METHOD FOR THE PRODUCTION OF NON-FLUORATED URETHANE-BASED COATINGS

Description

FIELD OF INVENTION

[0001] This invention relates to a composition comprising an organic urethane compound useful for imparting durable water repellency and optionally stain release to textiles, the compound derived from isocyanates and bio-based organic compounds such as sorbitans and citrates.BACKGROUND OF THE INVENTION

[0002] Various compositions are known to be useful as treating agents to provide water repellency and optionally stain release to textile substrates. Many such treating agents are fluorinated polymers and copolymers, or non-fluorinated polymers and copolymers. Non-fluorinated compounds are predominately polyacrylate-based or urethane-based copolymers.

[0003] Fluorinated copolymers provide good repellency to water and oil. Various attempts have been made to produce a non-fluorinated water repellent. Non-fluorinated copolymers are known to provide water repellency and optionally stain release to textiles, but are less effective than the fluorinated counterparts.

[0004] Moore, in U.S. Patent No. 6,864,312, discloses a polyurethane polymer that provides moisture resistance. Moore claims polyurethane polymer particle dispersions, where the polyurethane polymers are isocyanate-terminated prepolymers prepared from a formulation including a polyisocyanate and a polyol.SUMMARY OF INVENTION

[0005] The need exists for non-fluorinated compounds that provide water repellency and optionally stain release for textiles, with performance results comparable to fluorinated treating agents. Also desirable is a non-fluorinated compound that can be bio-based derived. The present invention meets these needs.

[0006] The present invention provides a method comprising: (i) reacting (a) at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia) or (Ib) in a dry organic solvent free of isocyanate-reactive groups: wherein each R is independently a -H or -C(O)R 1< and two or three of R are -C(O)R 1< ; each R 1< is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R 3< is independently a -H; -R 1< ; - C(O)R 1< ; -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' R 2< ; or -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' C(O)R 1< ; each R 4< is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' R 2< ; or -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' C(O)R 1< ; each n' is independently 0 to 20; each m' is independently 0 to 20; m'+n' is greater than 0; each R 2< is independently -H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; or a mixture thereof, provided when the compound is Formula (Ib), then the compound is di-substituted, or tri-substituted with alkyl groups, and at least one R 2< , R 3< or R 4< is a -H. The method may further comprise additional reactants such as a second organic compound and / or water. Water can be used to cross-link unreacted isocyanates to create urea linkages. DETAILED DESCRIPTION OF INVENTION

[0007] Herein all trademarks are designated with capital letters.

[0008] The present invention provides a method comprising: (i) reacting (a) at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia) or (Ib) in a dry organic solvent free of isocyanate-reactive groups: wherein each R is independently a -H or -C(O)R 1< , and two or three of R are -C(O)R 1< ; each R 1< is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R 3< is independently a -H; -R 1< ; - C(O)R 1< ; -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' R 2< ; or -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' C(O)R 1< ; each R 4< is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' R 2< ; or -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' C(O)R 1< ; each n' is independently 0 to 20; each m' is independently 0 to 20; m'+n' is greater than 0; each R 2< is independently -H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; or a mixture thereof, provided when the compound is Formula (Ib), then the compound is di-substituted, or tri-substituted with alkyl groups, and at least one R 2< , R 3< or R 4< is a -H.

[0009] For compounds of Formula (Ia) or (Ib), the -(CH 2 CH 2 O)- represents oxyethylene groups (EO) and -(CH(CH 3 )CH 2 O)- represents oxypropylene groups (PO). These compounds can contain only EO groups, only PO groups, or mixtures thereof. These compounds can also be present as a tri-block copolymer designated PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol), for example.

[0010] In one embodiment, the invention relates to a method comprising: (i) reacting (a) at least one isocyanate group-containing isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and compounds of Formula (Ia). Compounds of Formula (Ia) where at least one of R is -H and at least one R is selected from -C(O)R 1< are commonly known as alkyl sorbitans. These sorbitans can be mono-substituted, di-substituted, or tri-substituted with -C(O)R 1< . It is known that commercially available sorbitans, such as SPAN, contain a mixture of the various sorbitans ranging from where each R is H (un-substituted), and sorbitans where each R is -C(O)R 1< (fully substituted); wherein R 1< is a linear or branched alkyl group having 5 to 29 carbons; and mixtures of various substitutions thereof. The commercially available sorbitans may also include amounts of sorbitol, isosorbide, or other intermediates or byproducts.

[0011] In one preferred embodiment, two or three of R are -C(O)R 1< , and R 1< is a linear branched alkyl group having 5 to 29 carbons, more preferably 7 to 21 carbons, and most preferably 11 to 21 carbons. Preferred compounds include mono-, di-, and tri-substituted sorbitans derived from caprylic acid, capric acid, lauric acid, mysteric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and mixtures thereof. Particularly preferred compounds include mono-, di-, and tri-substituted sorbitan stearates or sorbitan behenins.

[0012] R 1< is a linear or branched alkyl group having 5 to 29 carbons comprising at least 1 unsaturated bond. Examples of compounds of Formula (Ia) wherein two or three of R are -C(O)R 1< ; and R 1< contains least 1 unsaturated bond, include, but are not limited to, sorbitan trioleate (i.e., wherein R 1< is -C 7 H 14 CH=CHC 8 H 17 ). Other examples include but are not limited to mono-, di-, and tri-substituted sorbitans derived from palmitoleic acid, lineolic acid, arachidonic acid, and erucic acid.

[0013] It is known that commercially available polysorbates, contain a mixture of the various polysorbates ranging from where each R 2< is H (unsubsituted), and polysorbates where each R 1< is a linear or branched alkyl group having 5 to 29 carbons (fully substituted); and mixtures of various substitutions thereof. Examples of compounds of Formula (Ia) include polysorbates such as polysorbate tristearate, and polysorbate monostearate. Examples of compounds of Formula (Ia) wherein m+n is greater than 0, and wherein R 1< comprises at least 1 unsaturated bond, but not limited to, polysorbate trioleate (wherein R 1< is C 7 H 14 CH=CHC 8 H 17 ) and are sold commercially under the name Polysorbate 80. Reagents may include mixtures of compounds having various values for R, R 1< , and R 2< , and may also include mixtures of compounds where R 1< comprises at least one unsaturated bond with compounds where R 1< is fully saturated.

[0014] Compounds of Formula (Ib) are known as alkyl citrates. These citrates can be present as a di-substituted or tri-substituted with alkyl groups. It is known that commercially available citrates contain a mixture of the various citrates as well as citric acids from where R 3< and each R 4< is -H, ranging to citrates where each R 4< is a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; and mixtures of various substitutions thereof. Mixtures of citrates having various values for R 1< , R 2< , R 3< , and R 4< may be used, and may also include mixtures of compounds where R 1< comprises at least one unsaturated bond with compounds where R 1< is fully saturated. Alkyl citrates are also commercially available wherein m'+n' is greater than 0, R 4< is -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' R 2< ; or -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' C(O)R 1< and are present in the various substitutions from wherein R 3< and each R 2< is H to wherein each R 1< and / or R 2< is a linear or branched alkyl group having 5 to 30 carbons optionally comprising at least 1 unsaturated bond. Examples of compounds of Formula (Ib) include, but are not limited to, trialkyl citrates.

[0015] Compounds of Formulas (Ia) or (Ib) can all be bio-based derived. By "bio-based derived", it is meant that at least 10% of the material can be produced from non-crude oil sources, such as plants, other vegetation, and tallow. In one embodiment, the compounds of formulas (Ia) and (Ib) are from about 10% to 100% bio-based. In one embodiment, the compounds of formulas (Ia) and (Ib) are from about 35% to 100% bio-based. In one embodiment, the compounds of formulas (Ia) and (Ib) are from about 50% to 100% bio-based. In one embodiment, the compounds of formulas (Ia) and (Ib) are from about 75% to 100% bio-based. In one embodiment, the compounds of formulas (Ia) and (Ib) are 100% bio-based. At least one R, R 3< , R 4< of each of Formulas (Ia) or (Ib) is -H to allow reactivity with isocyanate groups. The average OH value of the compounds can range from just greater than 0 to about 230, preferably about 10 to about 175, and most preferably from about 25 to about 140.

[0016] In methods of the present invention, a compound of formula (Ia) or (Ib), or mixtures thereof, is reacted with an isocyanate group-containing isocyanate, diisocyanate, polyisocyanate, or mixture thereof. The isocyanate group-containing compound adds to the branched nature of the polymer. The term "polyisocyanate" is defined as di- and higherfunctional isocyanates, and the term includes oligomers. Any monoisocyanate or polyisocyanate having predominately two or more isocyanate groups, or any isocyanate precursor of a polyisocyanate having predominately two or more isocyanate groups, is suitable for use in this invention. For example, hexamethylene diisocyanate homopolymers are suitable for use herein and are commercially available. It is recognized that minor amounts of diisocyanates can remain in products having multiple isocyanate groups. An example of this is a biuret containing residual small amounts of hexamethylene diisocyanate.

[0017] Also suitable for use as the polyisocyanate reactant are hydrocarbon diisocyanate-derived isocyanurate trimers. Preferred is DESMODUR N-100 (a hexamethylene diisocyanate-based vailable from Bayer Corporation, Pittsburgh, PA). Other triisocyanates useful for the purposes of this invention are those obtained by reacting three moles of toluene diisocyanate. The isocyanurate trimer of toluene diisocyanate and that of 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate are other examples of triisocyanates useful for the purposes of this invention, as is methane-tris-(phenylisocyanate). Precursors of polyisocyanate, such as diisocyanate, are also suitable for use in the present invention as substrates for the polyisocyanates. DESMODUR N-3300, DESMODUR N-3600, DESMODUR Z-4470, DESMODUR H, DESMODUR N3790, and DESMODUR XP 2410, from Bayer Corporation, Pittsburgh, PA, and bis-(4-isocyanatocylohexyl)methane are also suitable in the invention.

[0018] Preferred polyisocyanate reactants are the aliphatic and aromatic polyisocyanates containing biuret structures, or polydimethyl siloxane containing isocyanates. Such polyisocyanates can also contain both aliphatic and aromatic substituents.

[0019] Particularly preferred as the (poly)isocyanate reactant for all the embodiments of the invention herein are hexamethylene diisocyanate homopolymers commercially available, for instance as DESMODUR N-100, DESMODUR N-75 and DESMODUR N-3200 from Bayer Corporation, Pittsburgh, PA; 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate available, for instance as DESMODUR I (Bayer Corporation); bis-(4-isocyanatocylohexyl)methane available, for instance as DESMODUR W (Bayer Corporation) and diisocyanate trimers of formulas (IIa), (IIb), (IIc) and (IId):

[0020] The diisocyanate trimers (IIa-d) are available, for instance as DESMODUR Z4470, DESMODUR IL, DESMODUR N-3300, and DESMODUR XP2410, respectively, from Bayer Corporation.

[0021] In one embodiment, the reaction product of (a) an isocyanatecontaining compound with (b) an isocyanate-reactive compound contains unreacted isocyanate groups which are further reacted with (c) at least one second compound selected from water, organic compounds of Formula (IIIa)         R 5< -X     (IIIa), organic compounds of Formula (IIIb)         R 15< -(OCH 2 CH(OR 15< )CH 2 ) z -OR 17<      (IIIb), or mixtures thereof, wherein R 5< is selected from a -C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group, a hydroxy-functional C 1 to C 30 linear or branched alkyl, a hydroxy-functional linear or branched C 1 to C 30 polyether, a hydroxy-functional linear or branched polyester, a hydroxy-functional linear or branched organosiloxane, a thiol-functional C 1 to C 30 linear or branched alkyl, an amine-functional C 1 to C 30 linear or branched alkyl, wherein R 7< , R 8< , and R 9< are each independently, -H, -C 1 to C 6 alkyl, or combinations thereof; R 10< is a divalent alkyl group of 1 to 20 carbons; X is an isocyanate-reactive functional group such as -OH, -C(O)OH, -SH, - NH(R 12< ), -O-(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t -H or -[C(O)]-O-(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t -H; R 12< is -H or a monovalent C 1 to C 6 alkyl group; R 15< , R 16< , and R 17< are each independently a -H; -R 18< ; - C(O)R 18< provided that at least one R 15< , R 16< , or R 17< is a -H; R 18< is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; z is 1 to 15; Y is -Cl; s is an integer of 0 to 50; t is an integer of 0 to 50; s+t is greater than 0. The term "branched", as used herein, means that the functional chain can be branched at any point, for example as a quarternary substituted carbon, and can contain any number of branched substitutions.

[0022] In one embodiment, the second compound is present and reacts with about 0.1 mol % to about 60 mol % of said isocyanate groups. Preferably the concentration of compounds of isocyanate-reactive compound (b) is greater than the concentration of second compound(s) (c).

[0023] In one embodiment, the second compound (c) is water. Water may be used to crosslink unreacted isocyanate groups by urea linkage. In a further embodiment, the second compound (c) is of Formula (Illa). The compound of formula (Illa) can be a hydrophilic water-solvatable material comprising at least one hydroxy-terminated polyether of formula (IIIa) wherein isocyanate-reactive group X is -O-(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t -H or -[C(O)]-O-(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t -H. In this embodiment, - (CH 2 CH 2 O)- represents oxyethylene groups (EO) and -(CH(CH 3 )CH 2 O)-represents oxypropylene groups (PO). These polyethers can contain only EO groups, only PO groups, or mixtures thereof. These polyethers can also be present as a tri-block copolymer designated PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). Preferably, the polyethers are the commercially available methoxypolyethylene glycols (MPEG's), or mixtures thereof. Also commercially available, and suitable for the preparation of the compositions of the present invention, are butoxypolyoxyalkylenes containing equal amounts by weight of oxyethylene and oxypropylene groups (Union Carbide Corp. 50-HB Series UCON Fluids and Lubricants) and having an average molecular weight greater than about 1000. The hydroxy-terminal polyethers of Formula (IIIa) preferably have an average molecular weight equal to or greater than about 200, and most preferably between 350 and 2000.

[0024] In another embodiment, the second compound (c) is an organic compound of Formula (IIIa), where isocyanate-reactive group X is -OH, - C(O)OH, -SH, -NH(R 12< ); and R 5< is selected from a -C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group, a hydroxy-functional C 1 to C 30 linear or branched alkyl, a hydroxy-functional linear or branched C 1 to C 30 polyether, a hydroxy-functional linear or branched polyester, a hydroxy- or amine-functional linear or branched organosiloxane, a thiol-functional C 1 to C 30 linear or branched alkyl, an amine-functional C 1 to C 30 linear or branched alkyl.

[0025] Where isocyanate-reactive group X is -OH, examples of Formula (IIIa) include but are not limited to alkyl alcohols such as propanol, butanol, or fatty alcohols including stearyl alcohol (R 5< is a -C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group); alkyl diols or polyols such as ethanediol, propanediol, butanediol, or hexanediol (R 5< is a hydroxy-functional C 1 to C 30 linear or branched alkyl); alkylene glycol ethers such as triethylene glycol, tetraethylene glycol, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(tetrahydrofuran), or glycol ethers having mixtures of PEG, PPG, or THF units (R 5< is a hydroxy-functional linear or branched C 1 to C 30 polyether); polyester polyols (R 5< is a hydroxy-functional linear or branched polyester); silicone prepolymer polyols (R 5< is a hydroxy-functional linear or branched organosiloxane); N,N-dimethylaminoethanol (R 5< is an amine-functional C 1 to C 30 linear or branched alkyl); choline chloride or betaine HCl (R 5< is Y- (R 7< )(R 8< )(R 9< )N +< R 10< -); butanone oxime (R 5< is (R 7< )(R 8< )C=N-). The polyether polyols can contain only EO groups, only PO groups, only THF groups, or mixtures thereof. These polyethers can also be present as a block copolymer, such as that designated by PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). Preferably, the polyether glycols have an average molecular weight equal to or greater than about 200, and most preferably between 350 and 2000.

[0026] Where isocyanate-reactive group X is -C(O)OH, examples of Formula (IIIa) include but are not limited to fatty acids such as caprylic acid, capric acid, lauric acid, mysteric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, lineolic acid, arachidonic acid, oleic acid, or erucic acid (R 5< is a -C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group); hydroxy-containing acids such as hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxymysteric acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxylignoceric acid, hydroxypalmitoleic acid, hydroxylineolic acid, hydroxyarachidonic acid, hydroxyoleic acid, or hydroxyerucic acid (R 5< is a hydroxy-functional C 1 to C 30 linear or branched alkyl); and mercaptoalkanoic acids such as mercaptopropionic acid (R 5< is a thiol-functional C 1 to C 30 linear or branched alkyl).

[0027] Where isocyanate-reactive group X is -SH, specific examples of Formula (IIIa) include but are not limited to alkyl thiols such as lauryl mercaptan or dodecyl mercaptan (R 5< is a -C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group). Where isocyanate-reactive group X is -NH(R 12< ), specific examples of Formula (Illa) include but are not limited to alkyl amines such as diisopropylamine, propylamine, hexylmine, or laurylamine (R 5< is a -C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group); alkanolamines such as ethanolamine or propanolamine (R 5< is a hydroxy-functional C 1 to C 30 linear or branched alkyl); silicone prepolymer polyamines (R 5< is a amine-functional linear or branched organosiloxane); alkyl diamines (R 5< is an amine-functional C 1 to C 30 linear or branched alkyl); and aminoalkanesulfonic acids such as 2-aminoethanesulfonic acid (R 5< is HO-S(O) 2 R 10< -).

[0028] In a further embodiment, the second compound (c) is of formula (IIIb). These compounds are commonly referred to as polyglycerols. These polyglycerols can be present where R 15< , R 16< , and R 17< are each independently a -H; -R 18< ; -C(O)R 18< provided that at least one R 15< , R 16< , or R 17< is a -H; and wherein R 18< is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond. Specific examples include but are not limited to triglycerol monostearate, triglycerol distearate, hexaglycerol monostearate, hexaglycerol distearate, decaglyceryl mono(carpylate / caprate), decaglyceryl di(carpylate / caprate), decaglycerol, polyglycerol-3, and C18 diglyceride.

[0029] In one embodiment, the reaction product of (a) an isocyanatecontaining compound with (b) an isocyanate-reactive compound contains unreacted isocyanate groups which are further reacted with multiple second compounds (c) comprising both compounds of formula (IIIa) or (IIIb) and water. The compounds produced by the method of the present invention can be made in one step. The compounds produced by the method of the present invention comprising more than one organic compound of Formula (Ia) or (Ib) and / or one or more second compounds (c) can be also made in one step. Preferably, if more than one organic compounds of Formula (Ia) or (Ib) and / or one or more second compounds (c) are used, then the synthesis can be completed sequentially. A sequential addition is especially useful when employing compounds of Formula (Ia) or (Ib) with high OH numbers, or when using polyfunctional compounds (c). These steps comprise reacting (a) at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia) or (Ib) wherein each R is independently a -H or -C(O)R 1< , and two or three of R are -C(O)R 1< ; each R 1< is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R 3< is independently a -H; - R 1< ; -C(O)R 1< ; -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' R 2< ; or -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' C(O)R 1< ; each R 4< is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' R 2< ; or -(CH 2 CH 2 O) n' (CH(CH 3 )CH 2 O) m' C(O)R 1< ; each n' is independently 0 to 20; each m' is independently 0 to 20; m'+n' is greater than 0; each R 2< is independently -H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; or a mixture thereof; provided when the compound is Formula (Ib), then the compound is di-substituted, or tri-substituted with alkyl groups, and at least one R 2< , R 3< or R 4< is a -H.

[0030] The at least one isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia) or (Ib) or mixture thereof, are reacted. This reaction is typically conducted by charging a reaction vessel with the isocyanate, diisocyanate, or polyisocyanate, and at least one compound selected from formula (Ia) or (Ib) or mixture thereof, and optionally a second compound (c). The order of reagent addition is not critical, but if water is used, the water should be added after the isocyanates and at least one compound selected from formula (Ia) or (Ib) or mixture thereof are reacted.

[0031] The specific weight of the reactants charged is based on their equivalent weights and on the working capacity of the reaction vessel, and is adjusted so that compound selected from formula (Ia) or (Ib) will be consumed in the first step. A suitable dry organic solvent free of isocyanate-reactive groups is used as a solvent. Ketones are the preferred solvents, and methylisobutylketone (MIBK) is particularly preferred for convenience and availability. The charge is agitated, and temperature adjusted to about 40 °C to 70 °C. Typically, a catalyst such as iron(III) chloride in an organic solvent is then added, typically in an amount of from about 0.01 to about 1.0 weight % based on the dry weight of the composition, and the temperature is raised to about 80 °C to 100 °C. A co-catalyst, such as sodium carbonate, may also be used. If water is to be added, the initial reaction is conducted so that less than 100% of the isocyanate groups are reacted. In the second step after holding for several hours, additional solvent, water, and optionally a second compound (c) are added, and the mixture is allowed to react for several more hours or until all of the isocyanate has been reacted.

[0032] It will be apparent to one skilled in the art that many changes to any or all of the above procedures can also be used to optimize the reaction conditions for obtaining maximum yield, productivity, or product quality.

[0033] The method of the present invention is useful to produce products that can provide excellent water repellency and optionally stain release to treated substrates. The surface properties are obtained using a non-fluorinated organic urethane produced according to the method defined above. The use of the non-fluorinated organic urethanes has been found to provide superior water repellency and durable water repellency compared to traditional non-fluorinated water repellents, and they are comparable to commercially available fluorinated water repellents. The treated substrates are useful in a variety of applications and products such as clothing, protective garments, carpet, upholstery, furnishings, and other uses. The excellent surface properties described above help to maintain surface cleanliness and therefore can permit longer use.Test Methods and Materials

[0034] All solvents and reagents, unless otherwise indicated, were purchased from Sigma-Aldrich, St. Louis, MO, and used directly as supplied. MPEG 750 and MPEG 1000 are defined as poly(ethylene glycol) methyl ether 750 and poly(ethylene glycol) methyl ether 1000, respectively, and are commercially available from Sigma-Aldrich, St. Louis, MO. Tergitol ®< TMN-10 is commercially available from Sigma-Aldrich, St. Louis, MO.

[0035] Sorbitan tristearate and sorbitan monostearate are commercially available from Croda, East Yorkshire, England, or DuPont Nutrition & Health, Copenhagen, Denmark. Low-OH sorbitan tristearate (OH value <65), dipentaerythritol esters, sorbitan ester - lauric acid, sorbitan tribehenin 40, sorbitan tribehenin 50, sorbitan tribehenin 88, and glycerol distearate was obtained from DuPont Nutrition & Health, Copenhagen, Denmark.

[0036] DESMODUR N-100, DESMODUR H, DESMODUR I, DESMODUR N3300, DESMODUR N3790BA, DESMODUR Z4470, and DESMODUR XP2410 were obtained from Bayer Corporation, Pittsburgh, PA.

[0037] JEFFAMINE M-1000, JEFFAMINE M-2070, and PHOBOL XAN were obtained from Huntsman Corp., Salt Lake City, UT.

[0038] PRIPOL 2033 (amorphous dimer diol), PRIAMINE 1075 (dimer diamine), PRIPLAST 3293 (semicrystalline polyester polyol), sorbitan trioleate, polyoxyethylenesorbitan tristearate, polyoxyethylenesorbitan trioleate, tetraethoxysorbitan monostearate, polyoxyethylenesorbitan monostearate, and polyoxyethylene(4) sorbitan monostearate were obtained from Croda, East Yorkshire, England.

[0039] Tri(2-octadodecyl) citrate is commercially available from Lubrizol, Wickliffe, Ohio.

[0040] SILMER OH Di-10 (a small linear di-functional hydroxyl-terminated silicone pre-polymer) and SILMER NH Di-8 (a linear silicone with reactive amine terminal groups) are available from Siltech Corporation, Toronto, Canada.

[0041] PLURONIC L35 is commercially available from BASF, Ludwigshafen, Germany. ARMEEN DM-18D was obtained from Akzo-Nobel, Bridgewater, NJ.

[0042] Triglycerol monostearate and hexaglycerol distearate were obtained from Lonza, Allendale, NJ.

[0043] Decaglyceryl mono(caprylate / caprate) was obtained from Stepan, Northfield, Illinois.

[0044] Polyglycerol-3 was obtained from Solvay Chemicals, Houston, TX.

[0045] The following test methods and materials were used in the examples herein.Test Method 1 - Water Repellency

[0046] The water repellency of a treated substrate was measured according to the DuPont Technical Laboratory Method as outlined in the TEFLON Global Specifications and Quality Control Tests information packet. The test determines the resistance of a treated substrate to wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the fabric and the extent of surface wetting is determined visually. The test provides a rough index of aqueous stain resistance. The higher the water repellency rating, the better the resistance the finished substrate has to staining by water-based substances. The composition of standard test liquids is shown in the following Table 1. Ratings of 0.5 increments are determined by subtracting one half from the numbers in Table 1 for borderline passing of the test liquid. Table 1. Standard Test Liquids Water Repellency Rating NumberComposition Vol.%, Isopropyl AlcoholComposition, Vol. % Distilled Water1298259531090420805307064060750508604097030108020119010121000 Test Method 2 - Spray Test

[0047] The dynamic water repellency of treated substrates was measured according to the American Association of Textile Chemists and Colorists (AATCC) TM-22. Samples are visually scored by reference to published standards, with a rating of 100 denoting no water penetration or surface adhesion. A rating of 90 denotes slight random sticking or wetting without penetration; lower values indicate progressively greater wetting and penetration. Test Method 2, the dynamic water repellency test, is a demanding and realistic test of water repellency.Test Method 3 - Stain Release

[0048] This test measures the ability of a fabric to release oily stains during home laundering.

[0049] Treated textiles are placed on a flat surface. Using an eyedropper, 5 drops of MAZOLA Corn Oil or mineral oil (0.2 mL) were placed onto the fabric to form 1 drop of oil. A weight (5 lb, 2.27 kg) is placed on top of the oil drop with a piece of glassine paper separating the oil drop. The weight was left in place for 60 seconds. After 60 seconds, the weight and glassine paper are removed. The textiles samples were then washed using a automatic washer high for 12 minutes with AATCC 1993 Standard Reference Detergent WOB12 or granular detergent (100 g). The textiles were then dried on high for 45-50 minutes. The textiles were then evaluated for residual stain of 1 to 5, 1 having the largest residual stain remaining and 5 being no stain residual was visible.Test Method 4 - Fabric Treatment

[0050] The fabrics treated in this study were 100% by weight khaki cotton twill available from SDL Atlas Textile Testing Solutions, Rock Hill, South Carolina 29732 and 100% by weight red polyester fabric available from L. Michael OY, Finland. The fabric was treated with the aqueous dispersions various emulsion polymer using a conventional pad bath (dipping) process. The prepared concentrated dispersion of the polymer emulsions were diluted with deionized water to achieve a pad bath having 60 g / L or 100 g / L of the final emulsion in the bath.

[0051] Examples of the compounds and compositions that can be made from the method of the instant invention follow. The present invention is not to be limited by the examples below.

[0052] *Examples marked with an asterisk do not apply the method of the present invention.Preparation of Trioctadecyl Citrate

[0053] In a 4-neck round bottom flask equipped with an overhead stirrer, thermocouple, dean-stark / condenser was added stearyl alcohol (100.0 g), citric acid (20 g), toluene (150 g) and sulfuric acid (2 g). The solution was refluxed for 8 hours to facility the removal of the water generated during the esterification. After the 8 hours, the crude citrate was precipitated at 0 °C, filtered, and recrystallized using ethanol.Example 1

[0054] In a 4-neck round bottom flask equipped with an overhead stirrer, thermocouple, dean-stark / condenser was added sorbitan tristearate (116.0 g; Hydroxy Number = 77.2 mgKOH / g) and 4-methyl-2-pentanone (MIBK, 150 g). The solution was refluxed for 1 hour to remove any residual moisture. After the hour, the solution was cooled to 50 °C and DESMODUR N-100 (30 g) was added followed by a catalyst and the solution was heated to 80 °C over one hour.Example 2

[0055] An aqueous dispersion of the compound as described in Example 1 was prepared. Water (300 g), ARMEEN DM-18D (5.6 g), TERGITOL TMN-10 (2.8 g), and acetic acid (3.4 g) was added to a beaker and stirred to from a surfactant solution. The solution was heated to 60 °C. The sorbitan urethane / MIBK solution, as prepared in Example 1, was cooled to 60 °C and the surfactant solution was added slowly to produce a milky emulsion. The mixture was homogenized at 6000 psi, and the resulting emulsion was distilled under reduced pressure to remove the solvent, yielding a non-flammable urethane dispersion at 25% solids. This urethane dispersion was applied to textiles and tested according to the test methods above.Examples 3 to 23

[0056] Examples 3 to 23 demonstrate various compounds of the present invention prepared as described in Examples 1 (compounds) and Example 2 (dispersions) with an isocyanate (DESMODUR N100) and one or more different compounds of Formula (Ia) such as sorbitan tristearate, sorbitan trioleate, sorbitain monostearate, and mixtures thereof. When more than one sorbitan ester reagent was used, the second sorbitan reagent was added, and the reaction mixture was heated at 80 °C for an additional four hours. Examples 3 to 23 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods above.Comparative Example A

[0057] Comparative Example A represents an aqueous dispersion made using the compound of Formula (Ia), without an isocyanate compound. Water (166.0 g), ARMEEN DM-18D (2.29 g), TERGITOL TMN-10 (1.6 g), and acetic acid (1.4 g) were added to a beaker and stirred to form a surfactant solution. The solution was heated to 60 °C. Sorbitan tristearate (60.52 g; Hydroxy Number = 69.5 mgKOH / g), was heated to 80 °C and the surfactant solution was added slowly to produce a milky emulsion. The mixture was homogenized at 6000 psi, and the resulting emulsion was distilled under reduced pressure to remove the solvent, yielding a non-flammable dispersion at 25% solids. This dispersion was applied to textiles and tested according to the test methods above. Table 2. Compositions of Examples 2 to 23. Component (a) Component (b) Desmodur N100 (g) Sorbitan Tristearate (g) Sorbitan Trioleate (g) Sorbitan Monostearate (g) Ex. 2 30.0116.000Ex. 3 30.10147.00Ex. 4 30.058.070.00Ex. 5 30.0113.501.2Ex. 6 30.081.2010.8Ex. 7 30.098.605.4Ex. 8 30.00102.511.2Ex. 9 30.20125.05.4Ex. 10 30.0113.501.2Ex. 11 30.249.362.05.4Ex. 12 30.049.362.05.4Ex. 13 30.149.362.05.4Ex. 14 30.049.359.55.4Ex. 15 30.040.649.010.8Ex. 16 30.049.359.55.4Ex. 17 30.074.045.01.4Ex. 18 30.01.2135.250Ex. 19 30.0105.503.5Ex. 20 30.0127.501.25Ex. 21 30.0115.401.25Ex. 22 30.0113.801.25Ex. 23 15.060.100.61Comp. Ex. A 060.5200 Table 3. Performance Data of Examples 2 to 23 and Comparative Example A Cotton Polyester Water Drop Spray Water Drop Spray Ex. 2 4100----Ex. 3 275080Ex. 4 3--3--Ex. 5 4100----Ex. 6 3--3--Ex. 7 3--3--Ex. 8 28020Ex. 9 27500Ex. 10 3803100Ex. 11 4903100Ex. 12 4903100Ex. 13 4903100Ex. 14 3--3--Ex. 15 3--3--Ex. 16 3--3--Ex. 17 4100----Ex. 18 380----Ex. 19 4100----Ex. 20 3803100Ex. 21 31003100Ex. 22 31003100Ex. 23 390----Comp. Ex. A 350150 Examples 24 to 31

[0058] Examples 24 to 31 follow the procedures of Examples 1 (compounds) and Example 2 (dispersions), using various isocyanates and from one to two different compounds of Formula (Ia) as described in Table 4. When more than one compounds of Formula (Ia) was used, the second compound was added, and the reaction mixture was heated at 80 °C for an additional four hours. Examples 24 to 31 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 4. Compositions of Examples 24 to 31 Component (a) Component (b) Compound Amount (g) Sorbitan Tristearate (g) Sorbitan Trioleate (g) Sorbitan Monostearate (g) Ex. 24 Desmodur H26.4113.501.2Ex. 25 Desmodur I24.70212.80Ex. 26 Desmodur N330030.40135.251.2Ex. 27 Desmodur N3790BA15.045.3500.5Ex. 28 Desmodur Z4470BA22.544.2500.75Ex. 29 Desmodur XP241015.059.500.9Ex. 30 Desmodur I24.70212.80Ex. 31 Desmodur I30.2113.501.2 Table 5. Performance Data of Examples 24 to 31 Cotton Polyester Water Drop Spray Water Drop Spray Ex. 24 3853100Ex. 25 370380Ex. 26 375----Ex. 27 390----Ex. 28 3100----Ex. 29 3100----Ex. 30 4100----Ex. 31 370---- Examples 32 to 36

[0059] Examples 32 to 36 follow the procedures of Examples 1 (compounds) and Example 2 (dispersions), using DESMODUR N-100 isocyanate, one to two different compounds of Formula (Ia), and an acid monomer as described in Table 6. Example 36 also included a stearyl alcohol monomer. The acid monomer, stearyl alcohol, and any additional compounds of Formula (Ia) were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 1 hour, and the reaction mixture was heated at 80 °C for an additional four hours. Examples 32 to 36 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 6. Compositions of Examples 32 to 36 Comp. (a) Component (b) Component (c) Desmodur N100 (g) Sorbitan Tristearate (g) Sorbitan Monostearate (g) Compound Amt (g) Ex. 32 29.972.21.4Behenic Acid16.5Ex. 33 30.073.31.4Erucic Acid16.8Ex. 34 30.036.11.4Behenic Acid41.5Ex. 35 29.941.11.4Behenic Acid45.5Ex. 36 30.073.41.4Behenic Acid / Stearyl Alcohol8.2 / 6.8 Table 7. Performance Data of Examples 32 to 36 Cotton Polyester Water Drop Spray Water Drop Spray Ex. 32 3853100Ex. 33 3903100Ex. 34 3802100Ex. 35 350250Ex. 36 385385 Examples 37 to 54

[0060] Examples 37 to 54 follow the procedures of Examples 1 (compounds) and Example 2 (dispersions), using an isocyanate, one to two different compounds of Formula (Ia), and MPEG 750 as described in Table 8. The MPEG 750 and any additional compounds of Formula (Ia) were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 1 hour, and the reaction mixture was heated at 80 °C for an additional four hours. Examples 37 to 54 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 8. Compositions of Examples 37 to 54 Component (a) Component (b) Component (c) Compound Amount (9) Sorbitan Tristearate (g) Sorbitan Monostearate (g) Sorbitan Distearate (g) Sorbitan Tetrastearate (g) MPEG 750 (g) Ex. 37 Desmodur N10027.450.01.30051.6Ex. 38 Desmodur N10022.850.01.10034.4Ex. 39 Desmodur N10034.250.01.70077.5Ex. 40 Desmodur N330024.950.04.20046.5Ex. 41 Desmodur H10.850.04.20046.5Ex. 42 N3790BA30.550.04.20046.5Ex. 43 Z4470BA45.650.04.20046.5Ex. 44 Desmodur N10024.650.04.20046.5Ex. 45 Desmodur N10024.650.000046.5Ex. 46 Desmodur N10012.017.22.20023.6Ex. 47* Desmodur N10012.004.50033.0Ex. 48 Desmodur N10012.536.900014.7Ex. 49 Desmodur N330012.015.100032.6Ex. 50 Desmodur N330012.020.04.40013.9Ex. 51 Desmodur N10012.315.600033.9Ex. 52 Desmodur N330012.035.100014.0Ex. 53 Desmodur N10012.70023.0024.9Ex. 54* Desmodur N10012.100040.823.8 Table 9. Performance Data of Examples 37 to 54 Cotton Water Drop Corn Oil Mineral Oil Spray Ex. 37 33.5375Ex. 38 33.5375Ex. 39 33.5375Ex. 40 343--Ex. 41 243--Ex. 42 33.53--Ex. 43 33.53--Ex. 44 24.54.5--Ex. 45 244--Ex. 46 34370Ex. 47* 13.53.50Ex. 48 3.52185Ex. 49 34.5350Ex. 50 3.53185Ex. 51 34.5350Ex. 52 3.53185Ex. 53 43275Ex. 54* 42.5180 Examples 55 to 62

[0061] Examples 55 to 62 follow the procedures of Examples 1 (compounds) and Example 2 (dispersions), using DESMODUR N-100 isocyanate, sorbitan tristearate, a glycol or alkoxylated monomer, and up to one additional reagent as described in Table 10. The glycol or alkoxylated monomer and additional reagents were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 1 hour, and the reaction mixture was heated at 80 °C for an additional four hours. Examples 55 to 62 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 10. Compositions of Examples 55 to 62 Component (a) Component (b) Component (c) Formula (IIIa) Component (c) Additional Desmodur N100 (g) Sorbitan Tristearate (g) Compound Amount (g) Compound Amount (g) Ex. 55 12.714.6MPEG 100044.2N,N-Dimethylaminoethanol0.3Ex. 56 12.514.3MPEG 100043.5Choline Chloride0.5Ex. 57 13.315.2MPEG 100046.22-aminoethanesulfonic acid0.4Ex. 58 12.114.6Jeffamine M-100044.3Ex. 59 12.314.8Jeffamine M-207090.1Ex. 60 1.76.2polypropylene glycol0.1Ex. 61 1.76.2tetrathylene glycol dodecyl ether0.2Ex. 62 1.75.9tetrathylene glycol dodecyl ether0.3 Table 11. Performance Data of Examples 55 to 62 Cotton Polyester Water Drop Corn Oil Mineral Oil Spray Water Drop Spray Ex. 55 13350----Ex. 56 24350----Ex. 57 232.550----Ex. 58 23.5360----Ex. 59 0.53.5325----Ex. 60 3----80395Ex. 61 3----85365Ex. 62 3----80390 Examples 63 and 64

[0062] Examples 63 and 64 follow the procedures of Examples 1 (compounds) and Example 2 (dispersions), using DESMODUR N-100 isocyanate, an alkoxylated sorbitan ester, and up to one additional reagent as described in Table 12. The additional reagents were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 1 hour, and the reaction mixture was heated at 80 °C for an additional four hours. Examples 63 and 64 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above.Example 65

[0063] Example 65 employs the use of DESMODUR N-100 isocyanate, an alkoxylated sorbitan ester, and MPEG 750 as described in Table 12. To a 40 mL scintillation vial, placed on a hotplate / stirrer and equipped with a nitrogen line and stir bar, tetraethoxysorbitan monostearate (0.8 g), and 8.5 g 4-methyl-2-pentanone (MIBK) were charged. The solution was stirred and heated to 55 °C for 10 minutes under nitrogen. Desmodur N-100 (1.7 g) was added and the reaction temperature was increased to 80 °C. A 0.5 wt% Iron(III) chloride solution (in MIBK) was added and the reaction temperature was increased to 95 °C. After six hours, MPEG 750 (4.5 g) was added. The reaction temperature was decreased to 80 °C and stirred overnight. The resulting mixture was standardized to 25% solids, applied to textiles at 60 g / L and tested according to the test methods above.Examples 66 to 69

[0064] Examples 66 to 69 follow the procedures of Example 65, using DESMODUR N-100 isocyanate, an alkoxylated sorbitan ester, and up to one additional reagent as described in Table 12. The additional reagents were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 6 hours, and the reaction mixture was heated at 80 °C overnight. Examples 66 to 69 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 12. Compositions of Examples 63 to 69 Component (a) Component (b) Component (c) Desmodur N100 (g) Polyoxyethylene sorbitan tristearate (g) Polyoxyethylene sorbitan trioleate (g) Tetra-ethoxy sorbitan monostearate (g) Polyoxyethylene sorbitan monostearate (g) Polyoxyethylene(4) sorbitan monostearate (g) Laurylamine (9) MPEG 750 (9) Ex. 63 8.250001.1000Ex. 64 7.2050.000000Ex. 65* 1.7000.80004.5Ex. 66 1.54.800000.360Ex. 67 1.59.100000.040Ex. 68* 1.500000.120Ex. 69* 1.500000.240 Table 13. Performance Data of Examples 63 to 69 Cotton Polyester Water Drop Corn Oil Mineral Oil Spray Water Drop Spray Ex. 63 0430----Ex. 64 03.530----Ex. 65* 0----25----Ex. 66 3----70350Ex. 67 3----70350Ex. 68* 3----70390Ex. 69* 3----903100 Examples 70 to 94

[0065] Examples 70 to 94 follow the procedures of Examples 1 (compounds) and Example 2 (dispersions), using an isocyanate, a compound of Formula (Ia), at least one alcohol reagent, and up to one additional reagent as described in Table 14. The alcohol reagent and additional reagents were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 1 hour, and the reaction mixture was heated at 80 °C for an additional four hours. In Examples 88 to 91, sodium carbonate (0.5% by total reagent weight) was combined with the sorbitan tristearate before reaction. Examples 70 to 94 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above.Example 95

[0066] Example 95 follows the procedure of Example 65, using DESMODUR N-100 isocyanate, sorbitan tristearate, and PRIPOL 2033 as described in Table 14. The PRIPOL 2033 was added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 6 hours, and the reaction mixture was heated at 80 °C overnight. Example 93 was applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 14. Compositions of Examples 70 to 95 Component (a) Component (b) Component (c) Desmodur N100 (g) Desmodur H (g) Sorbitan Tristearate (g) Compound Amount (g) Compound Amount (g) Ex. 70 24.6050.0MPEG 75046.51,3-propanediol0.8Ex. 71 24.6050.0MPEG 75046.5Silmer OH Di-1010.6Ex. 72 24.6050.0MPEG 75046.5Silmer NH Di-89.9Ex. 73 24.6050.0MPEG 75046.5triethylene glycol1.6Ex. 74 24.6050.0MPEG 75046.5polypropylene glycol2.3Ex. 75 24.6050.0MPEG 75046.5Pripol 20332.9Ex. 76 24.6050.0MPEG 75046.5Priamine 10755.6Ex. 77 24.6050.0MPEG 75046.5Pluronics F6888.7Ex. 78 24.6050.0MPEG 75046.5Pluronics L3520.1Ex. 79 24.6050.0MPEG 75046.512-hydroxystearic acid4.0Ex. 80 24.6050.0MPEG 75046.5decaglycerol8.0Ex. 81 24.6050.0MPEG 75046.5poly(tetrahydrofuran) 2502.6Ex. 82 24.6050.0MPEG 75046.5poly(tetrahydrofuran) 6506.7Ex. 83 30.00113.4t-butanol1.66--Ex. 84 30.00113.4water0.4--Ex. 85 30.10102.12water1.71Ex. 86 15.0047.68t-butanol0.32Ex. 87 010.178.63water0.91Ex. 88 25.1099.80n-butanol0.50Ex. 89 25.10100.33water0.72Ex. 90 15.5057.41n-butanol0.31Ex. 91 15.0055.48PRIPLAST 32933.87Ex. 92 15.0055.75n-butanol0.285Ex. 93 15.00105.5n-butanol0.285Ex. 94 15.0052.05n-butanol0.285Ex. 95 1.505.6Pripol 20330.06 Table 15. Performance Data of Examples 70 to 95 Cotton Polyester Water Drop Corn Oil Mineral Oil Spray Water Drop Spray Ex. 70 24.54.5------Ex. 71 24.54.5------Ex. 72 23.53------Ex. 73 243------Ex. 74 24.54------Ex. 75 243------Ex. 76 243------Ex. 77 23.53------Ex. 78 23.53------Ex. 79 243.5------Ex. 80 23.53------Ex. 81 243------Ex. 82 24.54------Ex. 83 3----100390Ex. 84 3----1003100Ex. 85 3----1003100Ex. 86 4----100490Ex. 87 3----75370Ex. 88 3----1003100Ex. 89 3----1003100Ex. 90 3----100Ex. 91 3----95395Ex. 92 3----100390Ex. 93 3----1003100Ex. 94 4----1003100Ex. 95 3----90390 Examples 96 to 102 and 108 to 110 (with example 100 not according to the invention).

[0067] Examples 96 to 102 and 108 to 110 follow the procedures of Examples 1 (compounds) and Example 2 (dispersions), using DESMODUR N-100 isocyanate, one or more compounds of Formula (Ia) or Formula (Ib), and at least one additional reagent as described in Table 16. The additional reagents were added to the reaction after the initial compound of Formula (Ia) and (Ib) and isocyanate had reacted for 1 hour, and the reaction mixture was heated at 80 °C for an additional four hours. Examples 96 to 102 and 108 to 110 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above.Examples 103 to 107

[0068] Example 103 to 107 follow the procedure of Example 65, using DESMODUR N-100 isocyanate, one or more compounds of Formula (Ia) or Formula (Ib), and at least one additional reagent as described in Table 16. The additional reagents were added to the reaction after the initial compound of Formula (Ia) and (Ib) and isocyanate had reacted for 6 hours, and the reaction mixture was heated at 80 °C overnight. In Example 105, sodium carbonate (0.07 g) was combined with the sorbitan tristearate and sorbitan citrate before the isocyanate addition. Examples 103 to 104 and 106 to 107 were applied as dispersions to textiles at 60 g / L (Example 105 was applied at 100 g / L), and tested according to the test methods described above. Table 16. Compositions of Examples 96 to 110 Component (a) Component (b) Component (c) Desmodur N100 (g) Compound(s) Amount(s) (g) Compound(s) Amount(s) (g) Ex. 96 30.0Sorbitan tribehenin 40 / sorbitan monostearate123.66 / 1.25Ex. 97 15.0Sorbitan tribehenin 5062.5n-butanol0.285Ex. 98 15.0Sorbitan tribehenin 8869.1n-butanol0.285Ex. 99 15.0Sorbitan tribehenin 4066.3n-butanol0.285Ex. 100 15.0Dipentaerythritol esters68.05n-butanol0.855Ex. 101 15.0Sorbitan tristearate, low OH value171.1n-butanol0.855Ex. 102 15.0Sorbitan ester - lauric acid145.9n-butanol0.855Ex. 103 1.5Tri(2-octyldodecyl) citrate7.54Hexylamine0.02Ex. 1041.5Tri(2-octyldodecyl) citrate4.0Hexylamine0.2Ex. 105 1.5Sorbitan tristearate / trioctyldodecyl citrate2.75 / 3.81n-butanol0.11Ex. 106 1.5Trioctadecyl citrate6.9stearyl mercaptan0.11Ex. 107 1.5Trioctadecyl citrate3.65stearyl mercaptan1.1Ex. 108 12.0Sorbitan tribehenin 5026.5MPEG 75023.6Ex. 109 12.1Sorbitan tribehenin 8829.6MPEG 75023.8Ex. 110 12.4Sorbitan tribehenin 4029.0MPEG 75024.3 Table 17. Performance Data of Examples 96 to 110 Cotton Polyester Water Drop Corn Oil Mineral Oil Spray Water Drop Spray Ex. 96 3----803100Ex. 97 3----100390Ex. 98 3----100385Ex. 99 3----1003100Ex. 100 3----100395Ex. 101 3----603100Ex. 102 3----60250Ex. 103 3----70350Ex. 104 3----70350Ex. 105 3----80360Ex. 106 3----1003100Ex. 107 3----803100Ex. 108 43275----Ex. 109 43180----Ex. 110 43175---- Examples 111 to 114

[0069] Examples 111 to 114 follow the procedures of Examples 1 (compounds) and Example 2 (dispersions), using DESMODUR N-100 isocyanate, one or more compounds of Formula (Ia), and at least one additional reagent as described in Table 18. The additional reagents were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 1 hour, and the reaction mixture was heated at 80 °C for an additional four hours. Examples 111 to 114 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above.Examples 115 to 117

[0070] Examples 115 to 117 follow the procedure of Example 65, using DESMODUR N-100 isocyanate, one or more compounds of Formula (Ia), and at least one additional reagent as described in Table 18. The additional reagents were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 6 hours, and the reaction mixture was heated at 80 °C overnight. Examples 115 to 117 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 18. Compositions of Examples 111 to 117 Component (a) Component (b) Component (c) Desmodur N100 (g) Sorbitan tristearate (g) Sorbitan monostearate (g) Compound(s) Amount(s) (g) Ex. 111 30.0108.29betaine HCl1.21Ex. 112 30.4973.241.4stearyl alcohol13.49Ex. 113 30.11102.59betaine HCl2.41Ex. 114 30.25100.19butanone oxime0.75Ex. 115 1.95.60N,N-dimethylaminoethanol0.04Ex. 116 1.55.98diisopropylamine0.04Ex. 117 1.53.15diisopropylamine0.4 Table 19. Performance Data of Examples 111 to 117 Cotton Polyester Water Drop Spray Water Drop Spray Ex. 111 3853100Ex. 112 3803100Ex. 113 3853100Ex. 114 490490Ex. 115 31003100Ex. 116 375390Ex. 117 385385 Example 118

[0071] Example 118 follows the procedures of Examples 1 (compounds) and Example 2 (dispersions), reacting DESMODUR N-100 isocyanate with sorbitan tristearate according to Table 20, and incorporating sodium carbonate as a co-catalyst (0.375 g) during reaction. Example 118 was applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above.Examples 119 and 120

[0072] Examples 119 and 120 follow the procedure of Example 65, using DESMODUR N-100 isocyanate, sorbitan tristearate, and lauric acid as described in Table 20. The lauric acid was added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 6 hours, and the reaction mixture was heated at 80 °C overnight. Examples 119 and 120 were applied as dispersions to textiles at 100 g / L, and tested according to the test methods described above. Table 20. Compositions of Examples 118 to 120 Component. (a) Component (b) Component (c) Desmodur N100 (g) Compound Amount (g) Lauric acid (g) Ex. 118 15.0sorbitan tristearate59.87Ex. 119 1.5sorbitan tristearate5.680.08Ex. 120 2.2sorbitan tristearate5.950.68 Table 21. Performance Data of Examples 118 to 120 Cotton Polyester Water Drop Spray Water Drop Spray Ex. 118 31003100Ex. 119 380390Ex. 120 270290 Examples 121 to 124

[0073] Examples 121 to 124 follow the procedure of Example 65, using DESMODUR N-100 isocyanate, sorbitan tristearate, and an additional reagent as described in Table 22. The additional reagent was added to the reaction after the sorbitan tristearate and isocyanate had reacted for 6 hours, and the reaction mixture was heated at 80 °C overnight. Examples 121 to 124 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 22. Compositions of Examples 121 to 124 Component (a) Component (b) Component (c) Desmodur N100 (g) sorbitan tristearate (g) dodecane mercaptan (g) 3-mercaptopropionic acid (g) Ex. 121 1.56.00.080Ex. 122 1.53.20.780Ex. 123 1.56.000.05Ex. 124 1.53.200.41 Table 23. Performance Data of Examples 122 to 125 Cotton Polyester Water Drop Spray Water Drop Spray Ex. 121 3903100Ex. 122 380385Ex. 123 4753100Ex. 124 485390 Examples 125 to 131

[0074] Examples 125 to 131 follow the procedure of Example 65, using DESMODUR N-100 isocyanate, sorbitan tristearate, and an additional reagent as described in Table 24. The additional reagent was added to the reaction after the sorbitan tristearate and isocyanate had reacted for 6 hours, and the reaction mixture was heated at 80 °C overnight. For examples 130 to 132, sodium carbonate (0.075 g) was included during the reaction of isocyanate and sorbitan tristearate. Examples 125 to 131 were applied as dispersions to textiles at 60 g / L (Examples 125 to 128) or 100 g / L (Examples 129 to 131), and tested according to the test methods described above.Example 132

[0075] Example 132 follows the procedures of Examples 1 (compounds) and Example 2 (dispersions), using DESMODUR N-3300 isocyanate, two compounds of Formula (Ia), and a C18 diglyceride as described in Table 24. The C18 diglyceride and sorbitan monostearate were added to the reaction after the initial compound of Formula (Ia) and isocyanate had reacted for 1 hour, and the reaction mixture was heated at 80 °C for an additional four hours. Example 132 were applied as dispersions to textiles at 60 g / L, and tested according to the test methods described above. Table 24 Compositions of Examples 125 to 132 Component (a) Component (b) Component (c) Desmodur N100 (g) Desmodur N3300 (g) Compound(s) Amount(s) (g) Compound(s) Amount(s) (g) Ex. 125 1.50sorbitan trisearate6.0triglycerol monostearate0.05Ex. 126 1.50sorbitan trisearate3.15triglycerol monostearate0.5Ex. 127 1.50sorbitan trisearate6.0Hexaglycerol distearate0.07Ex. 128 1.50sorbitan trisearate3.15Hexaglycerol distearate0.65Ex. 129 1.50sorbitan tristearate5.55decaglyceryl mono(caprylate / caprate)0.38Ex. 130 1.60sorbitan tristearate4.67decaglyceryl mono(caprylate / caprate)1.58Ex. 131 1.50sorbitan tristearate5.56Polyglycerol-30.21Ex. 132 15.00sorbitan tristearate / sorbitan monostearate48.08 / 1.35Glycerol distearate12.69 Table 25. Performance Data of Examples 126 to 133 Cotton Polyester Water Drop Spray Water Drop Spray Ex. 125 385390Ex. 126 385390Ex. 127 385390Ex. 128 375385Ex. 129 380390Ex. 130 370370Ex. 131 370395Ex. 132 480385

Claims

1. A method comprising: (i) reacting (a) at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or a mixture thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia) or (Ib) in a dry organic solvent free of isocyanate-reactive groups: wherein each R is independently a -H or -C(O)R1, and two or three of R are -C(O)R1; each R1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R3 is independently a -H; -R1; -C(O)R1; -(CH2CH2O)n'(CH(CH3)CH2O)m'R2; or -(CH2CH2O)n'(CH(CH3)CH2O)m'C(O)R1; each R4 is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH2CH2O)n'(CH(CH3)CH2O)m'R2; or -(CH2CH2O)n'(CH(CH3)CH2O)m'C(O)R1; each n' is independently 0 to 20; each m' is independently 0 to 20; m'+n' is greater than 0; each R2 is independently -H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; or a mixture thereof, provided when the compound is Formula (Ib), then the compound is di-substituted, or tri-substituted with alkyl groups, and at least one R2, R3 or R4 is a -H.

2. The method of claim 1, wherein the dry organic solvent is a ketone, preferably methylisobutylketone (MIBK).

3. The method of claim 1 wherein the compounds of formula (Ia) and (Ib) are at least 50% bio-based derived.

4. The method of claim 1 wherein the diioscyanate or polyisocyanate is selected from the group consisting of hexamethylene diisocyanate homopolymer, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of formulas (IIa), (IIb), (IIc) and (IId):

5. The method of claim 1, further comprising reacting the product thereof with (c) at least one second compound selected from water, at least one organic compound of Formula (IIIa)         R5-X     (IIIa), at least one organic compound of Formula (IIIb)         R15-(OCH2CH(OR15)CH2)z-OR17     (IIIb), or mixtures thereof; wherein R5 is selected from a -C1 to C30 linear or branched alkyl optionally comprising at least one unstaturated group, a hydroxy-functional C1 to C30 linear or branched alkyl, a hydroxy-functional linear or branched C1 to C30 polyether, a hydroxy-functional linear or branched polyester, a hydroxy- or amine-functional linear or branched organosiloxane, a thiol-functional C1 to C30 linear or branched alkyl, an amine-functional C1 to C30 linear or branched alkyl, wherein R7, R8, and R9 are each independently, -H, -C1 to C6 alkyl, or combinations thereof; R10 is a divalent alkyl group of 1 to 20 carbons; X is an isocyanate-reactive group selected from -OH, -C(O)OH, -SH, - NH(R12), -O-(CH2CH2O)s(CH(CH3)CH2O)t-H or -[C(O)]-O-(CH2CH2O)s(CH(CH3)CH2O)t-H; R12 is -H or a monovalent C1 to C6 alkyl group; R15, R16, and R17 are each independently a -H; -R18; -C(O)R18 provided that at least one R15, R16, or R17 is a -H; R18 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; z is 1 to 15; Y is -Cl; s is an integer of 0 to 50; t is an integer of 0 to 50; s+t is greater than 0.

6. The method of claim 5, wherein the second compound (c) is of Formula (IIIa), and X is -O-(CH2CH2O)s(CH(CH3)CH2O)t-H; or -[C(O)]-O-(CH2CH2O)s(CH(CH3)CH2O)t-H.

7. The method of claim 5, wherein the second compound (c) is of Formula (IIIb).

8. The method of claim 1 wherein (b) is at least one compound selected from formula (la).

9. The method of claim 1 wherein (b) is at least one compound selected from formula (Ib).

10. The method of any one of claims 5 to 7, wherein the second compound (c) reacts with 0.1 mol% to 60 mol% of the isocyanate groups.

11. The method of claim 10, wherein the concentration of the compounds of isocyanate-reactive compound (b) is greater than the concentration of second compound(s) (c).