the polyol compound, the polyamine compound, or mixture thereof) and the polyurea-containing compound represented by structure (1) obtained in step (i) or (ii); and iv) providing side A as defined herein.

[0094] The aminolysis agent and polyurethane material are as described above. The conditions required for the reaction are generally known to those skilled in the art and are also described above. The step of isolating the polyurea-containing compound represented by structure (1) is optional as the slurry itself may be used in side B.

[0095] [Method of producing a polyurethane-based polymer]

[0096] The present disclosure provides a method of producing a polymer, the method comprising the following steps: i) mixing side A with side B of the reaction system as defined herein to form a reactive mixture; and ii) curing the reactive mixture to form a polymer.

[0097] The present disclosure also provides a polymer obtainable by the method.

[0098] The skilled person would know how to mix side A with side B in order to form a reactive mixture, and the skilled person would know the conditions under which to cure the reactive mixture to form a polymer.

[0099] In one embodiment, the polymer which is formed is a polyurethane-based polymer. In this case, mixing the side A and side B at room temperature and allowing up to 48 hours, or up to 24 hours, to cure is suitable. In one embodiment, the isocyanate index may range from 70 to 150, or from 80 to 120, or from 90 to 115, or from 95 to 110. The exact isocyanate index used depends on the purpose of the polyurethane-based polymer, and the skilled person would know how to choose an appropriate value for the isocyanate index.

[0100] The use of a polyurea-containing compound represented by structure (I) in side B allows for a reaction profile which can be tailored, because curing can be tailored to a timeframe which is more suited for the application of the resultant polymer.

[0101] In one embodiment, the method further comprises a step of spraying or coating the reactive mixture formed in step i) onto a surface, followed by step ii), optionally wherein the step ofmixing of side A with side B is performed during spraying or coating the reactive mixture onto a surface.

[0102] In one embodiment, the tensile strength of the polymer is at least about 3 MPa, preferably at least 4 MPa, more preferably at least 4.5 MPa, when measured according to DIN 53504 using a polymer film having a thickness of 100 microns.

[0103] [Use of polyurea-containing compound according to structure (1) in a reaction system for producing a polyurethane-based polymer to increase the tensile strength of the polymer]

[0104] The present disclosure provides a use of a polyurea-containing compound according to structure (1) as defined herein in a reaction system for producing a polymer to increase the tensile strength of the polymer. This is particularly relevant when the polymer is a polyurethane-based polymer.

[0105] [Non-limiting embodiments]

[0106] In one embodiment, there is provided a reaction system for producing a polyurethane-based polymer, the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: i) a polyol compound, a polyamine compound, or a mixture thereof, wherein said compounds are different from the polyurea-containing compound represented by structure (1); and ii) a polyurea-containing compound represented by structure (1):wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is H or a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; Y is a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; R" is an isocyanate-reactive group; and n is from 2 to 10.

[0107] In one embodiment, there is provided a reaction system for producing a polyurethane-based polymer, the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: i) a polyol compound and a polyamine compound, wherein said compounds are different from the polyurea-containing compound represented by structure (1); and ii) a polyurea-containing compound represented by structure (1):wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylalkyl; Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl, a polyether group, or a hydrocarbon group containing an ether functional group; and R" is independently -OH or -NHR, wherein R is an alkyl group having from 1 to 10 carbon atoms; and n is from 2 to 10.

[0108] In one embodiment, there is provided a reaction system for producing a polyurethane-based polymer, the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: i) a polyol compound and a polyamine compound, wherein said compounds are different from the polyurea-containing compound represented by structure (1); and ii) a polyurea-containing compound represented by structure (1):wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylalkyl; Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl, a polyether group, or a hydrocarbon group containing an ether functional group; and R" is independently -OH or -NHR, wherein R is an alkyl group having from 1 to 10 carbon atoms; and n is from 2 to 10, and wherein the polyamine compound is (i) a polymer terminated with an amine group and having a weight average molecular weight of 500 g / mol or above, (ii) a polyamine having a molar mass of below 500 g / mol, or (iii) a combination thereof.

[0109] In one embodiment, there is provided a reaction system for producing a polyurethane-based polymer, the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: i) a polyol compound and a polyamine compound, wherein said compounds are different from the polyurea-containing compound represented by structure (1); and ii) a polyurea-containing compound represented by structure (1):wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is a substituted or unsubstituted alkyl group having from 1 to 10 carbonatoms; Y is a substituted or unsubstituted alkyl group having 1-10 carbon atoms; and R" is -OH; and n is 1, and wherein the polyamine compound is (i) a polymer terminated with an amine group and having a weight average molecular weight of 500 g / mol or above, (ii) a polyamine having a molar mass of below 500 g / mol, or (iii) a combination thereof, and wherein the polyurea-containing compound represented by structure (1) is present in side B in an amount of at least 20 weight%, based upon 100 weight% of side B.

[0110] In one embodiment, there is provided a method of producing a polyurethane-based polymer, the method comprising the following steps: i) mixing side A with side B of the reaction system as defined herein to form a reactive mixture; ii) spraying or coating the reactive mixture formed in step i) onto a surface, optionally wherein the step of mixing of side A with side B is performed during spraying or coating the reactive mixture onto a surface; and iii) curing the reactive mixture to form the polyurethane-based polymer.

[0111] [Examples]

[0112] The present disclosure will be described in more detail with reference to the Examples. The present disclosure is not limited to the following Examples.

[0113] Synthesis Example 1: Synthesis of polyurea-containing compound represented by structure (1) by recycling method according to present disclosure:

[0114] 150g of N-MEA (N-methylethanolamine) and 0.1g of KOH were added into a 4-neck reaction flask equipped with stirrer, head mixer, Nj inlet and thermometer. 100g of ground MDI-based polyurethane flexible foam was then added into the N-MEA / KOH mixture. The mixture was heated up to 150°C and stirred for 2 hours. The unreacted N-MEA was then distilled off between 140-150°C at 30 mbar. The obtained product (slurry) contained 53 weight% of polyurea-containing compound represented by structure (1) and recovered polyols, diols, and surfactants. The obtained slurry contained 64 weight% recycled content. The slurry was then washed with toluene, the powder was filtered off, dried at 50°C under vacuum and pure polyurea-containing compound represented by structure (1) (98 weight% purity) was obtained (powder). The recycled content of the purified polyurea-containing compound represented by structure (1) was 62 weight%.

[0115] Production of polyurethane-based polymer films:

[0116] A side B (an isocyanate-reactive component) and a comparative side B (an isocyanate-reactive component which is not in accordance with the present disclosure) were formed by mixingtogether at 50°C the materials listed in the below Table 1. The polyurea-containing compound represented by structure (1) was first dispersed in Daltocel®F456 at 50°C for 30 mins using a mechanical stirrer.Table 1:All values in Table 1 refer to weight%Materials listed:Daltocel®F456 - 2000 Mw polyoxypropylene diol (available from Huntsman Corporation).Daltocel®F613 - ethylene oxide / propylene oxide polyether polyol (available from Huntsman Corporation)Jeffamine® D2000 - 2000 Mw aliphatic primary amine terminated polyoxypropylene diamine (available from Huntsman Corporation).Unilink® 4200 - 4,4'-methylenebis [N-sec-butylaniline] (available from Dorf Ketal).

[0117] Side A contained Suprasec®2332 (an MDI prepolymer having isocyanate value of 15 weight%, available from Huntsman Corporation).

[0118] Example 1:

[0119] A polyurethane-based polymer film according to the present disclosure was prepared by mixing side A with side B (1) at an isocyanate index of 105. Side A and side B were mixed together for 30 seconds at 1000 rpm in a speedmixer. A film, with a thickness of 100 microns, was prepared on a polyethylene substrate and allowed to cure for 24 hours at room temperature.

[0120] Curing time and conversion after 24 hours were measured. Conversion was assessed based on the presence of residual NCO groups, indicated by the presence of 2270 cm1band in FTIR-ATR analysis of the film. The film was detached from the substrate and the tensile strength was measured. The tensile test method was as follows: the film was cut into "dog-bone" shaped specimen. The selected geometry had a cross section of 4 x 2 mm. The specimen was strained at 100 mm / min with an Instron device (using standard DIN 53504).

[0121] Comparative Example 1:

[0122] A comparative polyurethane-based polymer film (not in accordance with the present disclosure) was prepared by mixing side A with comparative side B (1) in the same manner as for Example1. The curing time, conversion after 24 hours and tensile strength of the comparative polyurethane-based polymer film were also measured.

[0123] Example 2:

[0124] A polyurethane-based polymer film according to the present disclosure was prepared by mixing side A with side B (2) at an isocyanate index of 105. Side A and side B were mixed together for 30 seconds at 1000 rpm in a speed mixer. A film, with a thickness of 100 microns, was prepared on a polyethylene substrate and allowed to cure for 24 hours at room temperature.

[0125] Curing time and conversion after 24 hours were measured. Conversion was assessed based on the presence of residual NCO groups, indicated by the presence of 2270 cm1band in FTIR-ATR analysis of the film. The film was detached from the substrate and the tensile strength was measured. The tensile test method was as follows: the film was cut into "dog-bone" shaped specimen. The selected geometry had a cross section of 4 x 2 mm. The specimen was strained at 100 mm / min with an Instron device (using standard DIN 53504).

[0126] Comparative Example 2:

[0127] A comparative polyurethane-based polymer film (not in accordance with the present disclosure) was prepared by mixing side A with comparative side B (2) in the same manner as for Example 1. The curing time, conversion after 24 hours and tensile strength of the comparative polyurethane-based polymer film were also measured.

[0128] The results for the polyurethane-based polymer films and the comparative polyurethane-based polymer films are summarized in Table 2.Table 2:

[0129] As can be seen from Table 2, using the polyurea-containing compound represented by structure (1) according to the present disclosure resulted in improved tensile strength of the polyurethane-based polymer films (see Example 1 vs Comparative Example 1, and Example 2 vs Comparative Example 2) and a slower curing time, which allows for more tunability in terms of curing. Moreover, the recycled content of the polyurethane-based polymer films was higher when using the polyurea-containing compound represented by structure (1) according to the present disclosure.

[0130] Example 3:

[0131] The slurry prepared in Synthesis Example 1 was used directly in side B (3) to make a polyurethane-based polymer film according to the present disclosure. Side B (3) was prepared in same manner as described above and contained 21.7 weight% Daltocel®F456, 21.7 weight% Jeffamine®D2000, 15.8 weight% Unilink®4200 and 40.8 weight% slurry from Synthesis Example 1. Side B (3) contained 21.7 weight% polyurea-containing compound represented by structure (1).

[0132] A polyurethane-based polymer film according to the present disclosure was made in the same manner as for Example 1, using side B (3) containing the slurry and Side A as described above. The curing time, conversion after 24 hours and tensile strength of the polyurethane-based polymer film were also measured in the same manner as for Example 1 and are listed in below Table 3.Table 3:

[0133] Thus, when compared with Comparative Example 1 which has a tensile strength of 4.4 MPa, there is a clear improvement in tensile strength when using the slurry prepared in Synthesis Example 1 without the need for purification, which also yields a higher total recycled content.

[0134] All ranges described herein are exemplary in nature and include any and all values in between. The terms "substantially", "approximately" and "about" used herein are interchangeable and refer to a measurement that includes the stated measurement and any measurements reasonably close to the stated measurement. Measurements that are reasonably close to the stated measurement deviate from the stated measurement by a reasonably small amount as understood and readily ascertained by individuals having ordinary skill in the relevant art. Such deviations may be attributable to measurement error, differences in measurement and / or manufacturing equipment calibrations, human error in reading and / or setting measurements, minor adjustments made to optimize performance and / or structural parameters in view of differences in measurement associated with other components, particular implementation scenarios, imprecise adjustment and / or manipulation of objects by a person or machine. In the event it is determined that individuals having ordinary skill in the relevant art would not readily ascertain values for such reasonably small differences, the terms "about" and "approximately" can be understood to mean plus or minus 10% of the stated value.

[0135] Throughout the description and claims, the terms take the meanings explicitly defined herein, unless the context clearly dictates otherwise.

[0136] The phrases "in one embodiment" "in an embodiment" and "in some embodiments" etc. as used herein do not necessarily refer to the same embodiment(s), though they may. Furthermore, the phrases "in another embodiment" and "in some other embodiments" as used herein do not necessarily refer to a different embodiment, though they may. All embodiments of the present disclosure are intended to be combinable.

[0137] The terms "comprises" and "comprising" mean to include but not limited to, such that further features may be present. The terms may also mean to consist of or consist essentially of.

[0138] All references and test methods cited herein are incorporated by reference in their entireties.-END OF DESCRIPTION-

Claims

CLAIMS1. A reaction system for producing a polymer, the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: iii) a polyol compound, a polyamine compound, or a mixture thereof; and iv) a polyurea-containing compound represented by structure (1):wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is H or a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; Y is a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; R" is an isocyanate-reactive group; and n is from 2 to 10.

2. A reaction system according to Claim 1, wherein the polyurea-containing compound is represented by structure (2), or preferably structure (2a), structure (2b), structure (2c), or a combination thereof: structure (2):structure (2a):structure (2b):structure (2c):wherein X, R', Y and R" are as defined in Claim 1.

3. A reaction system according to Claim 1 or Claim 2, wherein R' is H or a substituted or unsubstituted alkyl group; Y is a substituted or unsubstituted alkyl group; and R" is independently -OH, -COOH, -NHR, or -NHz, wherein R is a substituted or unsubstituted alkyl group.

4. A reaction system according to any preceding claim, wherein R' is H or a substituted or unsubstituted alkyl group containing from 1-5 carbon atoms; Y is a substituted or unsubstituted alkyl group containing from 1-10 carbon atoms; and R" is -OH.

5. A reaction system according to any preceding claim, wherein the polyurea-containing compound represented by structure (1) is obtainable by aminolysis of a polyurethane material, wherein the aminolysis comprises mixing the polyurethane material with an aminolysis agent having the following structure:R"-Y-NHR' wherein R', Y and R" are as defined in any preceding claim.

6. A reaction system according to any preceding claim, wherein the polyurea-containing compound represented by structure (1) is present in side B in an amount of at least 15 weight%, preferably at least 20 weight%, based upon 100 weight% of side B.

7. A reaction system according to any preceding claim, wherein side B comprises a polyol compound which is different from the polyurea-containing compound according to structure (1), wherein the polyol compound is a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polyester-polyether polyol, or a combination thereof.

8. A reaction system according to any preceding claim, wherein the polyol compound is present in side B in an amount of at least 15 weight%, preferably at least 20 weight%, based upon 100 weight% of side B.

9. A reaction system according to any preceding claim, wherein the polyisocyanate compound is an aromatic polyisocyanate, an alkyl polyisocyanate, a cycloalkyl polyisocyanate, or a combination thereof, preferably wherein the polyisocyanate compound is an aromatic polyisocyanate.

10. A reaction system according to any preceding claim, wherein side B comprises a polyamine compound which is different from the polyurea-containing compound according to structure (1), wherein the polyamine compound is (i) a polymer terminated with an amine group and having a weight average molecular weight of 500 g / mol or above, (ii) a polyamine having a molar mass of below 500 g / mol, or (iii) a combination thereof.

11. A reaction system according to any preceding claim, wherein the polyamine compound is present in side B in an amount of at least 10 weight%, preferably at least 35 weight%, based upon 100 weight% of side B.

12. A reaction system according to any preceding claim, wherein the tensile strength of the polymer is at least about 3 MPa, preferably at least 4 MPa, more preferably at least 4.5 MPa, when measured according to DIN 53504 using a polymer film having a thickness of 100 microns.

13. A method of preparing the reaction system as defined in any preceding claim, comprising: i) recycling a polyurethane material by mixing the polyurethane material with an aminolysis agent having the following structure:R"-Y-NHR' wherein R', Y and R" are as defined in any preceding claim, under the conditions required to obtain a slurry comprising a polyurea-containing compound represented by structure (1) as defined in any preceding claim; ii) optionally isolating the polyurea-containing compound represented by structure (1); iii) providing side B as defined in any preceding claim by mixing component (i) of side B as defined in Claim 1 and polyurea-containing compound represented by structure (1) obtained in step (i) or (ii); and iv) providing side A as defined in any preceding claim.

14. A method of producing a polymer, the method comprising the following steps: i) mixing side A with side B of the reaction system as defined in any of Claims 1-12 to form a reactive mixture; and ii) curing the reactive mixture to form a polymer.

15. A method of producing a polymer according to Claim 14, comprising a step of spraying or coating the reactive mixture formed in step i) onto a surface, followed by step ii), optionally wherein the step of mixing of side A with side B is performed during spraying or coating the reactive mixture onto a surface.

16. A polymer obtainable by the method as defined in Claim 14.

17. Use of a polyurea-containing compound according to structure (1) in a reaction system for producing a polymer to increase the tensile strength of the polymer, wherein structure (1) is as follows:wherein X is a substituted or unsubstituted aromatic group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted alicyclic group, or a substituted or unsubstituted polymeric group; R' is H or a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; Y is a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; R" is an isocyanate-reactive group; and n is from 2 to 10.

18. A reaction system for producing a polymer, the reaction system comprising: side A) an isocyanate component comprising a polyisocyanate compound; and side B) an isocyanate-reactive component comprising: iii) a polyol compound, a polyamine compound, or a mixture thereof; and iv) a polyurea-containing compound obtainable by aminolysis of a polyurethane material, wherein the aminolysis comprises mixing the polyurethane material with an aminolysis agent having the following structure:R"-Y-NHR' wherein R' is H or a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; Y is a substituted or unsubstituted hydrocarbon group which may contain one or more unsaturated carbon to carbon bonds and / or one or more heteroatoms in a main chain of the hydrocarbon group; and R" is an isocyanate-reactive group.

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