ZA200408013B - Breathable polyurethanes, blends and articles - Google Patents

Description

BREATHABLE POLYURETHANES, BLENDS, AND ARTICLES

RELATED APPLICATION

This application claims the priority filing date of U.S. Provisional

Application Serial No. 60/370135 filed April 5, 2002.

FIELD OF THE INVENTION

This invention relates to waterborne polyurethane dispersions used to make polyurethanes having excellent breathability, i.e., high moisture vapor transmission rates (MVTR). Such polyurethanes comprise (a) poly(alkylene oxide) side-chain units in an amount comprising about 12 wt.% to about 80 wt.% of the polyurethane, wherein (i) alkylene oxide groups in said poly(alkylene oxide) side-chain units have from 2 to 10 carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, (ii) at least about 50 wt.% of said alkylene oxide groups are ethylene oxide, and ) (iii) the amount of side-chain units is at least about 30 wt.% when the molecular weight of side-chain units is less than about 600 grams/mole, at least about 15 wt.% when the molecular weight of side-chain units is from about 600 to about 1,000 grams/mole, and at least about 12 wt.% when the molecular weight of side-chain units is more than about 1,000 grams/mcie, and (0) poiylethyiene oxide) main-chain units in an amount comprising less than about 25 wt.% of the polyurethane.

BACKGROUND OF THE INVENTION

U.S. Patent No. 5,700,867 relates to an aqueous polyurethane dispersion having an ionic functional group, polyoxyethylene units and hydrazine groups and used as a composition for ink, coating or adhesive.

The polyoxyethylene units can be in the main chain, at the end of the main chain or in side chains of the aqueous polyurethane. The content of polyoxyethylene units is about 20% by weight or less of the weight of the resin. Desirable properties of the composition include storage stability, water resistance, pigment dispersibility, and adhesion. There is no teaching or suggestion regarding breathability properties of the composition or the importance of amounts and length of side-chain and main-chain polyoxyethylene in achieving both breathability and other suitable polyurethane properties.

U.S. Patent No. 5,043,381 relates to an aqueous dispersion of a nonionic water-dispersible polyurethane having pendant polyoxyethylene i chains and one crosslink per 3,000 to 100,000 atomic weight units. U.S.

Patent 4,992,507 relates to an aqueous dispersion of a nonionic, water- ] dispersible polyurethane having pendant polyoxyethylene chains and free acid or free tertiary amino groups. Diols and diisocyanates having pendant polyoxyethylene chains are mentionec generaiy on 3th Sf the ater two patents, such as those in U.S. Patent Nos. 3,905,929 and 3,920,598 respectively. The dispersions are useful as coating compositions, but there is no teaching or suggestion in any of the latter four references regarding breathability properties of the compositions or the importance of amounts and length of side-chain and main-chain polyoxyethylene in achieving both breathability and other suitable polyurethane properties.

U.S. Patent 4,983,662 relates to an aqueous selfcrosslinkable coating composition comprising an aqueous dispersion of at least one polyurethane and having hydrazine (or hydrazone) functional groups and carbonyl functional groups disposed therein to provide a selfcrosslinkable reaction, in which the polyurethane polymer takes part, via azomethine formation during oo and/or after film formation. There is no teaching or suggestion regarding breathability properties of the composition or the importance of amounts and length of side-chain and main-chain polyoxyethylene in achieving both breathability and other suitable polyurethane properties. In addition,

Applicants’ breathable polyurethanes do not contain hydrazine functional groups or hydrazone functional groups.

U.S. Patent No. 4,190,566 relates to non-ionic, water-dispersible polyurethanes having a substantially linear molecular structure and lateral polyalkylene oxide chains having about 3 to 30% by weight of lateral polyalkylene oxide polyether chains. The chains consist of about 40-95% ’ ethylene oxides units and B-ZC9% certain other aikyiene oxide units selected from the group consisting of propylene oxide, butylene oxide and styrene oxide). Coatings are among the many uses listed, but there is no teaching regarding breathability properties of the composition or the importance of amounts and length of side-chain and main-chain polyoxyethylene in achieving both breathability and other suitable polyurethane properties.

U.S. Patent 4,092,286 relates to water-dispersible polyurethane elastomers having a substantially linear molecular structure, characterized by (a) lateral polyalkylene oxide units of from about 0.5 to 10% by weight, based on the polyurethane as a whole and (b) a content of =N* =, --COO or --S0, groups of from about 0.1 to 15 milliequivalents per 100 g. Coatings are among the many uses listed, but there is no teaching or suggestion regarding breathability properties of the composition or the importance of amounts and length of side-chain and main-chain polyoxyethylene in achieving both breathability and other suitable polyurethane properties.

A waterborne polyurethane dispersion is desired that can be used to produce films, coatings and other compositions having improved moisture vapor transmission rates and other improved properties compared to polyurethanes of the prior art. ) SUMMARY OF THE INVENTION

Breathable polyurethanes comprise (a) poly(alkylene oxide) side-chain units in an amount comprising about 72 wt.% tc about 80 wt.% of the polyurethane, wherein (i) alkylene oxide groups in said poly(alkylene oxide)

side-chain units have from 2 to 10 carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, (ii) at least about 50 wt.% of said alkylene oxide groups are ethylene oxide, and (iii} the amount of side-chain units is (i) at least about 30 wt.% when the molecular weight 5 of side-chain units is less than about 600 grams/mole, {ii} at least about 15 wt.% when the molecular weight of side-chain units is from about 600 to about 1,000 grams/mole, and {iii} at ieast about 12 wt.% when the molecular weight of side-chain units is more than about 1,000 grams/mole, and (b) poly(ethylene oxide) main-chain units in an amount comprising less than about 25 wt. % of the polyurethane.

A preferred process for making such breathable polyurethanes comprises:

A) reacting to form an isocyanate-terminated prepolymer [1) at least one polyisocyanate having an average of about two or more isocyanate groups; (2) at least one active hydrogen-containing compound comprising (a) polylalkylene oxide) side-chain units in an amount comprising about 12 wt.% to about 80 wt.% of said polyurethane, wherein (i) alkylene oxide groups in said poly(alkylene oxide) side-chain units have from 2 to 10 carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, {ii} at least about 50 wt.% of said alkylene oxide groups are ethylene oxide, and (iii) said amount of said side-cinaln units is at 'sast 2kowt wi.% when the molecular weight of said side-chain units is (ess than about 600 grams/mole, at least about 15 wt.% when the molecular weight of said side-chain units is from about 600 to about 1,000 grams/mole, and at least about 12 wt.% when the molecular weight of said side-chain units is more than about 1,000 grams/mole, and (b) polylalkylene oxide) main- chain units in an amount comprising less than about 25 wt.% of said polyurethane; (3) preferably at least one other active hydrogen-containing compound not containing polylaikylene oxide) side-chain units; and (4) optionally at least one compound having at least one crosslinkable functional group, in order to form an isocyanate-terminated prepolymer; (B) dispersing said prepolymer in water, and chain extending said prepolymer by reaction with at least one of water, inorganic or organic polyamine having an average of about 2 or more primary and/or secondary amine groups, polyalcohols, ureas, or combinations thereof; and (C) thereafter further processing the chain-extended dispersion of step } 15 (B) in order to form a composition or article having an upright moisture vapor transmission rate (MVTR) of more than about 500 gms/m?/24 hours.

Coatings and other articles made using such dispersions have excellent breathability, i.e., high moisture vapor transmission rates (MVTR) and can be made without volatile organic compounds such as solvents, neutralizing amines, or both.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to breathable polyurethanes prepared in a preferred process comprising: (A) reacting to form an isocyanate-terminated prepolymer {1} at least one polyisocyanate having an average of about two or more isocyanate groups; (2) at least one active hydrogen-containing compound comprising (a) poly(alkylene oxide) side-chain units in ar amount comprising about 12 wt.% to about 80 wt.% of said polyurethane, wherein (i) alkylene oxide groups in said poly(alkylene oxide) side-chain units have from 2 to 10 carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, (ii) at least about 50 wt.% of said alkylene oxide groups are ethylene oxide, and (iii) said amount of said side-chain units is at least about 30 wt.% when the molecular weight of said side-chain units is less than about 600 grams/mole, at least about 15 wt.% when the molecular weight of said side-chain units is from about 600 to about 1,000 grams/mole, and at least about 12 wt.% when the molecular weight of said side-chain units - is more than about 1,000 grams/mole, and (b} poly(ethylene oxide} main- chain units in an amount comprising less than about 25 wt.% of said polyurethane; (3) preferably at least one other active hydrogen-containing compound not containing poly(alkylene oxide) side-chain units; and (4) optionally at ieast one compoung raving &: east cine crossunkacie functicnal group, in order to form an isocyanate-terminated prepolymer;

(B) dispersing said prepolymer in water, and chain extending said prepolymer by reaction with at least one of water, inorganic or organic polyamine having an average of about 2 or more primary and/or secondary amine groups, polyalcohols, ureas, or combinations thereof; and (C) thereafter further processing the chain-extended dispersion of step (B) in order to form a composition or article having an upright moisture vapor transmission rate (MV TR) of more than about 500 gms/m?/24 hr.

Optionally at least one plasticizer is introduced into the reaction mixture at any time during prepolymer formation, before the prepolymer is dispersed in water. It can also be added to a finished dispersion. The process typically is conducted in the substantial absence and preferably in the complete absence of an organic solvent or a diluent other than the plasticizer.

Before continuing with discussion of the preferred process, it is noted that other processes can also be used to manufacture the breathable polyurethanes of the present invention, including but not limited to the } following: 1. Dispersing prepolymer by shear forces with emulsifiers (external emulsifiers, such as surfactants, or internal emulsifiers having anionic and/or cationic groups as part of or pendant to the polyurethane backbcne, anc/or as end groups on the polyurethane backbone).

2. Acetone process.

A prepolymer is formed with or without the presence of acetone, MEK, and/or other polar solvents that are non-reactive and easily distilled.

The prepolymer is further diluted in said solvents as necessary, and chain extended with an active hydrogen-containing compound.

Water is added to the chain- extended polyurethane, and the solvents are distilled off.

A variation on this process wouid be to chain extend the prepolymer after its dispersion into water. 3. Melt dispersion process.

An isocyanate-terminated prepolymer is formed, and then reacted with an excess of ammonia or urea to form a low molecular weight oligomer having terminal urea or biuret groups.

This oligomer is dispersed in water and chain extended by methylolation of the biuret groups with formaldehyde. 4. Ketazine and ketimine processes.

Hydrazines or diamines are reacted with ketones to form ketazines or ketimines.

These are added to a prepolymer, and remain inert to the isocyanate.

As the prepolymer is dispersed in water, the hydrazine or diamine is ] liberated, and chain extension takes place as the dispersion is taking place. 5. Continuous process polymerization.

An isccyanate-terminated prepolymer is formed.

This prepolymer is pumped through high shear mixing head(s) and dispersed into water and then chain extended at said mixing heads), or dispersed and chain extended simultaneously at said mixing head(s}. This is accomplished by multiple streams consisting of prepolymer (or neutralized prepolymer), optional neutralizing agent, water, and optional chain extender and/or surfactant. 6. Reverse feed process. Water and optional! neutralizing agent(s) and/or extender amine(s) are charged to the prepolymer under agitation. The prepolymer can be neutralized before water and/or diamine chain extender are added. 7. Solution polymerization. 8. Bulk polymerization, including but not limited to extrusion processes.

The breathable compositions of the present invention are conveniently referred to as polyurethanes because they contain urethane groups. They can be more accurately described as poly(urethane/ureals if the active ” hydrogen-containing compounds are polyols and polyamines. It is well understood by those skilled in the art that “polyurethanes” is a generic term used to describe polymers obtained by reacting isocyanates with at least one hydroxyl-containing compound, amine-containing compound, or mixture thereof. It aiso is weii undeistccd oy those skilled Im tha art that polyurethanes also include allophanate, biuret, carbodiimide, oxazolidinyl,

isocyanurate, uretdione, and other linkages in addition to urethane and urea linkages.

As used herein, the term “wt.%” means the number of parts by weight of monomer per 100 parts by weight of polymer on a dry weight basis, or the number of parts by weight of ingredient per 100 parts by weight of specified composition. As used herein, the term “molecular weight” means number average molecular weight.

Polyisocyanates

Suitable polyisocyanates have an average of about two or more isocyanate groups, preferably an average of about two to about four isocyanate groups and include aliphatic, cycloaliphatic, araliphatic, and aromatic polyisocyanates, used alone or in mixtures of two or more.

Diisocyanates are more preferred.

Specific examples of suitable aliphatic polyisocyanates include alpha, omega-alkylene diisocyanates having from 5 to ZO carbon atoms, such as = hexamethylene-1,6-diisocyanate, 1,12-dodecane diisocyanate, 2,2,4- trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, and the like.

Polyisocyanates having fewer than 5 carbon atoms can be used but are less : 20 preferred because of their high volatility and toxicity. Preferred aliphatic polyisocyanates include hexamethylene-1,6-diisocyanate, 2,2,4-trimethyl-

hexamethylene-diisocyanate, and 2,4 ,4-trimethyl-hexamethylene diisocyanate.

Specific examples of suitable cycloaliphatic polyisocyanates include dicyclohexylmethane diisocyanate, (commercially available as Desmodur™ W from Bayer Corporation), isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-bis-(isocyanatomethyl) cyclohexane, and the like.

Preferred cycloaliphatic polyisocyanates include dicyclohexylmethane diisocyanate and isophorone diisocyanate.

Specific examples of suitable araliphatic polyisocyanates include m- tetramethyl xylylene diisocyanate, p-tetramethyl xylylene diisocyanate, 1,4- xylylene diisocyanate, 1,3-xylylene diisocyanate, and the like. A preferred araliphatic polyisocyanate is tetramethyl xylylene diisocyanate.

Examples of suitable aromatic polyisocyanates include 4,4'- diphenylmethylene diisocyanate), toluene diisocyanate, their isomers, naphthalene diisocyanate, and the like. A preferred aromatic polyisocyanate is toluene diisocyanate. -

Active Hydrogen-containing Compounds

The term “active hydrogen-containing” refers to compounds that are a source of active hydrogen and that can react with isocyanate groups via the following reaction: —NCO + H X => —NH —-C(=0) -X. Examples of suitable active hydrogen-ccntaining compounds inc.uce cut ae mot limited to polyols, poythiols and polyamines.

As used herein, the term “alkylene oxide” includes both alkylene oxides and substituted alkylene oxides having 2 to 10 carbon atoms. The active hydrogen-containing compounds used in this invention have poly(alkylene oxide) side chains sufficient in amount to comprise about 12 wt.% to about 80 wt.%, preferably about 15 wt.% to about 60 wt.%, and more preferably about 20 wt.% to about 50 wt.%, of poly(alkylene oxide) units in the final polyurethane or a dry weight basis. At least about 50 wt. %, preferably at least about 70 wt.%, and more preferably at least about 90 wt.% of the poly(alkylene oxide) side-chain units comprise poly(ethylene oxide), and the remainder of the side-chain poly{alkylene oxide) units can comprise alkylene oxide and substituted alkylene oxide units having from 3 to about 10 carbon atoms, such as propylene oxide, tetramethylene oxide, butylene oxides, epichlorohydrin, epibromohydrin, allyl glycidyl ether, styrene oxide, and the like, and mixtures thereof. The term “final polyurethane” means the polyurethane produced after formation of the prepolymer followed by the chain extension step as described more fully hereafter. )

Preferably such active hydrogen-containing compounds provide less than about 25 wt.%, more preferably less than about 15 wt.% and most preferably less than about 5 wt.% poly(ethylene oxide) units in the backbone (main chain) based upon the dry weight of final polyurethane, since such main-chain poly{ethylene oxide} units itenc to cause swelling ct polyduretnane particles in the waterborne polyurethane dispersion and also contribute to lower in-use tensile strength of articles made from the polyurethane dispersion. Preferably the amount of the side-chain units is (i} at least about 30 wt.% when the molecular weight of the side-chain units is less than about 600 grams/mole, (ii) at least about 15 wt.% when the molecular weight of the side-chain units is from about 600 to about 1,000 grams/mole, and (iil) at least about 12 wt.% when the molecular weight of said side-chain units is more than about 1,000 grams/mole. Mixtures of active hydrogen-containing compounds having such poly(alkylene oxide) side chains can be used with active hydrogen-containing compounds not having such side chains.

Preferably the polyurethanes of the present invention also have reacted therein at least one active hydrogen-containing compound not having said side chains and typically ranging widely in molecular weight from about 50 to about 10,000 grams/mole, preferably about 200 to about 6,000 grams/mole, and more preferably about 300 to about 3,000 grams/mole.

Suitable active-hydrogen containing compounds not having said side chains ) include any of the amines and polyols described hereafter.

The term “polyol” denotes any high molecular weight product having an average of about two or more hydroxyl groups per molecule. Examples of such polyols that can be used in the present invention include higher polymeric poiyols sucn as posyester pGiveis and gelyeinel SCly sis, a8 wel as polyhydroxy polyester amides, hydroxyl-containing polycaprolactones,

hydroxyl-containing acrylic interpolymers, hydroxyl-containing epoxides, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polythioethers, polysiloxane polyols, ethoxylated polysiloxane polyols, polybutadiene polyols and hydrogenated polybutadiene polyols, polyacrylate polyols, halogenated polyesters and polyethers, and the like, and mixtures thereof. The polyester polyols, polyether polyols, polycarbonate polyols, polysiloxane polyols, and ethoxyiated polysiloxane polyols are preferred.

Poly(alkylene oxide) side chains can be incorporated into such polyols by methods well known to those skilled in the art. For example, active hydrogen-containing compounds having poly(alkylene oxide) side chains include diols having poly(ethylene oxide) side chains such as those described in U.S. Patent No. 3,905,929 (incorporated herein by reference in its entirety). Further, U.S. Patent No. 5,700,867 (incorporated herein by reference in its entirety) teaches methods for incorporation of poly(ethylene oxide) side chains at col. 4, line 35 to col. 5, line 45. A preferred active hydrogen-containing compound having poly(ethylene oxide) side chains is trimethylol propane monoethoxylate mether ether, available as Tegomer D- 3403 from Degussa-Goldschmidt.

The polyester polyols typically are esterification products prepared by the reaction of organic polycarboxylic acids or their anhydrides with a stoichiometric excess of a dioi. Exampies of suitable polyols for use in the reaction include poly(glycol adipate)s, poly(ethylene terephthalate) polyols,

polycaprolactone polyols, orthophthalic polyols, sulfonated and phosphonated polyols, and the like, and mixtures thereof.

The diols used in making the polyester polyols include alkylene glycols, e.g., ethylene glycol, 1,2- and 1,3-propylene glycols, 1,2-, 1,3-, 1,4-, and 2,3-butylene glycols, hexane diols, neopentyl glycol, 1,6- hexanediol, 1,8-octanediol, and other glycols such as bisphenol-A, cyclohexane diol, cyclohexane dimethanol {1,4-bis- hydroxymethylcycohexane}, 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3- pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, dimerate diol, hydroxylated bisphenals, polyether glycols, halogenated diols, and the like, and mixtures thereof. Preferred diols include ethylene glycol, diethylene glycol, butylene glycol, hexane diol, and neopentyl glycol. } 15 Suitable carboxylic acids used in making the polyester polyols include dicarboxylic acids and tricarboxylic acids and anhydrides, e.g., maleic acid, maleic anhydride, succinic acid, glutaric acid, glutaric anhydride, adipic acid, suberic acid, pimelic acid, azelaic acid, sebacic acid, chlorendic acid, 1,2,4- butane-tricarboxylic acid, phthalic acid, the isomers of phthalic acid, phthalic anhydride, fumaric acid, dimeric fatty acids such as oleic acid, and the like, and mixtures thereof. Preferred polycarboxy:ic acids used in making the polyester polyols include aliphatic or aromatic dibasic acids.

The preferred polyester polyol is a diol. Preferred polyester diols include poly(butanediol adipate); hexane diol adipic acid and isophthalic acid polyesters such as hexane adipate isophthalate polyester; hexane diol neopentyl glycol adipic acid polyester diols, e.g., Piothane 67-3000 HNA (Panolam Industries) and Piothane 67-1000 HNA; as well as propylene glycol maleic anyhydride adipic acid polyester diols, e.g., Piothane 50-1000 PMA; and hexane diol neopenty! glycol fumaric acid polyester diols, e.g., Piothane 67-500 HNF. Other preferred polyester diols include Rucoflex® S1015-35,

S$1040-35, and S-1040-110 (Bayer Corporation).

Polyether diols may be substituted in whole or in part for the polyester diols. Polyether polyols are obtained in known manner by the reaction of (A) the starting compounds that contain reactive hydrogen atoms, such as water or the diols set forth for preparing the polyester polyols, and (B) alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, and the like, and mixtures thereof. Preferred polyethers include poly(propylene glycol), h polytetrahydrofuran, and copolymers of poly(ethylene glycol) and poly(propylene glycol).

Polycarbonates include those obtained from the reaction of (A) diols such 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethyiene giycoi, anc the ike, and mixtures therest with (B) diarylcarbonates such as diphenylcarbonate or phosgene.

Polyacetals include the compounds that can be prepared from the reaction of (A) aldehydes, such as formaldehyde and the like, and (B) glycols such as diethylene glycol, triethylene glycol, ethoxylated 4,4'-dihydroxy- diphenyldimethylmethane, 1,6-hexanediol, and the like. Polyacetals can also . be prepared by the polymerization of cyclic acetals.

The aforementioned diols useful in making polyester polyols can also be used as additional reactants tc prepare the isocyanate terminated prepolymer.

Instead of a long-chain polyol, a long-chain amine may also be used to prepare the isocyanate-terminated prepolymer. Suitable long-chain amines include polyester amides and polyamides, such as the predominantly linear condensates obtained from reaction of (A) polybasic saturated and unsaturated carboxylic acids or their anyhydrides, and (B) polyvalent saturated or unsaturated aminoalcohols, diamines, polyamines, and the like, and mixtures thereof.

E Diamines and polyamines are among the preferred compounds useful ) in preparing the aforesaid polyester amides and polyamides. Suitable diamines and polyamines include 1,2-diaminoethane, 1,6-diaminohexane, 2- methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 1,12- diaminododecane, 2-aminoethanol, 2-[(2-aminoethyl)amino]-ethanol, piperazine, Z2,3-Cirneiny. siperazing, T-aminc-3-amincnetnyi-3,5,5- trimethylcyclohexane (isophorone diamine or IPDA), bis-{4-aminocyclohexyl)-

methane, bis (4-amino-3-methyl-cyclohexyl}-methane, 1,4- diaminocyclohexane, |,2-propylenediamine, hydrazine, urea, amino acid hydrazides, hydrazides of semicarbazidocarboxylic acids, bis-hydrazides and bis-semicarbazides, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, N,N,N-tris-{2-aminoethyllamine, N-{2- piperazinoethyl)-ethylene diamine, N,N'-bis-{2-aminoethyl}-piperazine,

N,N, N'-tris-(2-aminoethyl)ethylene diamine, N-[N-{2-aminoethyl}-2- aminoethyl]-N'-{2-aminoethyl}-piperazine, N-{2-aminoethyl)-N*'-{2- piperazinoethyl}-ethylene diamine, N,N-bis-(2-aminoethyl)-N-(2- piperazinoethyl)amine, N,N-bis-(2-piperazinoethyl)-amine, polyethylene imines, iminobispropylamine, guanidine, melamine, N-(2-aminoethyl)-1,3- propane diamine, 3,3'-diaminobenzidine, 2,4,6-triaminopyrimidine, polyoxypropylene amines, tetrapropylenepentamine, tripropylenetetramine,

N,N-bis-(6-aminohexyl)amine, N,N'-bis-(3-aminopropyl)ethylene diamine, and 2,4-bis-(4'-aminobenzyl)-aniline, and the like, and mixtures thereof.

Preferred diamines and polyamines include 1-amino-3-aminomethyl-3,5,5- trimethyl-cyclohexane {isophorone diamine or IPDA), bis-{4- aminocyclohexyl})-methane, bis-(4-amino-3-methylcyclohexyl)-methane, ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine, and the like, and mixtures thereof.

Other suitaoie diamines and pclyamires include Jeffamine® D-2000 and D- 4000, which are amine-terminated polypropylene glycols, differing only by molecular weight, and which are available from Huntsman Chemical

Company.

Prepolymer Ratios of isocyanate to Active Hydrogen

The ratio of isocyanate to active hydrogen in the prepolymer typically ranges from about 1.3/1 to about 2.5/1, preferably from about 1.5/1 to about 2.1/1, and more preferably from about 1.7/1 to about 2/1. :

Compounds Having at Least One Crosslinkabie Functional Group

Compounds having at least one crosslinkable functional group include those having carboxylic, carbonyl, amine, hydroxyl, and hydrazide groups, and the like, and mixtures of such groups. The typical amount of such optional compound is up to about 1 milliequivalent, preferably from about 0.05 to about 0.5 milliequivalent, and more preferably from about 0.1 to about 0.3 milliequivalent per gram of final polyurethane on a dry weight basis.

The preferred monomers for incorporation into the isocyanate- terminated prepolymer are hydroxy-carboxylic acids having the general formula (HO),Q(COOH),, wherein Q is a straight or branched hydrocarbon radical having 1 to 12 carbon atoms, and x and y are 1 to 3. Examples of such hydroxy-carboxylic acids include citric acid, dimethylolpropanoic acid (DMPA), dimethylol butanoic acid (DMBA), glycolic acid, lactic acid, malic acid, dihydroxymalic acid, tartaric acid, hydroxypivalic acid, and the like, and mixtures thereof. Dihydroxy-carboxylic acids are more preferred with dimethylolpropanoic acid (DMPA) being most preferred.

Other suitable compounds providing crosslinkability include thioglycolic acid, 2,6-dihydroxybenzoic acid, and the like, and mixtures thereof.

Catalysts

The formation of the isocyanate-terminated prepolymer may be achieved without the use of a catalyst. However, a catalyst is preferred in some instances. Examples of suitable catalysts include stannous octoate, dibutyl tin dilaurate, and tertiary amine compounds such as triethylamine and bis-(dimethylaminoethyl) ether, morpholine compounds such as @,'- dimorpholinodiethyl ether, bismuth carboxylates, zinc bismuth carboxylates, iron (ll) chloride, potassium octoate, potassium acetate, and DABCO® (diazabicyclo[2.2.2]octane), from Air Products. The preferred catalyst is a mixture of 2-ethylhexanoic acid and stannous octoate, e.g., FASCAT® 2003 from Elf Atochem North America. The amount of catalyst used is typically from about 5 to about 200 parts per million of the total weight of prepolymer reactants.

Prepolymer Neutralization

Optional neutralization of the prepolymer having pendant carboxyl groups converts the carboxyl groups to carboxylate anions, thus having a water-dispersibility enhancing effect. Suitable neutralizing agents include tertiary amines, metal hydroxides, ammonium hydroxide, phosphines, and other agents well known to those skilled in the art. Tertiary amines and ammonium hydroxide are preferred, such as triethyl amine (TEA), dimethyl ethanolamine (DMEA), N-methyl morpholine, and the like, and mixtures thereof. It is recognized that primary or secondary amines may be used in place of tertiary amines, if they are sufficiently hindered to avoid interfering with the chain extension process.

Chain Extenders

As a chain extender, at least one of water, inorganic or organic polyamine having an average of about 2 or more primary and/or secondary amine groups, polyalcohols, ureas, or combinations thereof is suitable for use in the present invention. Suitable organic amines for use as a chain extender include diethylene triamine (DETA), ethylene diamine (EDA), meta- xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA)}, 2-methyl pentane diamine, and the like, and mixtures thereof. Also suitable for practice in the present invention are propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, 3,3-dichlorobenzidene, 4,4’-methylene-bis-{2-chloroaniline), 3,3- dichloro-4,4-diamino diphenylmethane, sulfonated primary and/or secondary amines, and the like, and mixtures thereof. Suitable inorganic amines include nydrazine, substituted nydrazines, and nydrazine reaction products, and the like, and mixtures thereof. Suitable polyalcohols include those having from 2 to 12 carbon atoms, preferably from 2 to 8 carbon atoms, such as ethylene glycol, diethylene glycol, neopenty! glycol, butanediols, hexanediol, and the like, and mixtures thereof. Suitable ureas include urea and it derivatives, and the like, and mixtures thereof. Hydrazine is preferred and is most preferably used as a solution in water. The amount of chain extender typically ranges from about 0.5 to about 0.95 equivalents based on available isocyanate.

Polymer Branching

A degree of branching of the polymer may be beneficial, but is not required to maintain a high tensile strength and improve resistance to creep — that is, recovery to that of or near its original length after stretching. This degree of branching may be accomplished during the prepolymer step or the extension step. For branching during the extension step, the chain extender

DETA is preferred, but other amines having an average of about two or more primary and/or secondary amine groups may also be used. For branching during the prepolymer step, it is preferred that trimethylo! propane (TMP) and other polyols having an average of about two or more hydroxyl groups be used. The branching monomers can be present in amounts up to about 4 wt.% of the polymer backbone.

Plasticizers

The polyurethane of the present invention can be prepared in the presence of a plasticizer. The plasticizer can be added at any time during

Claims (1)

1. A polyurethane composition having an upright moisture vapor transmission rate (MVTR) of more than about 500 gms/m?/24 hr and comprising: (a) polylalkylene oxide) side-chain units in an amount comprising about 12 wt.% to about 80 wt.% of said polyurethane, wherein {i} alkylene oxide groups in said poly(alkylenc oxide} side-chain units have from 2 to 10 carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, {ii) at least about 50 wt.% of said alkylene oxide groups are ethylene oxide, and (iii) said amount of said side-chain units is at least about 30 wt.% when the molecular weight of said side-chain units is less than about 600 grams/mole, at least about 15 wt.% when the molecular weight of said side-chain units is from about 600 to about 1,000 grams/mole, and at least about 12 wt.% when the molecular weight of said side-chain units is more than about 1,000 grams/mole, and {b) poly(ethylene oxide) main-chain units in an amount comprising less than about 25 wt.% of said polyurethane.

2. A composition of Claim 1 wherein said poly{alkylene oxide} side- chain units comprise about 15 wt.% to about 60 wt.% of said polyurethane, gerd szid Toilet lene vide! —ainoohein units comnrien lags than about 15 wt. % of said polyurethane.

3. A composition of Claim 2 wherein said poly{alkylene oxide) side- chain units comprise about 20 wt.% to about 50 wt.% of said polyurethane, and said poly(ethylene oxide) main-chain units comprise less than about 5 wt.% of said polyurethane.

4. A composition of Claim 1 wherein said poly(alkylene oxide) side- chain units comprise poly(ethylene oxide) units.

5. A composition of Claim 2 wherein said poly(alkylene oxide) side- chain units comprise poly(ethylene oxide) units.

6. A composition of Claim 3 wherein said poly(alkylene oxide) side- chain units comprise poly(ethylene oxide) units.

7. A composition of Claim 1 wherein said polyurethane comprises the i reaction product of (1) at least one polyisocyanate having an average of about 2 or more isocyanate groups and (2) at least one polyol having an average of two or more hydroxyl groups per molecule,

8. A aomneogition of Clair 7 andharain aaid maoliicatha-a qo nrizgas thy reaction product of (1) at least one polyisocyanate having an average of about 2 to about 4 isocyanate groups, (2) at least one polyester polyol, polyether polyol, or combinations thereof, and (3) at least one chain extender comprising water, an inorganic or organic polyamine having an average of about 2 or more primary or secondary amine groups or combinations thereof, a polyalcohol, a urea, or combinations thereof.

9. A composition of Claim 8 wherein said chain extender comprises hydrazine.

10. A composition of Claim 8 wherein said polyurethane has reacted therein at ieast one active hydrogen-containing compound not having said side chains, and said compound has a molecular weight from about 50 to about 10,000 grams/mole.

11. A composition of Claim 10 wherein said active hydrogen- containing compound not having said side chains has a molecular weight from about 200 to about 6,000 grams/mole.

12. A composition of Claim 11 wherein said active hydrogen- containing compound not having said side chains comprises a polyol or nolamine sino = ommzisoilzr siz Troon osizot IID tz oamzut 5.0232 grams/mole.

13. A composition of Claim 12 wherein said active hydrogen- containing compound not having said side chains comprises polytetrahydrofuran, polyethylene glycol, polypropylene glycol, poly(ethylene oxide), poly(butanediol adipate), hexane adipate isophthalate polyester, hexane neopentyl adipate polyester, or combinations thereof.

14. A composition of Claim 12 wherein said polyisocyanate comprises a diisocyanate.

15. A composition of Claim 14 wherein said diisocyanate comprises 1,1'-methylenebis-4-(isocyanato cyclohexane), isophorone diisocyanate, 4,4'-diphenylmethylene diisocyanate, toluene diisocyanate, or combinations thereof.

16. A composition of Claim 10 wherein said polyurethane also has - reacted therein at least one compound having at least one crosslinkable functional group.

17. A composition of Claim 16 wherein said crosslinkable functional grouz comzrizes ozrholin carhont amine mediaset leedeanida ay combinations thereof.

18. A composition of Claim 17 wherein said compound having at least one crosslinkable functional group has the formula (HO),Q(COOH), wherein Q is a straight or branched hydrocarbon radical having 1 to 12 carbon atoms, and x and y are 1 to 3.

19. A composition of Claim 18 wherein said compound having at least one crosslinkable functional group comprises at least one dihydroxy- carboxylic acid.

20. A composition of Claim 19 wherein said dihydroxy-carboxylic acid comprises dimethylolpropanoic acid.

21. A composition of Claim 13 wherein said chain extender comprises hydrazine.

22. A composition of Claim 19 wherein said chain extender comprises hydrazine.

23. A composition comprising a blend of the composition of Claim 1 with at least one cther nolymer,

24. A composition of Claim 23 wherein said other polymer comprises natural rubber, a conjugated-diene-containing polymer, polychlorobutadiene, a hydrogenated styrene-butadiene triblock copolymer, chlorosulfonated polyethylene, an ethylene copolymer, an acrylic ester copolymer, a methacrylic ester copolymer, a vinyl chloride and vinylidene chloride copolymer, a vinylidene copolymer, polyisobutylene, a polyurethane, a polyurea, a poly(urethane/urea), or combinations thereof.

25. A composition of Claim 24 wherein said other polymer comprises an acrylic ester copolymer, a methacrylic ester copolymer, or combinations thereof.

26. An article comprising a polyurethane having an upright moisture vapor transmission rate (MVTR) of more than about 500 gms/m?/24 hr and comprising: (a) polylalkylene oxide) side-chain units in an amount comprising about 12 wit.% to about 80 wit.% of said polyurethane, wherein (i) alkylene oxide groups in said poly(alkylene oxide) side-chain units have from 2 to 10 carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, (ii) at least about 50 wt.% of said alkylene oxide groups are gto lens suis znd UY z2id smoumt of ssid sidechains unite ie ot least about wt.% when the moiecular weight of said side-chain units is less than about 600 grams/mole, at least about 15 wt.% when the molecular weight of said side-chain units is from about 600 to about 1,000 grams/mole, and at least about 12 wt.% when the molecular weight of said side-chain units is more than about 1,000 grams/mole, and (b) poly(ethylene oxide) main-chain units in an amount comprising less than about 25 wt.% of said polyurethane.

27. An article of Claim 26 wherein said poly(alkylene oxide) side-chain units comprise about 15 wt.% to about 60 wt.% of said polyurethane, and said poly(ethylene oxide) main-chain units comprise less than about 15 wt.% of said polyurethane.

28. An article of Claim 27 wherein said poly(alkylene oxide) side-chain units comprise about 20 wt.% to about 50 wt.% of said polyurethane, and said poly(ethylene oxide) main-chain units comprise less than about 5 wt. % of said polyurethane. i

29. An article of Claim 26 wherein said poly(alkylene oxide) side-chain units comprise poly(ethylene oxide) units.

30. An article of Claim 27 wiharain eaid nabiiginilana avidat aida atais units comprise poly(ethylene oxide) units.

31. An article of Claim 28 wherein said poly(alkylene oxide) side-chain units comprise poly(ethylene oxide) units.

32. An article of Claim 26 wherein said polyurethane comprises the reaction product of (1) at least one polyisocyanate having an average of about 2 or more isocyanate groups and (2) at least one polyol having an average of two or more hydroxy! groups per molecule.

33. An article of Claim 32 wherein said pclyurethane comprises the reaction product of (1) at least one polyisocyanate having an average of about 2 to about 4 isocyanate groups, (2) a polyester polyol, a polyether polyol, or combinations thereof, and (3) a chain extender comprising water, an inorganic or organic polyamine having an average of about 2 or more primary or secondary amine groups or combinations thereof, a polyalcohol, a urea, or combinations thereof.

34. An article of Claim 33 wherein said chain extender comprises hydrazine.

35. An article of Claim 22 wibgrain said ootocotbhooz hon coos therein at ‘east one active hydroegen-containing compound not having said side chains, and said compound has a molecular weight from about 50 to about 10,000 grams/mole.

36. An article of Claim 35 wherein said active hydrogen-containing compound not having said side chains comprises a polyol or polyamine having a molecular weight from about 200 to about 6,000 grams/mole.

37. An article of Claim 36 wherein said active hydrogen-containing compound not having said side chains has a molecular weight from about 300 to about 3,000 grams/mole.

38. An article of Claim 37 wherein said active hydrogen-containing compound not having said side chains comprises polytetrahydrofuran, polyethylene glycol, polypropylene glycol, poly(ethylene oxide), poly(butanediol adipate), hexane adipate isophthalate polyester, hexane ) neopentyl adipate polyester, or combinations thereof. )

39. An article of Claim 37 wherein said polyisocyanate comprises a diisocyanate.

49. Ar 2rticla of Claim 20 wvharein gaid digoava-ata an-sasizag 117] methylenebis-4-(isccyanatc cyclohexane), isophorcne diisocyanate, 4,4'-

diphenylmethylene diisocyanate, toluene diisocyanate, or combinations thereof.

41. An article of Claim 3b wherein said polyurethane also has reacted therein at ieast one compound having at least one crosslinkable functional group.

42. An article of Claim 41 wherein said crosslinkable functional group comprises one of carboxylic, carbonyl, amine, hydroxyl, hydrazide, or combinations thereof.

43. An article of Claim 42 wherein said compound having at least one crosslinkable functional group has the formula (HO), Q(COOH), wherein Q is a straight or branched hydrocarbon radical having 1 to 12 carbon atoms, and x and y are 1 to 3.

44. An article of Claim 43 wherein said compound having at least one crosslinkable functional group comprises at least one dihydroxy-carboxylic acid.

LZ. Am ozmtiziz If Zizi L& mErEicozsll In Zozovo-zerziil zo=siZ comprises dimethylolpropanoic acid.

46. An article of Claim 38 wherein said chain extender comprises hydrazine.

47. An article of Claim 44 wherein said chain extender comprises hydrazine.

48. An article comprising a blend of the polyurethane of Claim 26 with at least one other polymer.

49. An article of Claim 48 wherein said other polymer comprises natural rubber, a conjugated-diene-containing polymer, polychiorobutadiene, a hydrogenated styrene-butadiene triblock copolymer, chlorosulfonated polyethylene, an ethylene copolymer, an acrylic ester copolymer, a methacrylic ester copolymer, a vinyl chloride and vinylidene chloride ) copolymer, a vinylidene copolymer, a polyisobutylene, a polyurethane, a - polyurea, a poly(urethane/urea), or combinations thereof.

50. An article of Claim 49 wherein said other polymer comprises an acrylic ester copolymer, a methacrylic ester copolymer, or combinations thereof,

51. An article of claim 26 comprising a porous or nonporous substrate treated with said polyurethane.

52. An article of claim 51 comprising a porous substrate treated with said polyurethane.

53. An article of claim 52 comprising a textile impregnated, saturated, sprayed or coated with said polyurethane.

54. A personal care composition comprising a topically acceptable phase, together with a polyurethane having an upright moisture vapor transmission rate (MVTR) of more than about 500 gms/m?/24 hr and comprising: {a) poly(alkylene oxide) side-chain units in an amount comprising ' about 12 wt.% to about 80 wt.% of said polyurethane, wherein (i) alkylene oxide groups in said poly(alkylene oxide) side-chain units have from 2 to 10 B carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, (ii) at least about 50 wt.% of said alkylene oxide groups are ethylene oxide, and (iii) said amount of said side-chain units is at least about wt.% when the molecular weight of said side-chain units is less than about 600 gramse/molg. at least about 15 wt % whan the molecular waicht of said side-chair units is from about 8C0C to abcut 1,00C grams/mose, and at least about 12 wt.% when the molecular weight of said side-chain units is more than about 1,000 grams/mole, and (b) poly(ethylene oxide) main-chain units in an amount comprising less than about 25 wt.% of said polyurethane.

55. A personal care composition of Claim 54 wherein said poly(alkylene oxide) side-chain units comprise about 15 wt.% to about 60 wt.% of said polyurethane, and said poly(ethylene oxide) main-chain units comprise less than about 15 wt.% of said polyurethane.

56. A personai care composition of Claim 55 wherein said poly(alkylene oxide) side-chain units comprise about 20 wt.% to about 50 wt.% of said polyurethane, and said poly(ethylene oxide} main-chain units comprise less than about 5 wt.% of said polyurethane.

57. A personal care composition of Claim 54 wherein said poly(alkylene oxide) side-chain units comprise poly(ethylene oxide) units.

58. A personal care composition of Claim 55 wherein said . 20 polylalkylene oxide) side-chain units comprise poly(ethylene oxide) units.

59. A personal care composition of Claim 56 wherein said poly(alkylene oxide) side-chain units comprise poly(ethylene oxide) units.

60. A personal care composition of Claim 54 wherein said polyurethane comprises the reaction product of (1) at least one polyisocyanate having an average of about 2 or more isocyanate groups and (2) at least one polyol having an average of two or more hydroxyl groups per molecule.

61. A personal care composition of Claim 60 wherein said polyurethane comprises the reaction product of (1) at ieast one polyisocyanate having an average of about 2 to about 4 isocyanate groups, (2) a polyester polyol, polyether polyol, or combinations thereof, and (3) a chain extender comprising water, an inorganic or organic polyamine having an average of about 2 or more primary or secondary amine groups or combinations thereof, a polyalcohol, a urea, or combinations thereof. i

62. A personal care composition of Claim 61 wherein said chain extender comprises hydrazine.

2%. zferzzoz! zErE ocoohTIstiz- of Clg 20 orh-zraln zaid polyurethane has reacted therein at least cne active hydrogen-containing compound not having said side chains, and said compound has a molecular weight from about 50 to about 10,000 grams/mole.

64. A personal care composition of Claim 63 wherein said active hydrogen-containing compound not having said side chains comprises a polyol or polyamine having a molecular weight from about 200 to about 6,000 grams/mole.

65. A personal care composition of Claim 64 wherein said active hydrogen-containing compound net having said side chains has a molecular weight from about 300 to about 3,000 grams/mole.

66. A personal care composition of Claim 65 wherein said active hydrogen-containing compound not having said side chains comprises potytetrahydrofuran, polyethylene glycol, polypropylene glycol, poly(ethylene oxide), poly(butanediol adipate), hexane adipate isophthalate polyester, or - combinations thereof.

67. A personal care composition of Claim 65 wherein said polyisocyanate comprises a diisocyanate.

68. A personal care composition of Claim 67 wherein said diisocyanate comprises 1,1’-methylenebis-4-{isocyanato cyclohexane), isophorone diisocyanate, 4,4'-diphenylmethylene diisocyanate, toluene diisocyanate, or combinations thereof.

69. A personal care composition of Claim 63 wherein said polyurethane also has reacted therein at least one compound having at least one crosslinkable functional group.

70. A personal care composition of Claim 69 wherein said crosslinkable functional group comprises carboxylic, carbonyl, amine, hydroxyl, hydrazide, or combinations thereof.

71. A personal care composition of Claim 70 wherein said compound having at least one crosslinkable functional group has the formula {HO),Q(COOH), wherein Q is a straight or branched hydrocarbon radical ) having 1 to 12 carbon atoms, and x and y are 1 to 3.

72. A personal care composition of Claim 71 wherein said compound having at least one crosslinkable functional group comprises at least one aSiabideniodl altel dbataiaiii tod Sodtall

73. A personal care composition of Claim 72 wherein said dihydroxy- carboxylic acid comprises dimethylolpropanoic acid.

74. A personal care composition of Claim 66 wherein said chain extender comprises hydrazine.

75. A personal care composition of Claim 72 wherein said chain extender comprises hydrazine.

76. A process for producing a polyurethane, said process comprising: (A) reacting to form ar isccyanate-terminated prepolymer (1) at least one polyisocyanate having an average of about two or more isocyanate groups, and (2) at least one active hydrogen-containing compound comprising (a) poly(alkylene oxide) side-chain units in an amount comprising about 12 wt.% to about 80 wt.% of said polyurethane, wherein (i) alkylene oxide groups in said poly{alkylene oxide} side-chain units have from 2 to 10 B carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, (ii) at least about 50 wt.% of said alkylene oxide groups are ethylene oxide, and (iii) said amount of said side-chain units is at least about wt.% when the molecular weight of said side-chain units is less than about 600 grams/mole, at least about 15 wt.% when the molecular weicht of said side-crain units is from about 300 tc abcut 1,000 grams/mole, and at least about 12 wt.% when the molecular weight of said side-chain units is more than about 1,000 grams/mole, and (b} poly(ethylene oxide) main- chain units in an amount comprising less than about 25 wt.% of said polyurethane. (B) dispersing said prepolymer in water, and chain extending said prepolymer by reaction with water, an inorganic or organic polyamine having an average of about 2 or more primary and/or secondary amine groups, a polyalcohols, a urea, or combinations thereof; and {C) thereafter further processing the chain-extended dispersion of step (B) in order to form a composition or article having an upright moisture vapor transmission rate (MV TR) of more than about 50C gms/m-/24 hr.

77. A process of Claim 76 wherein said poly(alkylene oxide) side- chain units comprise about 15 wt.% to about 60 wt.% of said polyurethane, and said poly(ethylene oxide) main-chain units comprise less than about 15 wt. % of said polyurethane. B

78. A process of Claim 77 wherein said poly(alkylene oxide) side- chain units comprise about 20 wt.% to about 50 wt.% of said polyurethane, and said poly(ethylene oxide} main-chain units comprise less than about 5 wt Oh of gaid molhyoratharg,

79. A process of Claim 76 wherein said poly(alkylene oxide) side- chain units comprise poly(ethylene oxide) units.

80. A process of Claim 77 wherein said poly(alkylene oxide) side- chain units comprise poly(ethylene oxide) units.

81. A process of Claim 78 wherein said polylalkylene oxide) side- chain units comprise poly(ethylene oxide) units.

82. A process cf Claim 76 comprising reaction of (1) at least one polyisocyanate having an average of about 2 or more isocyanate groups and (2) at least one polyol having an average of two or more hydroxyl groups per molecule. ’

83. A process of Claim 82 comprising reaction of (1) at least one polyisocyanate having an average of about 2 to about 4 isocyanate groups, (2) a polyester polyol, polyether polyol, or combinations thereof, and (3) a chain extender comprising water, an inorganic or organic polyamine having an average of about 2 or more primary or secondary amine groups or combinations thereof, a polyalcohol, a urea, or combinations thereof.

84. A process of Claim 83 wherein said chain extender comprises hydrazine.

85. A process of Claim 83 wherein said polyurethane has reacted therein at least one active hydrogen-containing compound not having said side chains, and said compound has a molecular weight from about 50 to about 10,000 grams/mole.

86. A process of Claim 85 wherein said active hydrogen-containing compound not having said side chains has a molecular weight from about 200 to about 6,000 grams/mole.

87. A process of Claim 86 wherein said active hydrogen-containing compound not having said side chains has a molecular weight from about 300 to about 3,000 grams/mole.

88. A process of Claim 87 wherein said active hydrogen-containing compound not having said side chains comprises polytetrahydrofuran, polyethylene glycol, polypropylene glycol, poly(ethylene oxide), poly(butanediol adipatel, hexane adipate isophthalate polyester, hexane

89. A process of Claim 87 wherein said polyisocyanate comprises a diisocyanate.

90. A process of Claim 89 wherein said diisocyanate comprises 1,1’- methylenebis-4-(isocyanato cyclohexane), isophorone diisocyanate, 4,4'- diphenylmethylene diisocyanate, toluene diisocyanate, or combinations thereof.

91. A process of Claim 85 wherein said polyurethane also has reacted therein at least one compound having at least one crosslinkable functional group.

92. A process of Claim 91 wherein said crosslinkable functional group comprises carboxylic, carbonyl, amine, hydroxyl, hydrazide, or combinations thereof.

93. A process of Claim 92 wherein said compound having at least one crosslinkable functional group has the formula (HO),Q(COOH), wherein Q is a straight or branched hydrocarbon radical having 1 to 12 carbon atoms, and x and y are 1 to 3.

94. A process of Claim 93 wherein said compound having at least one crosslinkable functional group comprises at least one dihydroxy-carboxylic acid.

95. A process of Claim 94 wherein said dihydroxy-carboxylic acid comprises dimethylolpropanoic acid.

96. A process of Claim 88 wherein said chain extender comprises hydrazine.

97. A process of Claim 94 wherein said chain extender comprises hydrazine.

98. A process comprising blending the polyurethane of Claim 76 with at least one other polymer.

99. A process of Claim 98 wherein said other polymer comprises natural rubber, a conjugated-diene-containing polymer, polychlorobutadiene, a hydrogenated styrene-butadiene triblock copolymer, chlorosulfonated polyethylene, an ethylene copolymer, an acrylic ester copolymer, methacrylic == sgtzt oI ver oz Um zhaoridz end oinlidans oblovide conclvmer. 3 vinylidene copolymer, a polyisobutylene, a polyurethane, a polyurea, a polylurethane/urea), or combinations thereof.

100. A process of Claim 99 wherein said other polymer comprises an acrylic ester copolymer, methacrylic ester copolymer, or combinations thereof.