WO2010051293A1

WO2010051293A1 - Dispersion of hybrid polyurethane with olefin-acrylic copolymerization

Info

Publication number: WO2010051293A1
Application number: PCT/US2009/062289
Authority: WO
Inventors: Anthony D. Pajerski; Robert J. Pafford, Iv; Naser Pourahmady; Libin Du; James D. Burrington; Stuart L. Bartley
Original assignee: Lubrizol Advanced Materials, Inc.
Priority date: 2008-10-31
Filing date: 2009-10-28
Publication date: 2010-05-06
Also published as: US20110245399A1; KR20110090989A; TW201022295A; EP2350155A1; CN102232091A; EP2350155B1; US8575256B2; CN102232091B; TWI469995B; KR101741124B1

Abstract

A product and processes comprising urethane polymer and at least one copolymer from a hydrophobic ethylenically unsaturated C₄-C₃₀ olefins copolymerized with polar monomers such as acrylates. One process optionally utilizes an acid source to modify/catalyze the reactivity of the polar monomer and/or radically activated repeat unit from the polar monomer to promote incorporation of he ethylenically unsaturated olefin. Other processes vary depending on which polymer if formed and/or dispersed first. The hybrid copolymer shows excellent adhesion to a variety of polymeric and/or polar substrates such as polyolefins, acrylate coatings, wood, etc.

Description

DISPERSION OF HYBRID PO LYl' RETHANE WITH OLEFIN-ACRYLIC COPOLYMERIZATION

FIELD QF INVENTION

[00011 The field is the copolymerizatiσn of non-polar C₄-C₃₀ ethylenically unsaturated aliphatic olefins with monomers containing electron withdrawing groups such as acrylates/acrylics within a polyurethane dispersion, The dispersion media is preferably aqueous. The resulting copolymer is a stable emulsion or dispersion of hybrid polymer particles in aqueous media.

BACKGROUND QF THE INVENTION

[0002} Ethylenically unsaturated olefins without heteroatom substitution typically have low eopolymerization rates with polar monomers such as acrylates. The copolymerization technology of olefins with polar monomers is reviewed in WO 03/070783 and WO 2005/054305, both owned by PPG Industries Ohio, Inc. The olefins are described as electron donating type monomers and the acrylates are described as electron accepting monomers.

(00031 In WO 03/070783, Examples A and B of the copolymers they feed 3 or 4 different charges into a reaction vessel over several hours maintaining a temperature of 140- 16O⁰C and pressures from 5 psi to 62 psi in Example A and 40 to 360 psi in Example B. Molecular weights were number averages of 2293 and 4274 while the weight averages were 8317 and 12,856 gram/mole. These copolymers were blended with more conventional latexes and made into curable film forming compositions. [0004] In WO 2005O54305, Examples 1 -4 were 25'20'5S w/w/w of isobutyleπe/hydroxypropyl acryl ate/butyl acrylate polymerized into a copolymer by the method of the patent application, The monomers and di-t-amyl peroxide were prepared in three separate feed tanks and commingled in a feed line just prior to addition to the 5- gallon stirred reactor. The reactor was maintained between 200 and 21O⁰C and at a pressure of 500 psi for a residence time of 16 to 25 minutes. The resulting polymer was reported to have a composition of 21 wt.% isobutylene, 27 wt.% hydroxypropyl acrylate, and 52 wt.% butyl acrylate. The copolymer was reported to have number average molecular weights between 1446 and 1699 and weight average molecular weights between 278 1 and 3441 g/mole.

[0005] U.S. Patent No. 4,198,330 discloses the modification of polyurethane dispersions by polymerization of acrylic monomers in the presence of the waterborne polyurethane particle.

[0006] U.S. Patent No, 3,705,164 teaches the use of acetone as a diluent in the prepolymer to prepare aromatic polyurethane dispersions free of NMP that are further modified with a polyaciylic polymer.

[0007] U.S. Patent No, 5,662,966 teaches the preparation of aromatic polyυrethanes that are

NMP free using acetone tn the prepolymer using dimethyioi butanoic acid as a dispersing diol agent.

[0008] U.S. Patent No, 5,637,639 discloses NMP free polyurethane compositions that use low amounts of acetone as a diluent in the prepolymer.

[00091 U.S. Patent No. 4,655,030 discloses the preparation of aliphatic poiyurefhaπe-acrylic dispersions via a process that renders them free of NMP.

[0010] U.S. Patent No. 5,137,961 discloses the preparation of surfactant free and solvent free polyurethane-acrylic dispersions.

[0011] U.S. Patent Nυ. 4,927.876 discloses the preparation of waterborne polyurethane and urethane-acrylie compositions containing diphenyi methane diisocyanaie and using NMP as a diluent in the prepolymer.

[0012] U.S. Patent No. 6,239,209 leaches the preparation of oxidatively curable aromatic polyurethane-acrylics using NMP as a diluent in the prepolymer.

[0013] WO 99/16805 discloses aqueous polymer dispersions containing a water-dispersed polyureihanc polymer and a vinyl (preferably acrylic) polymer.

[0014] WO2006/002865 discloses NMP free aromatic polyurethane and urethane-aerylie compositions that use methyl ethyl ketone as a diluent in the prepolymer.

SUMMARY QF THE INVENTION

[0015] A polymeric reaction product resulted from free radically polymerizing a) at least one ethyl enically unsaturated aliphatic olefin with 2 or 4 to 30 carbon atoms with b) at least one ethylenically unsaturated monomer containing an electron withdrawing group, and c) optionally other ethyl enically unsaturated monomers forming a copolymer comprising repeating units within the same copolymer from said at least one aliphatic olefin and said at least one monomer containing electron withdrawing group(s) in a polyurethane prepolymer dispersion in water with a free radical initiator source, optionally in the presence of a Lewis or Brόnsted acid. This polymeric reaction product is a stable emulsion of hybrid urethane-olefin-acrylic particles in aqueous media with good film formation properties. A film from the hybrid particles was found to have many desirable properties such as variable glass transition temperature, good barrier properties with respect to water and solvents, and a relatively hydrophobic surface.

DETAILED DESCRIPTION OF THE INVENTION

[0016] This invention relates to compositions and processes io prepare waterborne polyurethane-polyolefin-acrylic hybrids and copolymers prepared using a waterborne polyurethane "seed" particle to host the oltjfin-acryiic polymerization. The polyurelhane portion of the composition would be similar to those conventionally used to prepare waterborne polyurethane dispersion and would be based on aliphatic and/or aromatic di or poly-isocyanates, polyols (typically polyester, polyeiher and/or polycarbonate), short chain diols, dispersing diols (anionic, cationic, non-ionic or combinations thereof), and optionally chain extended with a diamine (including hydrazine). The polyolefin-aerylic portion of the composition would be composed of C_{4 30} olefins, optimally alpha-olefins, in combination with acrylic (and optionally styrcne) monomers; the mole ratio of olefin to acrylic monomers would be between 80:20 to 20:S0, in another embodiment from 2:98 to 49:51 ; in a third embodiment between 3:97 or 4:96 to 35:65; and in a fourth embodiment from 5:95 to 20:80, An advantage of using a polyurethane seed as a component to carry out the olefm-acrylic polymerisation that the polyurethane can act as an effective carrier and polymerization platform for higher olefins (typically greater than Cl 2) which are known to be difficult to polymerize by conventional emulsion polymerization techniques.

{0017] The resulting polyurelhane-polyolefm-acrylic hybrid would give an IPN or interpenetrating polymer network of the polyurethane and polyolefϊn-acrylic, optionally with the more hydrophobic polyolefin-aerylic residing preferentially within the shell of the waterborne particle. However, it is also anticipated that copolymers of the polyurethane and polyolefin-acryiic can also be obtained by optionally using the Lubrizol RAFT diol or "mono-ol" as a component in the preparation of the polyurethane polymer as described in WO02/020281 for polyυrethane-acrylic copolymers. The RAFT based copolymers are anticipated to give a more uniform (e.g., homogeneous) distribution of the polyurethane urethane and poiyolefiii-acryhc components based on previous observations for RAFT based urethanc-acrylic (and mcthacrylate) copolymers. The waterbome polyurethane-polyolefm-acrylic hybrids could also be prepared using a starting polyurethane-oiefin-acrylic seed (instead of a polyurethane seed). The hybrid concept could help avoid the use of co-solvents such as N-methyl pyrrolidonc (NMP) which are often used to process conventional waterbome polyurethanes. The weight ratio of polyurethane to polyolefiivacrylic polymer would be in the range of 2:98 to 98:2, in another embodiment from 90:10 to 10:90, in a third embodiment from 20:80 to 80:20, in a fourth embodiment in the range of 30:70 to 50:50 to emphasis, the properties and advantages brought by the polyolefin-acrylic portion of the composition. These anticipated advantages include improved wetting and adhesion performance to various substrates, particularly those with low surface energy, improved chemical resistance and barrier properties and improved cost-performance characteristics for the final product. Moreover, the tactile properties can be affected by the use of larger olefins. [0018] Prior acrylate coatings provide many attractive performance properties, including good film-forming properties, balance of hard_' soft (glass transition), adhesion to polar substrates (wood, metal, paper, polyester, nylon, ABS. concrete, etc.), oil resistance (with acrylonitπle added as monomer), and some moisture resistance by adding styrene monomer. Prior art urethane coatings offered durable surfaces but some sensitivity to polar solvents was noted.

[0019] To add certain properties associated with olefinic monomers, it is necessary to incorporate hydrophobic (hydrocarbon-like aliphatic olefin(s)) components into the acrylic polymer. Some conventional ways of doing this include the use of acrylate esters of long chain alcohols, such as 2-ethylhexyl acr>late, or esters of versatates, such as dodecyl versatate, the use of an olefiiv'aerylate cυmpatibili/er such as polymeric surfactants and the use of a fatty acid chain transfer agent. Ethylhcxyl di esters of inaleic acid arc also thought to impart hydrophobicity and adhesion to olefins. These methods increase cost and are limited in the amount of hydrophilic component that can be incorporated.

[0020] The direct incorporation of aliphatic olefin into the acrylic (acrylate) polymer backbone within a urethane prepolymer provides the potential for a low cost, versatile method for achieving the properties of a hydrophobically modified hybrid urethane- acrylatc polymer coating. Although such a process has been a subject of study by polymer chemists for many years, these efforts have met with limited success.

[0021] This disclosure describes a free-radical system (optionally utilizing Brόnsted or Lewis acid) that can co-polymerize olefins in urethane prepolymer or urethane prepolymer dispersion in conventional copυlymerization reactors at conventional acrylate polymerization temperatures and pressures. The solid or soluble versions of

Lewis or Brόnsted acids are optionally part of the catalyst system with an aqueous media polymerization process, wherein the free radical initiator is selected from any known to those in this art, including peroxides (e.g., dibenzoylperoxide), hydroperoxides (e.g., t- butylhydroperoxide), persulfatcs (e.g., sodium pcrsulfate) or azo compounds (e.g., azobisisobutyronitrile, AIBN), redox initiator systems, and mixtures of these conventional free radical initiators.

[0022] ^'I he monomers (which will be described later in more detail) are independently selected from: a) an ethylenically unsaturated aliphatic alpha olefin, including but not limited to isobutylenc. diisobutylene, nonene, or any other olefin containing a terminal olefin group, olefins with the beta carbon di-alkyl-substituted are preferred in one embodiment, b) at least one ethylenically unsaturated monomer containing an electron withdrawing group, alternatively described as an ethylenically unsaturated monomer containing a carbon yl or nitrogen group, such as an acrylate acid or ester including acrylic acid, methyl acrylate or ethyl acrylate, 2-ethylhexyl acrylate, or any normal or branched alkyl acrylate with an alcohol component of 1 to 32 carbon atoms, and c) optionally niethacrylic acid or ester, slyrene, acrylonitrile, vinyl chloride, vinyl amide or any other free-radically-polymerizable olefin, and/or an electron rich olefin, including vinvl ethers or esters. [0023] More specifically, in one embodiment, the optional soluble or solid acid component can be any solid containing Lewis or Bronsted acid groups. Examples of solid Bronsted acids are acidified clays (e.g., Engelhard F -24, superfiitrol or Sud-Chcmie Tonsil® catalysts), sulfonated styrene divinylbenzene copolymers (Rohm and Haas Amberlyst® catalysts), heteropolyacids such as phosphotungstic acid (H₃PW₁₂Cu)), fumed silica, silica/aluminas or zeolites. Examples of Lewis acids include any transition metal compound that is soluble or dispersable in the emulsion media, (including naphthenates of Fe, Co, Ni, Mn, Cr, or Mo) or solid or solid supported versions containing transition metal ions such as Fe₂O₃ on alumina, or any of the above- mentioned soluble or dispersable transition compounds on a solid support such as montmorilinite (Bentonite) clays, silca, alumina, silica-aluminas and the like. [0024] In another embodiment, liquid or water soluble Lewis or Bronsted acids (to the extent that they are inherently or can be made to be stable in the presence of water or in an aqueous media) can be selected from those disclosed in the prior art. Liquid or soluble Lewis or Bronsted acids (when stable in a medium containing water) may be difficult to remove and may contribute to degradation or color in the polymer, which may be undesirable. Examples of liquid or water soluble Lewis or Bronsted acids include free radically polymeria, able acids such as monomers containing carboxylic acid, phosphonic acid, sulfonic acid, etc., such as acrylic acid, itaconic acid, maleic acid, AMPS (acrylamide(2 -methyl propane sulfonic acid) (available from Lubrizol Advanced Materials, Inc. in Cleveland, Ohio), etc. In one embodiment, the pKA value of the Lewis or Bronsted acid source is less than 6. In some limited embodiments, it may be desirable to exclude from the copolymer or reaction product (e.g., claim as free of, substantially free of, or having less than 100, 50, 25, 10, 5, 2, or 1 ppm based on the weight of all monomers to the polymerization recipe) either monomers containing acid groups (e.g., containing any of sulfonic, carboxylic, and phosphonic acid) or individually exclude using the same values the sulfonic, carboxylic, or phosphonic acid containing monomers. [0025] Definitions. Unless otherwise indicated, the following terms have the following meanings:

[0026] As used herein, the term "wt.%" means the number of parts by weight of monomer per 100 parts by weight of polymer or copolymer on a dry weight basis, or the number of parts by weight of ingredient per 100 parts by weight of specified composition.

[0027] As used herein, the term "molecular weight" means number average molecular weight unless otherwise specified.

[ΘO28| "Polymer" means a chemical substance consisting of one or more repeating units characterized by the sequence of one or more types of monomer derived units (monomer residues) and comprising a simple weight majority of molecules containing at least 3 monomer derived units which are covaiently bound to at least one other monomer derived unit or other reactant. Such molecules can be distributed over a range of molecular weights and can be characterized by number-average and/or weight-average molecular weights and polydispersity index.

[0029] In this document, "pol yurethane" is a generic term used to describe urethane polymers including oligomers (e.g., prepolymers) which contain multiple urethane groups, i.e., -O-C(=O)-NH-, regardless of how they are made. As well known, polyurethanes can contain additional groups such as urea, allophanate, amide, biuret, carbodiimide, carbonyl, oxazolidinyl, isocynaurate, uretdione, ether, ester, carbonate, etc., in addition to urethane groups. Typically, the prepolymers will be from about 1,000 to about 3,000 Dal tons in number average molecular weight and if chain extended during the processing can reach number average molecular weights in the millions of Daltons. |0030j "Aqueous medium" means a composition containing a substantial amount of water. It may contain other ingredients as well.

J0031] The ethylenically unsaturated aliphatic olefin monomer(s) that are copolymerized with the polar monomers optionally using the Brόnsted or Lewis acid of this disclosure are unsaturated olefins with in one embodiment from 2 to 30 carbon atoms, in another embodiment from 4 or 5 to 30 carbon atoms, and in third embodiment desirably 4 or 5 to 20 carbon atoms. Desirably they are monounsatυrated. They include branched and cyclic olefins but in preferred embodiments do not include styrenic monomers where the aliphatic nature is concluded after the first two carbon atoms of the ethylenic unsaturation. In one embodiment, the ethylenically unsaturated olefin monomer(s) do not include any atoms other than carbon and hydrogen, i.e., they are entirely hydrocarbon. In one embodiment, the formula of these molecules is CH₂=CR¹R" where R' is a linear or branched Ci to C 2s alkyl that may be linear, branched or cyclic and R^'' is hydrogen or a linear or branched alkyl as set forth for R'. with the proviso that R^s and R" together have no more than 28 carbon atoms. In one embodiment, it is desirable that R" is a linear or branched alkyl of 1 to 4 carbon atoms. Olefins where both R' and R" are Cj or higher are believed to be more co-polymerizable with the other monomers than olefins where one of R' or R'^' is hydrogen. Examples of ethylenically unsaturated aliphatic olefins include butylene, isobutylene. diisobutylene, pentene, hexene, octene, dodecenc and other linear and branched olefins. }0032] Free-Radical Polvmen/able Monomers. Examples of free radical co~ polymeri/able monomers which are useful in forming the copolymers of this invention include acrylic esters, methacrylic esters, unsaturated nitrites, styrenic monomers, vinyl esters, vinyl ethers, conjugated dienes. olefins, halogenated (e.g.. vinyl chloride and vinyiidene chloride), allyl and other monomers, and mixtures thereof, The preferred ethylenically unsaturated monomers for achieving copolymeruation with the ethylenically unsaturated aliphatic olefins, optionally in the presence of a Brδnstcd or Lewis acid are those with electron withdrawing groups or including carbonyl or nitrogen containing groups, such as the acrylates, ethylenically unsaturated monomers with carboxylic acid groups such as acrylic acid, nitrile monomers such as acrylonitrile, vinyl amides, etc. Desirably, the monomers with the electron withdrawing groups arc characterized by the electron withdrawing group having a sigma σ (inductive component) value from 0.1 to 0.9 according to Bromilow et a!.. J. Org. Chem., 44, 4766 f 1979). Later listed monomers that do not meet the definitions for achieving copolymerization with ethylenically unsaturated aliphatic olefins are listed as optional monomers to provide other properties to the copolymers). The list of monomers below includes some monomers that may have basic functional groups that interact unfavourably with the Lewis or Bronsted acids (possibly forming salts). It is anticipated that one skilled in the art would use such monomers with basic functional groups in such a way or in such limited amounts as not to interfere with the function of the Lewis or Bronsted acid in catalyzing the copolymerization of the ethylenically unsaturated olefin of 4 to 30 carbon atoms with the polar carbonyl containing monomer. [0033| Specific examples include acrylic esters and methacrylic acid esters having the formula I:

wherein Rj is hydrogen, methyl, or ethyl group, and R₂ contains about 1 to 100 carbon atoms, more typically ϊ to 50 or 1 to 25 or 32 carbon atoms, and optionally, also one or more sulfur, nitrogen, phosphorus, silicon, halogen or oxygen atoms. Examples of suitable (meth)acrylate esters include methyl (meth)acrylate, ethyl (meth) aery late, n- propyl (meth)acrylatc. n-butyl (meth)acrylate, isopropyϊ (metb)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)aerylate, n-hexyl (meth) acryl ate, isoamyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) acryl ate, 4-hydroxybutyl (meth)acrylate, N.N-dimethylaminoethyl (meth)acrylate, N, N- diethylaminoethyl (metb)acrylate, t-butylaminoethyl { meth) acryl ate, 2-sulfoethyl (meth)acrylate, trifluoro ethyl (meth)acrylate, glycidyl (meth) acryl ate, benzyl (meth)acrylate, allyl (meth)acrylate, 2-n-butoxyetbyl (meth)acrylate, 2-chloroethyI (meth)acrylate, sec-butyl-(meth)acrylate, tert-butyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, cinnamyl (meth) acryl ate, crotyl (meth)acrylate. cyclohexyl (meth)acrylatε, cyclopentyl (meth)acrylate, 2-ethoxyethyl (metb)acrylate, furfuryl (meth)acrylate, hexafiuoroisopropyl (meth) acryl ate, methallyl (meth)acrylate, 3- methoxybutyl (meth)acrylate, 2-methoxybutyl (meth)aerylate, 2-nitro-2-methylpropyl (meth)acrylate, n-octyl (metli)acrylate, 2-ethylhexyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-phenylethyl (meth)acrylate, phenyl (meth)acrylate, propargyl (meth)acrylate, tetrahydrofurfuryi (meth)acrylatc, norbornyl (meth)acrylatc, acrylamidc and its derivatives, and tetrahydropyranyl (meth)acrylate. Mixtures of acrylic and methacrylic acid esters may be used. The polymerized acrylic and methacrylic acid esters typically may comprise up to 50, 75, 90 or 95 wt.% of the copolymer, depending on the amount of ethylcnically unsaturated olefin desired in the copolymer. Esters similar to acrylic and methacrylic include esters of vinyl monomers have two or more carboxylic groups such as itaconic, fumaric. and maleic acids, [0034] Unsaturated nitrile monomers include aerylonitrile or an aikyl derivative thereof, the alkyl preferably having from i to 4 carbon atoms, such as aerylonitrile, methacrylonitrile, and the like, Also suitable are unsaturated monomers containing a cyano group such as those having the formula II:

CH₂-C(R³)CO(O)CH₂CH₂CN (II)

wherein R³ is H or

₃ and n is 1 to 4 carbon atoms. Other examples of unsaturated nitrile monomers include CHi-C(CN)₂, CH₃-CH=CH-CN, NC-CH=CH-CN. 4- pentenenitrilo, 3-methyl-4-pentenenitrile, 5-hcxcnciiitrile, 4-viiiyl-benzonitrile, 4-allyl- benzonitrile, 4-vinyl-cydohexanecarbonitrile, 4-cyanocyclohexene. and the like. Mixtures of the unsaturated nitriles may also be used. Aerylonitrile and methacrylonitrile are preferred. In some embodiments, the polymerized unsaturated nitrile monomers typically may comprise no more than about 60 wt %, more typically no more than 20 wt. %, 15 wt. %, 10 wt. %, 5 wt. % or 3 wt. % of the copolymer. [0035J The "styrenic monomers" useful in preparing the hydrophilic polymer(s) of this invention may be defined as monomers containing a carbon-carbon double bond in the alpha-position to an aromatic ring. For the purpose of this disclosure, styrenie monomers will be considered neither to be ethylenically unsaturated aliphatic olefins nor ethyl enically unsaturated monomers with electron withdrawing groups. Notwithstanding, styrenie monomers may be included as co-monomer(s) in making the copolymers of this invention. Examples of suitable styrenie monomers include styrenc, alpha-rnethylstyrene, tertiary butylstyrene, ortho, meta, and para-methylstyrene, ortho-, meta- and para-ethylstyrene, o-meth)l-p-isopropylstyrene, p-chlorostyrene, p- bromostyrene. o,ρ-dichlorostyrene, o,p-dibromostyrene, ortho-. meta- and para- mcthoxystyrene. indene and its derivatives, vinylnaphthalene, diverse vinyl (alkyl- naphthalenes) and vinyl (halonaphthaienes) and mixtures thereof, acenaplithylene, diphenylethylene, and vinyl anthracene. Mixtures of styrenie monomers also may be used. Styreπe and alpha-methylstyrene are preferred. In some embodiments where the -I t-

repeating units from styrene type monomers are undesirable, the polymerized styrenic monomers typically may comprise no more than about than 80 wt. %, 60 wt, %, 40 wt. %, 20 wt. %, 10 wt, % or 5 wt. % of the copolymer.

[0036] Vinyl ester monomers derived from carboxylic acids containing 1 to 100, more typically 1 to 50 or 1 to 25, carbon atoms also may be useful in preparing the vinyl polymer of the present invention. Examples of such vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl octanoate, vinyl pelargonate, vinyl caproate, neo esters of vinyl alcohol, vinyl laurate, vinyl versatate and the like, as well as mixtures thereof. The polymerized vinyl ester monomers typically may comprise from 0 wt. % to about 99.5 wt. % of the vinyl polymer of the present invention.

[0037] Vinyl ethers may be useful in preparing the copolymer of the present invention. Examples of vinyl ethers include methyl-, ethyl-, butyl, iso~butyl vinyl ethers and the like. In one embodiment, the polymerized vinyl ether monomers typically may comprise from 0 wt. % to about 60 wt. %, preferably from 0 wt. % to about 50 wt. %, of the vinyl polymer of the present invention.

[0Θ38J Conjugated diene monomers containing 4 to 12 carbon atoms, and preferably from 4 to 6 carbon atoms, also may be useful in preparing the polymer of the present invention. Examples of such conjugated diene monomers include butadiene, isoprene, pentadiene, and like, as well as mixtures thereof. Butadiene is preferred. As expressed earlier, diene monomers contribute to UV light sensitivity and possibly accelerate polymer degradation under UV light. Thus, in some embodiments where UV light will be present, the copolymers have less than 50, more desirably less than 30, more desirably less than 10 or 20, and preferably less than 5 wt.% repeating units from diene monomers. [0039] Olefin monomers outside one or more of the definition(s) of ethyl enically unsaturated aliphatic olefins containing 4 to 30 carbon atoms may also be useful in preparing the vinyl polymer of the present invention. Examples of such olefins include ethylene and propylene, as well as mixtures thereof. Cyclic olefins may also be used such as vinyl cyclohexane, cyclopcntene, cyclohexene, eyclooctadiene, norbornene, norbornadiene, pinene and like. In one embodiment, the copolymer may typically be comprised from 0 or 1 wt, % to about 50 wt. %, from 0 or 1 wt. % to about 20 or 30 wt. %, or from 0 wt. % to about 5 or 10 wt. %, of repeating units from ethylene, propylene or cyclic olefin monomers.

[0040] Ethylenically unsaturated monomers comprising fluorine, chlorine, bromine, and iodine may be useful in preparing the copolymer of the present invention. They may contain 2 to 100 carbon atoms and at least one halogen atom. Examples of such monomers include vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, halogenated (meth)acrylic and styrenic monomers, allyl chloride and like, as well as mixtures thereof. Sometimes halogenated monomers or their repeating units are sensitive to degradation catalyzed by Lewis or Brδnsted acids. Thus, in some embodiments, the copolymer of this invention will comprise less than 50 wt.%, more desirably less than 20 or 30 wt.% and more desirably still less than 5 or 10 wt.% of halogenated repeating units from these monomers.

[0041] Polar and Hydrophiiie Monomers. Another group of monomers which are useful in preparing the copolymers of the present invention are polar monomers such as hydroxyalkyl (mcth)acrylates, (meth)acrylamides and substituted (meth)acrylamides, sodium styrene sulfonate and sodium vinyl sulfonate, N-vinyl-2-pyiτolidonc, N-vinyl caproϊactam, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4~ hydroxybυtyl (meth)acrylate, (4-hydro.xymethylcyclohexyl)-methyl (meth)acryiate, acrolein, diacetone (meth)aerylaiτπde, l-(2-((2-hydroxy-3-(2- propenyloxy)propyl)amino)ethyl)-2-imidazolidinone, N-methyloi (meth)acrylamide, diallyl phosphate, Sipomer© WAM. WAM II (from Rhodia) and other uri do -containing monomers, dimethylaminoethyl (inetli)acrylate, and dimcthylaminopropyl (meth)acrylamide, acrylic acid, me th acrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, aerylamido (2-methyl propane sulfonic acid), and vinyl phosphonic acid. Mixtures of polar monomers also may be used.

[0042] Hydrophilie Monomers and Components. Hydrophiiie components (i.e., monomers, chain transfer agents, initiators) have at least one hydrophiiie, ionic or potentially ionic group is optionally included in the copolymer to assist dispersion of the polymer, thereby enhancing the stability of the dispersions so made. Typically, this is done by incorporating a compound bearing at least one hydrophiiie group or a group that - i j-

can be made hydrophilic (e.g., by chemical modifications such as neutralization or deblocking) into the polymer chain. These compounds may be of a non-ionic, anionic, cationic or zwitteriorπc nature or the combination thereof, [0043] For example, anionic groups such as carboxylate, sulfate, sulfonate, phosphate, and phosphonate can be incorporated into the polymer in an inactive foπn and subsequently activated by a salt-forming compound, such as ammonia, organic amines and alkali metal hydroxides. Other hydrophilic compounds can also be reacted into the polymer backbone, including lateral or terminal hydrophilic ethylene oxide, the organic amines and polyamϊne/polyimines previously described as chain extenders for polyurethanes, pyrrolidone or ureido units.

[0044] Hydrophilic compounds of particular interest are ihose which can incorporate acid groups into the polymer such as ethyl eiiical Iy unsaturated monomers having at least one carboxylic acid group, and preferably one or two carboxylic acid groups. Examples of such monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumarie acid, crotonic acid, vinyl acetic acid, mesaconic acid, citraconic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrene sulfonic acid, 2- sulfoethyl (mcth)acrylate, alkali metal salts of^* the above acids and amine or ammonium salts thereof such as sodium allyl sulfonate, sodium l-allyloxy-2-hydroxypropane sulfonate {COPS 1 ), 2-acrylamido-2 -methyl propane sulfonate (AMPS), sodium dodecyl allyl sulfosuccinate (TREM-LF40). sodium methallyl sulfonate, sodium styrene sulfonate, sodium vinyl sulfonate, sodium vinyl phosphonate, sodium sulfoethyl methacrylale.

[0045] Strong acid monomers are also desirable in the copolymer. Examples of ethylenically unsaturated strong acid monomers useful according to the invention include, but are not limited to, 2-acrylamido-2-methylpropane sulfonic acid. 1-allyloxy- 2-hydroxypropane sulfonic acid, vinylsulfonic acid, styrene sulfonic acid, alkyl allyl sulfosuccinic acid, sulphocthyl(mcth)acrylate, phosphoalkyl(meth)acrylates such as phosphoethyl methacrylate (phosphate ester of 2-hydroxycthyl methacrylate), phosphoethyl acrylate, phosphopropyl(meth)acrylate, phosphobutyl(rneth)acrylatc, phosphate ester of polyctlvyleneglycoi(mcth)acrylate, phosphate ester of polypropyleneglycol (meth)acrylate. phosphoalkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl(meth)acrylatcs, phosphodialkyl crotonates, vinyl phosphonic acid (VPA) and allyl phosphate. Salts of these unsaturated strong acid monomers are also useful, Di esters and blends of in on esters and diesters of the phosphate strong acids are useful also. The term "(mcth)acrylate," and the like, as used throughout means either an acrylate, or a methacrylate. or mixtures of both. In a preferred embodiment, the ethylenically unsaturated strong acid monomer is a phosphorous-containing monomer, and especially an unsaturated phosphate ester such as phosphoethyl methacrylate (phosphate ester of 2 -hydroxy ethyl methacrylate). [0046] Compounds/Monomers Having at Least One Crosslinkable Functional Group. Compounds having at least one crosslinkable functional group can also be incorporated into the vinyl polymers of the present invention, if desired. Examples of such compounds include N-methylol acryjamide (NMA), diacetone acrylamide (DAAM), acetoacetoxy ethyl methacrylate (AAEM), epoxy-containing compounds, -OH containing compounds, -COOH containing compounds, isocyanate-containing compounds (TMI). mercaptan-containing compounds, compounds containing olefinic unsaturation and the like. Mixtures can also be used. Polyurethane Prepolymer Ingredients

[0047] The polyurethane prepolymers of this invention are formed from at least one poiyisocyanate, at least one active hydrogen-containing compound containing two or more active hydrogens (e.g., an isocyanate reactive polyol), and optionally, at least one ionic and/or non-ionic water-dispersibility enhancing compound. Poiyisocyanate

[0048 j Desirably a large proportion of the polyisocyanates used to make the prepolymer and polyurethane of this disclosure are aromatic polyisocyanates. Expressed one way, desirable at least about 20 to 65 part of at least one aromatic poiyisocyanate is used, in one embodiment from about 30 to about 60 parts and in another embodiment from about 35 to about 55 parts of polyurethane. Expressed another way desirably at least 75 mole percent, in another embodiment at least 85 or 95 mole %, and in a third embodiment at least 98 mole percent of the total polyisocyanates used to form the prepolymer and polyurethane are aromatic isocyanates. The aromatic polyisocyanates can have two or more isocyanate groups. They may include isomers or oligomers of polyisocyanates that help reduce crystalliiiity of the as received material so that it is liquid rather than a crystalline solid at room temperature. Examples of suitable aromatic polyisocyanates include 4,4'-diphenylmethylcnc diisocyanate, its 2,4' isomer, its

2.2'isomer, mixtures thereof, toluene diisocyanate including it 2,4 and 2,6 version, phenyl ene diisocyanate, polymethylenc polyphenyl polyisocyanates, naphthalene diisocyanate, their oligomeric forms, mixtures thereof, and the like. Preferred aromatic polyisocyanates are toluene diisocyanate and diphenylvnethylene diisocyanate.

[0049] Suitable polyisocyanates in general have an average of about two or more isocyanate groups, preferably an average of about two to about four isocyanate groups per molecule and comprising about 5 to 20 carbon atoms {in addition to nitrogen, oxygen, and hydrogen) and include aliphatic, cyeloaliphatic, aryl-aliphatic, and aromatic polyisocyanates, as well as products of their oligomerization, used alone or in mixtures of two or more. Diisocyanates are more preferred. Aliphatic isocyanates generally tolerate UV exposure better than aromatic isocyanates in terms of low color development on exposure.

[005Oj Examples of aliphatic polyisocyanates include alpha, omega-alkylene diisocyanates having from 5 to 20 carbon atoms, such as hexamethylene-1 ,6- diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexarnethylene diisocyanate,

2,4,4-trimethyl-hexamethylene diisocyanate. 2 -methyl- 1 ,5-pentamethylene diisoeyanate, and the like.

[0051 j Examples of suitable cyeloaliphatic polyisocyanates include dicyclohexylmcthane diisocyanate, (commercially available as Desmodur^{i M} W from

Bayer Corporation), isophorone diisocyanate, 1 ,4-cyclohcxanc diisocyanate, 1 ,3-bis-

(isocyanatomethyl) cyclohexane, and the like.

[0052] Examples of araliphatic polyisocyanates include m-tetramethyl xylylene diisocyanate, p-tetramethyl xylylene diisocyanate, 1.4-xylylene diisocyanate, 1,3- xylylene diisocyanate, and the like.

(ii) Active Hydrogen-containing Compounds

[0053] Any compound that provides a source of active hydrogen for reacting with isocyanate groups via the following reaction: -NCO+H-X -> -NH-C(=O)-X, can be used as the active hydrogen-containing compound in this invention. Examples include but are not limited to poiyols, polythiols and polyamines.

{0054] "Polyol" in this context means any product having an average of about two or more hydroxyl groups per molecule (e.g., isocyanate reactive polyol). Examples include low molecular weight products called "extenders" with number average molecular weight less than about 500 Dalton such as aliphatic, cycloaliphatic and aromatic poiyols, especially diols, having 2-20 carbon atoms, more typically 2-10 carbon atoms, as well as "rnacroglycols," i.e., polymeric poiyols having molecular weights of at least 500 Daltons, more typically about 1,000-10,000 Daltons, or even 1 ,000-6,000 Daltons. Examples of such rnacroglycols include polyester poiyols including alkyds, polyether poiyols, polycarbonate poiyols, polyhydroxy polyester amides, hydroxyl -containing polycaprolactones, hydroxyl-containing acrylic polymers, hydroxyl -containing epoxides, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polythioethers, polysiloxane poiyols, ethoxylated polysiloxane poiyols, polybntadiene poiyols and hydrogenated polybutadienc poiyols, polyisυbutykne poiyols, polyacrylate poiyols, halogenated polyesters and polyethcrs, and the like, and mixtures thereof. The polyester poiyols, polyether poiyols, polycarbonate poiyols, polysiloxane poiyols, and ethoxylated polysiloxane poiyols are preferred.

[0055] In one embodiment, it is desirable to have 20 or 25 to 55 or 60 % by weight of isocyanate reactive poiyols incorporated in the prepolymcr or polyurethane component, ϊn one embodiment, these have a number average molecular weight above 500 Daltons per mole. In one embodiment, it is desirable to have one of the poiyols be derived from or characterized as a poly(propylene glycol) polyol, e.g., polypropylene oxide). In one embodiment, it is desirable that the weight ratio of poly(propylenc glycol) polyol to the other poiyols be from about 10:90 to 90: 10.

[0056] The polyester poiyols typically are esterification products prepared by the reaction of organic polycarboxylic acids or their anhydrides with a stoichiometric excess of a diol or diols. Examples of suitable poiyols for use in the reaction include poly(glycol adipate)s, poly(ethylene terephthalate) poiyols, polycapro lactone polyol s, alkyd poiyols, orthophthalic poiyols, sulfonated and phosphonated poiyols, and the like, and mixtures thereof. [0057] The diols used in making the polyester polyols include alkyiene glycols, e.g., ethylene glycol, 1,2- and 1 ,3-propylene glycols, 1,2-, 1.3-, 1.4-, and 2,3-butylcne 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- hydroxymcthylcycohexane), 2-mefhyl-l ,3 -propanediol, 2,2,4-trimcthyl-l ,3-pentanediol, diethylene glycol, Methylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol dimerate diol, hydroxylated bisphenols, polyether glycols, halogenated diols, and the like, and mixtures thereof Preferred diols include ethylene glycol, diethylene glycol, butyl cne glycol, hexane diol, and neopentyl glycol.

[0058] Suitable carboxylic acids used in making the polyester polyols include dicarboxylic acids and tricarboxylic acids and anhydrides, e.g., nialeic 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 polycarboxylic acids used in making the polyester polyols include aliphatic and/or aromatic dibasic acids,

[0059] Particularly interesting polyols arc the polyester diols, i.e., any compound containing the -C(=O}-0- group. Examples include poly(butanediol adipate), caprolactones, acid-containing polyols, polyesters made from hexane diol, adipic acid and isophthalic acid such as hexane adipate isophthalate polyester, hexane diol neopentyl glycol adipic acid polyester diols, e.g., Piothane 67-3000 HAI, Piothane 67-500 HAI, Piothane 67-3000 HNA (Panolam Industries) and Piothane 67-1000 HNA; as well as propylene glycol maleic anhydride adipic acid polyester diols, e.g., Piothane 50-1000 PMA; and hexane diol neopentyl glycol fumaric acid polyester diols, e.g., Piothane 67- 500 HNF. Other polyester diols include Rucoflex™. S 1015-35, S 1040-35, and S-1040- 1 10 (Bayer Corporation).

J0060] In one embodiment, the polyol component of the polyurethane is a polyol with air oxidizable or self-crosslinkablc unsaturation as described in paragraphs 0016 to 0034 of WO 2006/047746, hereby incorporated by reference. The unsaturation while avaϋable for air oxidative crosslmking after film formation is also available to copolymcrize with the free-radically polymcrizable monomers. To the extent that the free -radically polymcrizable monomers copolyincrize with oxidizable unsaturation incoφorated into the polyurethane. grafting between the two types of polymers will occur. This will occur during the polymerization of the acrylatc and olefin monomers initiated by free radical source and possibly by temperature. A preferred polyol is a natural oil modified polyol available from Pioneer Plastics, m Auburn, ME and sold under the name PiothaneOS S-500. Such grafting of a cry late type monomers to unsaturation within a oxidatively crosslinkable polyurethane during urethane hybrid formation is also disclosed in US Patent 6,4e>2,127. Another way to incorporate grafting sites into the polyurethane (for grafting between the polyurethane and olefm-aerylate polymer of this disclosure) Ls to incorporate components reactive in both urethane forming and in free radical polymerization, Such components (often monounsaturatcd but optionally polyunsaturated) but would also have groups reacthe with isocyanates (such as hydroxyls or amine groups) such as 2 -hydroxy ethyl acrylate. To the extent that such components only have a single isocyanatc reactive group, they would typically be chain ends on the urethane prepolymer rather than backbone components as with the oxidatively crosslinking polyols described above. This type of technology is explained in further detail m US Pat. 4,730,021.

(00611 The polycthcr polyols that can be used as the active hydrogen-containing compound in accordance with the present invention contain the -C-O-C- group. They can be obtained in a 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, butylcne oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, and the like, and mixtures thereof. Preferred polyethcrs include ρoly(propylene glycol), polytetrahydrofuran, and copolymers of poly( ethylene glycol) and polypropylene glycol).

[0062] Polycarbonate polyols include those containing the -O-C(=-Q)-O- group. They can be obtained, for example, from the reaction of (A) diols such 1.3-propancdiol, 1.4- butancdiol, 1 ,6-hcxanediol, diethyl cne glycol, triethylcnc glycol, tetraethylene glycol, and the like, and mixtures thereof with (B) diarylcarbonates such as diphenyl carbonate or phosgene. Aliphatic and cycloaliphatic polycarbonate polyols can also be used. [0063] Useful polyhydroxy 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, tri ethylene glycol, ethoxylated 4,4'-dihydroxy- diphenyldimethylmethane, 1 ,6-hexanediol, and the like. Polyacetals can also be prepared by the polymerization of cyclic acetals.

[0064] Instead of or in addition to a polyol, other compounds may also be used to prepare the prepolymer. Examples include polyamiπes, polyester amides and polyamides, such as the predominantly linear condensates obtained from reaction of (A) polybasic saturated and unsaturated carboxylic acids or their anhydrides, and (B) polyvalent saturated or unsaturated aminoalcohols, diamines, polyamines, and the like, and mixtures thereof.

[0065] 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-l ,5- pentanedi amine, 2,2,4-tπmethyl-l ,6-hexanediamine, 1 ,12-diaminododecane, 2- aminoethaπol, 2-[(2-ammoethyl)amino]~ethanol. piperazine, 2,5-dimethylpiperazine, 1- amino~3-anunomethyl-3,5,5-trimcthyl- cyclohexane (isophoronc diamine or JPDA), bis- (4-aminocyclohexyl)-mcthane, bis-(4-amino-3-methyl-cyclohexyl)-m ethane, 1,4- diaminocyclohexane, 1,2-propylenediamine, hydrazine, urea, amino acid hydrazides, hydrazides of serniearbazidocarboxylic acids, bis-hydrazides and bis-semicarbazides, diethylene triamine, tri ethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, N,N,N-tris-(2~aminoethyl)ami ne, N-(2-piperazinoethyl )-ethylene diamine, N,N'-bis-(2-avninoethyl)-piperazin- e, N,N,NMris-(2-aminoethyl)ethylcne diamine, N- [N-(2-aminoethyl)-2 -amino- ethyl]-N'-(2-aminoethyl)-pipcrazine, N-(2-aminoethyl)-N'- (2-piperaziπocthy- l)-ethylene diamine, N,K-bis-(2-aminoethyl)-N-(2- ρiperazinoethyl)amine, N,N-bis-(2-pipcrazinoethyl)-amine, polyethylene imines, iminobispropylamine, guanidine, melamine, N-(2-aminoethyl)-l ,3-propanc diamine, 3,3 '-diaminobenzidine, 2,4,6-triaminopyrimidine, polyoxypropylene amines, tetrapropylenepentamine, tripropylenefetramine, N,N-bis-(6-aminohexyl)amine, N, N '- bis-(3-aminopropyl)cthylene diamine, and 2,4-bis-(4'-aminobenzvl)-anihnc, and the like, and mixtures thereof. Preferred diamines and polyammes include l -amino-3- aminomethyl-3.5.5-tri- methyt-eyclohexane (isophorone diamine or IPDA), bis-(4- aminocycluhexyl)-m- ethane, bis-(4-amino-3-methylcyclohexyl)-methant;, ethylene diamine, diethyl ene tri amine, lri ethylene tetramine, tetraethylene pentamine, and pentacthylene hexamine, and the like, and mixtures thereof. Other suitable diamines and polyamines include Jeffamine™. D-2000 and D-4000, which are amine-tcrminated polypropylene glycols, differing only by molecular weight, and which were available from Huntsman Chemical Company.

[0066] Low molecular weight alkylene polyols (e.g.. glycerol, trimcthylol propane, etc ) can be used as urethane branching agents. Branching can provide beneficial properties to a urethane polymer and can provide additional functional (reactive) end groups (generally above 2 as one goes from a linear oligomers to a branched oligomers or polymer) for each urethane prcpolymer or polymer. Water-Dispersibility Enhancing Compounds

[0067] Polyurefhancs are generally hydrophobic and not water-dispersible, In accordance with one embodiment of the invention, therefore, at least one water- dispcrsibility enhancing compound (i.e., monomer), which has at least one, hydrophilic (e.g., poly( ethylene oxide)), ionic or potentially ionic group is optionally included in the polyurethane prepolymcr to assist dispersion of the polyurethane prepolymer as well as the chain-extended polyurethane made therefrom in water, thereby enhancing the stability of the dispersions so made. Often these are diols or polyols containing water- dispersibility enhancing functionality. Often these are of less than 500 number average molecular weight if ionizable. In one embodiment, it is desirable to have about 0, 1 or 2 to about 10 or 12% by weight of a diol polyol or polyols or combinations thereof bcarmg active hydrogen groups as and containing a ionizable or potentially ionizable water dispersing group solubilised in either b) a vinyl monomer or c) a reactive polyol or a combination thereof. Typically, this is done by incorporating a compound bearing at least one hydrophilic group or a group that can be made hydrophilic (e.g., by chemical modifications such as neutralization) into the polymer chain. These compounds may be of a non-ionic, anionic, cationic or zwittcπonic nature or the combination thereof. For example. anionic groups such as carboxylic acid groups can be incorporated into the prepolymcr in an inactive form and subsequently activated by a salt-forming compound, such as a tertiary amine defined more fully hereinafter, in order to create a prepolymer having an acid number from about 1 to about 60, typically 1 to about 40, or even 10 to 35 or 12 to 30 or 14 to 2.5 mg KOH/g. Other watcr-dispersibility enhancing compounds can also be reacted into the prepolymcr backbone through urcthane linkages or urea linkages, including lateral or terminal hydrophilic ethylene oxide or ureido units, f0068] Water dispersibiϊity enhancing compounds of particular interest are those which can incorporate carboxyi groups into the prepolymer. Normally, they are derived from hydroxy-carboxylic acids having the general formula (HO)_kQ(COOH}_y, wherein Q is a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y are 1 to 3. Examples of such hydroxy-carboxylic acids include dimethylolpropanoic acid (DMPA)₁ dimethylol butanoic acid (DMBA) (most preferred), citric acid, tartaric acid, glycolic acid, lactic acid, malic acid, dihydroxy malic acid, dihydroxytartaric acid, and the like, and mixtures thereof. Dihydroxy-carboxylic acids are more preferred with dimethylolproanoic acid (DMPA) and dimethylol butanoic acid (DMBA) being more preferred than the others.

[0069] Water dispersibiiity enhancing compounds may include reactive polymeric polyol components that contain pendant anionic groups which can be polymerized into the prepolymer backbone to impart water dispcrsiblc characteristics to the polyurethane subsequent to chain extension. The term anionic functional polymeric polyol includes anionic polyester poiyols, anionic polycther polyols, and anionic polycarbonate polyols. These polyols include moieties that contain active hydrogen atoms. Such polyols containing anionic groups are described in U.S. Patent No. 5.334,690, [0070] Another group of water-dispersibility enhancing compounds of particular interest are side chain hydrophilic monomers (non-ionic dispersibiiity enhancing components). Some examples include alkylene oxide polymers and copolymers in which the alkylene oxide groups have from 2- IO carbon atoms as shown, for example, in U.S. Published Patent Application No. 20030) 95293 to Noveon, Inc. for breathable polyurethane blends, the disclosure of which is incorporated herein by reference. [0071 J Other suitable water-dispersibihty enhancing compounds include thioglycolic acid, 2,6-dihydroxybenzoic acid, sulfoisophthalic acid (this component would preferably be incorporated as part of a polyester), polyethylene glycol, and the like, and mixtures thereof.

Compound.? Having at Least One Crosslinkahle Functional Group

[0072] Compounds having at least one crosslinkable functional group can also be incorporated into the polyurethane prepolymers of the present invention, if desired.

Examples of such compounds include those having carboxylic, carbonyl, amine, hydroxyl, epoxy. acetoacetoxy, urca-fomialdehyde, auto-oxidative groups that crosslink via oxidization, ethylenically unsatureated groups optionally with U.V. activation, olefinic and hydrazide groups, blocked isocyanatcs, and the like, and mixtures of such groups and the same gi'oups in protected forms (so erosslmkmg can be delayed until the composition is in its application (e.g., applied to a substrate) and coalescence of the particles has occurred) which can be reversed back into original groups from which they were derived (for crosslinking at the desired time).

[0073] Other suitable compounds providing crosslinkability include thioglycolic acid,

2,6-dihydroxybeπzoic acid, and the like, and mixtures thereof,

Catalysts

[0074] The prcpolymer may be formed without the use of a catalyst if desired.

Ingredient Proportions

J0075] Normally, the prepolymer produced in the present invention will be isocyanate- terminated. For this purpose, the ratio of isocyaπatc to active hydrogen in forming the prepolymer typically ranges from about 1.3/1 to about 2.5/1. in one embodiment from about 1.5/1 to about 2.1 /1 , and in another embodiment from about 1.65/1 to about 2''I .

[0076] The typical amount of water-dispersibility enhancing compound (total of all ionic and non-iomc) in the prepolymer will be up to about 50 wt.%, more typically from about 2 wt.% to about 30 wt.%, and more especially from about 2 wt.% to about 10 wt.% based on the total weight of the prepolymer.

[00771 The amount of optional compounds having crosslinkable functional groups in the prepolymer will typically be up to about 1 milheqυivalent, preferably from about 0.05 to about 1 milliequivaleiit, and more preferably from about 0.1 to about 0.8 milliequivaient per gram of final polyurethane on a dry weight, basis. |0078] Where the compositions of the invention incorporates non-polyurethanic non- vinylic polyhydrazine (or polyhydrazone) compoυnd(s) and/or oHgomeric urethane polyhydrazine (or polyhydrazone) compound(s), the level of such polyhydrazine (or polyhydrazone) compounds(s) in one embodiment is that to provide a range of 0.05 to 20 moles hydrazine (or hydrazone) groups present per mole of carbonyl groups present, in another embodiment 0.1 to 10 moles per mole, and in another embodiment 0.67 to 1.1 1 moles per mole. Examples of such suitable polyhydrazine (or polyhydrazone) compounds include dicarboxylic acid bishydrazides of formula

H₂ N-NH-C(O)-R⁹ -C(O)-NH-NH₂ and dicarboxylic acid bis-hydrazones of formula

R¹⁰ R^{1 1} C=N-NH-C(O)-R-C(O)-NH-N=CR¹⁰ R^{1 1} wherein R⁹ is a covalent bond or a polyalkylene (preferably polymethylene) or alicyclic group having from 1 to 34 carbon atoms or a divalent aromatic ring, and R^1C and R¹ are selected from the group consisting of H and (C [ to C_O) alkyl and alicyclic groups. Examples of suitable dihydrazides include oxalic acid dihydrazide, maloiiic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, cyclohexane dicarboxylic acid bis-hydrazide, azelaic acid bis-hydrazide, and sebacic acid dihydrazide. Other suitable compounds are set forth in U.S. Patent 4,983,662 at column 18, line 3 through column 18, line 42.

[0079] The compositions of the invention may optionally contain 0.0002 to 0.02 mole per mole of hydrazine group(s) of a heavy metal ion. This may be added in the form of suitable water-soluble metal salts, particularly chlorides, sulphates, metal hydrazide complexes, and acetates. Suitable heavy metal water-soluble salts are, in particular, those of Cu, Zn, Fe, Cr, Mn, Pb, V, Co and Ni.

[0080] The technology for inserting ketone functional groups as part of the polyurethane, part of the acrylic polymer or as a separate component is described more fully in U.S. Patent 4,983,662 to Overbeek et al, and Pajerski in WO 2006/047746, WO2006/08632 and WO2008/06843. Prepolymer Manufacture

[0081] Aqueous dispersions of polyurefhane composition particles are made in accordance with this invention by forming a polyurcthane prepolymer, optionally with a polyketoπe molecule, and dispersing this blend in aqueous medium. [0082] Typically, prepolymer formation will be done by bulk or solution polymerizing the ingredients of the prepolymer. Thus, the ingredients forming the prepolymer, e.g., the polyisocyanate(s), the active hydrogen-containing compound(s) and/or the water- dispersibility enhancing compound(s), are combined to foπn the prepolymer. [0083[ Bulk and solution polymerization are well known techniques and described, for example, in "Bulk Polymerization," VoL 2, pp. 500-514, and "Solution Polymerization," Vol. 15, pp, 402-418, Encyclopedia of Polymer Science and Engineerin^g, © 1989, John Wiley & Sons, New York. See, also, "Initiators," Vol. 13, pp. 355-373, Kirk-Othmer, Encyclopedia of Chemical Technology, © 1981, John Wiley & Sons, New York. The disclosures of these documents are also incorporated herein by reference.

Dispersion in an Aqueous Medium

{0084J Once the polyurethane prepolymer is formed, in one embodiment it is dispersed in an aqueous medium to form a dispersion of the blend.

[0085] Dispersing the prepolymer in aqueous medium can be done by any conventional technique, in the same way that other polyurethane prepolymers made by bulk or solution polymerization are dispersed in water. Normally, this will be done by combining the prepolymer blend, with water with mixing. When or if solvent polymerization is employed, the solvent and other volatile components can optionally be distilled off from the final dispersion, if desired. Chain extender and/or the hydrazine functional moiety for reacting with the ketone group can be added at this stage or later. [0086] In one embodiment of the invention, where the prepolymer includes enough water-dispersibility enhancing compound to form a stable dispersion without added emulsifiers (surfactants), the dispersion can be made without such compounds, i.e., substantially free of surfactants, if desired. The advantage of this approach is that the coatings or other products made from the polyurethane exhibit less water sensitivity, better film formation, less foaming and reduced growth of mold, bacteria and so forth. [0087J Alternatively, to dispersing the urethane prepolymer directly in water, it may first be formed or put in solution with a polar solvent that is non-reactive with isocyanate functionality and easily distilled. The prepolymer can then be diluted in said solvent(s) as necessary, optionally chain extended with an active hydrogen-containing compound. Water can then be added to the chain-extended polyurethane solution, and the solvent(s) are distilled off. A variation on this process would be to chain extend the prepolymer after its dispersion into water (e.g., with di or higher functionality amines). This process is often called the "Acetone process" in the patent literature as acetone is a popular solvent. Bayer has commercial polyurethane dispersions in water made by this process. Alternatively, there are melt dispersion processes, ketazine and ketiminc process, continuous process polymerizations, reverse feed process, solution polymerization and bulk polymerization processes (all disclosed in more detail in U.S. Patent 6,897,281 B2 column 4, lines 20-64) that might be used to make and/or disperse the urethane/prepolymer component of this disclosure.

Prepolymer Neutralization

[0088] In those instances in which the prepolymer includes water-dispersibility enhancing compounds which produce pendant carboxyl groups, these carboxyl groups can be converted to carboxylate anions for enhancing the water-dispersibility of the prepolymer.

[0089J Suitable neutralizing agents for this purpose 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 tri ethyl amine (TEA), dimethyl ethanolaminc (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 Extension

[0090] The polyurethane composition dispersions in water produced as described above can be used as is, if desired. Alternatively, they can be chain extended to convert the prepolymers in the composite particles to more complex polyurethanes. [0091] As a chain extender, at least one of water, inorganic or organic polyamme having an average of about 2 or more primary and/or secondary amine groups, amine functional polyols, ureas, or combinations thereof is suitable for use in this invention. Suitable organic amines for use as a chain extender include di ethylene 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 this invention arc propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, 3,3- dichlorobenzidene, 4.4'-methylcne-bis-(2~chIoroaniline), 3,3-dichloro-4,4-diamino diphenylmethane, sulfonated primary and/or secondary amines, and the like, and mixtures thereof. Suitable inorganic amines include hydrazine, substituted hydrazines, and hydrazine reaction products, and the like, and mixtures thereof. Suitable ureas include urea and it derivatives, and the like, and mixtures thereof. Hydrazine is most preferred or hydrazine combined with other extenders, preferably water soluble ones such as ethylene diamine and is most preferably used as a solution in water. The amount of chain extender, which can be added before or after dispersion, typically ranges from about 0.5 to about 1.15 equivalents based on available equivalents of isocyanate.

Additional Ingredients and Features

[0092] The polyurethane prepolymers, the product polyurethanes produced therefrom, and the aqueous prepolymer composition aqueous dispersions of the present invention as described above can be made with various additional ingredients and features in accordance with known polyurethane technology. Examples include: Polymer Branching

[0093] Branching of the ultimate polymer product, as well as the prepolymer, can be accomplished for aiding tensile strength and improving resistance to creep — that is, recovery to that of or near its original length after stretching. In this regard, see U.S. Pυblished Patent Application No. 20030195293, the disclosure of which has been incorporated herein by reference above,

Monofunctional Active Hydrogen-Containing Compounds

[0094J The prepolymers of this invention can also be made with mono functional active hydrogen-containing compounds to enhance dispersibility of the prepolymer in aqueous medium and impart other useful properties, for example cross-linkability, as well as to adjust the morphology and rheology of the polymer when coated onto a substrate, as also described in the above-noted U.S. Published Patent Application No. 20030195293.

PJasticizers

[0095} The polyurethane prepolymers aisd ultimate polyurethane products of this invention can be prepared in the presence of a plasticizer. The plastici/cr can be added at any time during prepolymer preparation or dispersion or to the polyurethane during or after its manufacture. Plastieizers well known to the art can be selected for use in this invention according to parameters sucli as compatibility with the particular polyurethane and desired properties of the final composition. See, for example, WO 02/08327 Al , as well as the above-noted U.S. Published Patent Application No. 20030195293.

Other Additives for Preparation of Dispersions

J0096J Other additives v, ell known to those skilled in the art can be used to aid in preparation of the dispersions of this invention. Such additives include stabilizers, defoamers, antioxidants (e.g.. Irgatiox 1010), UV absorbers, carbodiimides, activators, curing agents, stabilizers such as carbodiimide, colorants, pigments, neutralizing agents, thickeners, non-reactive and reactive plastieizers, coalescing agents, waxes, slip and release agents, antimicrobial agents, surfactants such as Pluronie^{I M} FoS-LF and ΪGEPAL™ CO630 and silicone surfactants, metals, coalescents. salts, flame retardant additives (e.g., antimony oxide), antiozouants, and the like. They can optionally be added as appropriate before and/or during the processing of the dispersions of this invention into finished products as is well known to those skilled in the art. Additives may also be used as appropriate in order to make articles or to treat oilier products (such as by impregnation, saturation, spraying, coating, or the like). The dispersions of this invention typically have total solids of at least about 20 wt. %, preferably at least about 25 wt. % and more preferably at least about 30 wt. %,

Blends Other Polymers and Polymer Dispersions

[0097] The dispersions of this invention can be combined with commercial polymers and polymer dispersions by methods well known to those skilled in the art, Such polymers and dispersions include those described in WIPO Publication WO 02/02657 A2, U.S. Patent No. 4,920, 176, U.S. Patent No. 4,292,420, U.S. Patent No. 6,020,438, U.S. Patent No. 6,017,997 and a review article by D. P. Tate and T. W. Bethea. Encyclopedia of Polymer Science and Engineering, Vol. 2, p.537, the disclosures of which are incorporated herein by reference.

Hybrids

[0097] The unsaturated olefin and acrylic monomers of the aqueous dispersions of this invention can be polymerized by conventional free radical sources to form an alpha- olefin- acrylic polymer. Acrylic will refer to acrylic acid, acrylates (being esters of acrylic acid), and alkacrylates such as methacrylates and cthacrylates. Designations with (alk)acrylate will indicate that the alkyl substituents on the beta carbon of the double bond are optionally present, Additional free radically polymerizable material (unsaturated monomers) may be added to the already present unsaturated monomers in the prepolymer dispersion either to copolymerize with the already present monomers or to subsequently polymerize into a second or third vinyl polymer in the same particle. The original polyurethane particles (either w Uh olefin-acrylic monomers present or absent) may be used as seed particles for further olefm-vinyl copolymerization. This can be done by forming the aqueous dispersions of polyurethane composite in the manner described above and then polymerizing additional monomers by emulsion or suspension polymerization in the presence of these dispersions, i.e., with the inventive dispersions being mixed with the additional monomers before polymerization is completed. Hybrids of polyurethancs and acrylics can be made to advantage by this approach, In one embodiment, the weight ratio of polymers from vinyl monomers to urethane polymers will be 10;90 to 90:10. In another embodiment, it will be 20:80 to 80:20 and in a third embodiment from 30:70 to 70:30.

[0098] Still another way of making hybrid polymers m accordance with the present invention is to include some or a portion of the ethyl cnic ally unsaturated monomers (alpha olefin and acrylic monomers) in the polynrethane prepolymer reaction system and to cause these monomer to polymerize before, during, and/or after the prepolymer is dispersed in aqueous medium. In one embodiment it is desirable to add at least 25, 50, or 75 mole % of the total alpha olefin monomer(s) to be used in ihe hybrid before the urethanc forming components are reacted together to form a prepolymer. One or more of the acrylic monomer(s) and optional other ethylenically unsaturated monomer(s) may be added at the same time or later. This embodiment seems to promote more incorporation of the alpha olefin monomer into the olefm-acrylic copolymer than when added later. When using non-polymerized monomers, the ethylenically unsaturated monomers act as a diluent during prepolymer formation. In the aqueous medium, these ethylenically unsaturated monomers can be polymerized to completion with or without additional monomers being added, Hybrids of polyurethanes and acrylics can be made to advantage by this approach, as well.

[0099] This type of technology is taught in U.S. Patent 4,644,030; U.S. Patent 4,730,021 ; U.S. Patent 5, 137,%1 ; and U.S. Patent 5,371,133. Another urethane-acrylic hybrid is often known as synthetic alloy urethanc- acrylic where a urethane polymer is dispersed into a waterborne polymer dispersion or emulsion. This is taught in WO 98/38249 and U.S. Patent 6,022,925.

[0100] Following polymerization of the ethylenically unsaturated aliphatic olefin with the at least one ethylenically unsaturated monomer containing an electron withdrawing group, it is often desirable to reduce the volatile organic content (VOC) of the polymerization product so that downstream products from the polymer dispersion can be formulated to be compliant with various volatile organic component limitations imposed by regional governments. By VOC, according to the present invention, it is meant the sum of the residual monomers and additional volatile organic compounds (e.g., diluents and degradation products) which are determined by the chromatographic gas method. While VOC may have a different definition by different groups, a preferred definition from the European Union Directive 2004/42/CE for VOC emissions from varnish defines VOC as an organic compound having an initial boiling point less than or equal to 250⁰C measured at a standard atmospheric pressure of 101.3 kPa, As defined hereunder; more precisely, the total VOC according to the present invention is desirably lower than ό()0, 500, 200, 100, 20, or 10 ppm and in particular the monomers, which are substances sometimes toxicologic^ Sy harmful, lower than 500, 200, 100, 50, 20. or 1 0 ppm. A low VOC is typically less than SOO ppm, more preferably less than 250 ppm and most preferably less than 50 ppm. There are commercial methods or technology for removing volatile organics and residual monomers such as steam stripping, coagulation and washing or drying, etc. Removing VOCs soon after polymerization also avoids more restrictive shipping and storage requirements that might be required if more significant amounts of volatile and potentially flammable organics are present in the headspace of partially filled containers, tanks, trucks, etc,

}O1G1] Other Additives for the Polymer, Other additives well known to those skilled in the ait can be used in combination with the copolymer. Such additives include stabilizers, defoamers. antioxidants (e.g., Irganox™ 1010), UV absorbers, activators, curing agents, stabilizers such as carbodiimide, colorants, neutralizing agents, thickeners, non-reactive and reactive plasticizers, coalescing agents such as di{proρylene glycol) methyl ether (DPM) and PM acetate, waxes, slip and release agents, antimicrobial agents, surfactants such as ionic and non-ionic surfactants (e.g.. Pluronic^{1 M} F68-LF, IGEPAL™ CO630) and silicone surfactants, metals, salts, antiozonants. and the like. [0102] Blends with Other Polymers and Polymer Dispersions. The polymers of this invention can be combined with commercial polymers and polymer dispersions by methods well known to those skilled in the art.

[0103] The polymer may be applied as a dispersion in a media to form a coating, adhesive, sealant, etc. It may be applied by brushing, dipping, flow coating, spraying, rolling, etc. It may contain conventional ingredients such as solvents, plasticizers, pigments, dyes, fillers, emulsifiers, surfactants, thickeners, rheology modifiers, heat and radiation stabilization additives, defoamers, levelling agents, anti-cratering agents, fillers, sedimentation inhibitors, U. V. absorbers, antioxidants, flame retardants, etc. It may contain other polymeric species such as additional polymers in the forms of blends, interpenetrating networks, etc.

[0104] In one embodiment, the polymerization temperature is 0 to about 100 or 150⁰C, preferably 5 to about 95⁰C and more preferably about 10 to about 90⁰C. hi one embodiment, the reactor pressure after charging the monomers and during polymerization is from atmospheric pressure (about 1 atmosphere) to about 10 atmosphere, more desirably from about atmospheric to about 2 or 3 atmosphere. In one embodiment, it is desirable that a conventionally equipped acrylate polymerization vessel designed for use at 1 or 2 atmospheres could be used so that equipment costs would not be a determent to using this technology.

[0105] In one embodiment, desirably the pH of the polymerization media would be from about 1 to about 10, 1 1 or 12 more desirably from about 1 to about 7, more desirably from about 2 to about 5. In another embodiment, desirably the pH of the polymerization media would be from about 5 to about 10, 11 or 12 more desirably from about 7 to about 10. more desirably from about 7,5 to about 8,5, In one embodiment, cmulsifiers/dispersants/surface active molecules, to the extent necessary, would be chosen so that they performed any necessary function at the desired or selected pH. [0106] In one embodiment, the polymerization media can be about any media that does not negatively interact with the monomers, initiators, and other components to the polymerization, and in particular including small or large amounts of water. Organic solvents (both polar and nonpolar) may be present but generally are not required. In one embodiment, the polymerization media is desirably at least 100 or 500 ppm or 1, 2, 5, 10, 15, or 20 to about 30, 50, 70, SO, 90 or 99 wt.% water based on the continuous media/aqueous media and any dispersed phase therein, e.g., monomers, surfactants, initiators, chain transfer agents, Lewis or Bronsted acid, copolymers, etc. Water, to the extent present, can be from any source, e.g., de-ionized, distilled, city water, etc. {0107] In one embodiment, the olefm-acrylic copolymers from this process desirably have a number average molecular weight in excess of 2,000; more desirably in excess of 3,000 or 5.000; and in other embodiments desirably in excess of 10,000; 25,000; 50,000; or 100.000 grams per mole. Molecular weights as stated will be determined by GPC analysis using polystyrene standards. Molecular weights from about 25,000 and higher often typical of emulsion polymerization. Typically, the weight average molecular weight of many polymers and polymerization mechanism will be about double the number average molecular weight. In one embodiment, desirably these copolymers will have a weight average molecular weight in excess of 4,000; more desirably In excess of 6,000 or 10,000; and in other embodiments desirably in excess of 20,000; 50,000; 100,000; or 200,000 grams per mole. These molecular weights may be claimed in combination with emulsion polymerization mechanisms.

[0108J The polymerization mechanism for the alpha-olefin acrylic copolymer can be any of those known to the art (e.g., dispersion, emulsion, bulk, solution, etc). In one embodiment, it is desirable for case of handling of the polymer that the final copolymer (e.g., in aqueous media) be a dispersion that can be pumped and handled as a liquid. It is desirable that the number average particle size be below 5 microns, more desirable below 1 micron, and in some embodiments less than 800, less than 500; less than 300, or less than 200 nanometers in diameter. The particles sizes of less than 500 nanometers and below are typical of emulsion polymerization and may be claimed in combination with an emulsion type polymerization mechanism. The particles sizes of less than 200 nanometers and below are typical of dispersion polymerization and may be claimed m combination with a dispersion type polymerization mechanism. [0109] Typically, one wants both olefin and acrylic co-monomers and the optional co-monomers to be chemically bonded into the same polymer chain, unless one wants an interpenetrating polymer network of two separate polymers. The copolymers can have randomly inserted monomers, alternating insertion of monomers, blocky insertion of repeating units from a single monomer, etc. As one goes from blocky insertion to random to perfectly alternating insertion, the percentage of any first type of repeating unit adjacent to another type of repeating unit increases. In one embodiment, desirable at least 5, 10, 15 or 20 weight percent of the copolymer are the sum of a) repeating units from said ethylenically unsaturated olefin are covalently bonded to at least one repeating unit from said ethylenically unsaturated monomer with electron withdrawing group (or carbonyl or nitrogen containing group) with b) repeating units from said ethylenically unsaturated monomer with electron withdrawing group covalently bonded to at least one repeating unit derived from said ethylenically unsaturated aliphatic olefin. In one embodiment, desirably at least 5, 10, 15 or 20 weight percent of the repeating units from said ethyleiiically unsaturated monomer with electron withdrawing group are covalentiy bonded to at least one repeating unit from said ethyjenicaily unsaturated olefin. Similarly, in one embodiment, desirably at least 5, 10, 15 or 20 weight percent of the repeating units from said ethylenically unsaturated olefin are covalentiy bonded to repeating units from said ethylenically unsaturated monomer with electron withdrawing groups.

{0110] While not wishing to be bound by theory, the mechanism by which this co- polymerization takes place is postulated to involve sequential formation of electron poor and electron rich terminal end groups on the growing polymer resulting from alternating addition of olefin and acrylate.

[0111] A unique feature of many of the examples in this invention is that generally in the NMR analysis of polymers from this process, alternating sequences of the a) ethylenically unsaturated aliphatic olefin with 4-30 carbon atoms with the b) at least one ethylenically unsaturated monomer containing an electron withdrawing group (alternately defined in some claims as an ethylenically unsaturated monomer containing a carbonyl or nitrogen group) exist in the copolymer, often along with sequences or blocks of the b) monomer. The presence of both alternating sequences of the two types of monomers and homopolymer blocks within the same reaction product seems unique. In on embodiment, it is desirable that at least 2, 5, 10, or 20 mole percent of all the repeating units in the copolymer are the sum of said a) ethylenically unsaturated aliphatic olefin with 4 or 5 to 30 carbon atoms covalentiy bonded to at least one of said b) at least one ethylenically unsaturated monomer containing an electron withdrawing group (alternately defined in some claims as an ethylenically unsaturated monomer containing a carbonyl or nitrogen group) combined with said b) at least one ethylenically unsaturated monomer containing an electron withdrawing group (alternately defined in some claims as an ethylenically unsaturated monomer containing a carbonyl or nitrogen group) covalentiy bonded to at least one of said a) ethylenically unsaturated aliphatic olefin with 4 or 5 to30 carbon atoms. Alternatively, in another embodiment (or in combination with the limitations above characterizing said alternating sequences), at least 2, 5, 10, or 20 mole percent of all the repeating units in the copolymer are the sum of said b) at least one ethylcnically unsaturated monomer containing an electron withdrawing group (alternately defined in some claims as an ethyl enical Iy unsaturated monomer containing a carbonyl or nitrogen group) covaleiitly bonded to repeat units from monomers other than said a} cthylenically unsaturated aliphatic olefin with 4 or 5 to 30 carbon atoms (e.g., the copolymers have the specified amount of blocks of said b) at least one ethylenically unsaturated monomer containing an electron withdrawing group (alternately defined in some claims as an ethylenically unsaturated monomer containing a carbonyl or nitrogen group) not alternating with said a) a) ethylenically unsaturated aliphatic olefin with 4 or 5 to 30 carbon atoms.

|0l 12} The copolymer product can be used in OEM (original equipment manufacturing) plastics including automotive and consumer electronics; weatherable coatings for building and the construction industry, adhesivcs, textile coatings for borne furnishings and automotive, printing inks and primers for flexible packaging. It may be used as a dispersion in aqueous media or precipitated to isolated the polymer (e.g., as a dry powder, bulk polymer, or slurry) and used as an additive, impact modifier, etc., for another plastics. It is particularly useful in applications requiring additional hydrophobic character in coatings, primers, inks, compatibilizers, adhesivcs, sealants, caulks, textile coatings, and composite materials. The copolymers could be used in personal care, pharmaceutical or pharmacologically active formulations to change the feel, viscosity, surface character, delivery mechanism, etc., of such formulations. [0113J The copolymer product can be used in adhesives, coatings, personal care compositions, graphic arts, and textile applications. Examples are the adhesion to both polar and non-polar substrates, high coefficient of frictions, resistance to most polar solvents, moisture repellencc, printability, and compatibility with various additives. Final uses may include; inkjet receptive coatings on low-surface energy substrates (different substrates); inks for low surface-energy substrates; flock adhesives for low surface-energy substrates; coatings and binders for polyolefin protective apparel and ballistic articles; construction membranes and scrims for low surface- energy fibers; low dirt-pickup coatings for high and low surface-energy substrates; anti-slip coatings for flooring, packaging, construction membranes, gloves, consumer articles; moisture- resistance oxygen barrier coatings for flexible films and paper substrates; improved chemical resistance for ail of the above; pressure sensitive and non pressure sensitive adhesive for rigid and flexible low surface-energy substrates; glass-sizing for olefin reinforcement; soft-feel coating for plastics substrates; primer coatings for rigid and flexible low surface- energy substrates; adhesion promoter for coatings for rigid and flexible low surface-energy substrates; compatibilizing agents for mixtures of olefmic and acrylic materials; and personal care compositions of urethane-acrylic-olefin copolymers comprising one or more components selected from chelators, conditioners, diluents, fragrances, pigments, colorings, antioxidants, humectant skin and hair conditioners, lubricants, moisture barriers and emollients, neutralizers, opacifiers, pharmaceutical actives, preservatives, solvents, spreading aids, sunscreens, surfactants selected from non-ionic, anionic, cationic, and zwuterionic surfactants, conditioning polymers, vitamins, viscosity adjusters, viscosity modifiers, and emulsifiers,

EXAMPLES

[0114j Example 1. The following is an example of the preparation of a polyurethane-polyacrylate hybrid dispersion, A polyurethane prepolymer was prepared by combining 1 -7 of the ingredients below at 70⁰C into a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The reaction below was run under a stream of dry air introduced through the gas inlet on the reactor. The temperature of the reaction mixture was raised to 82°C to 85°C and held at this temperature for 2 hours or until the theoretical NCO% was reached as indicated by titration of a small sample.

Item # Material Parts

1

Piothane 67-3000 HNA (OH# = 33.9) 186.1

2

Butane diol

3 Dimethylol butanoic acid 21.3

4

MMA 125.1

5 nBA 25.1

6 BHT 0.1

7 Di-cyclohexytmethane di-isocyanate 136.4 [0115] A polyurethane dispersion was prepared by neutralizing the above prepolymer with 17.1 parts of tricthylamine at 65°C-70°C and dispersing the neutralized prepolymer in water while maintaining the water/dispersion temperature below 28°C. The dispersed prepolymer was extended with an appropriate amount of hydrazine hydrate (35% hydrazine content) after the prepolymer was dispersed. After allowing about 30 minutes for chain extension, the temperature of the dispersion was adjusted to 33-35°C and 3 parts of a 1% solution Fe-EDTA complex, 40 parts of aqueous 3.5% tert- butyl hydrogen peroxide, and 55 parts of 2.0% aqueous erythorbic acid neutralized with tri ethyl amine. An cxotherm resulted, which indicated initiation and polymerization of the acrylic monomer present. This resulted in a 44.0 % solids polyurethane/polyacrylate dispersion with low sediment, a viscosity of 580 cps (25 ⁰C) at a pH of 9.4. The particle size was 52.9 ran,

[0116] Example 2. The following is an example of the preparation of polyurethane/poly(acrylate-co-olefm) hybrid dispersions using MMA.'BA with varied PU to acrylatc-olefsn copolymer ratios and acrylate to olefin ratios. A polyurethane prepolymer was prepared by combining 1-7 of the ingredients below at 70⁰C into a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The reaction below was run under a stream of dry air introduced through the gas inlet on the reactor. The temperature of the reaction mixture was raised to 82°C to 85°C and held at this temperature for 2 hours or until the theoretical NCO% was reached as indicated by titration of a small sample.

[0117] A polyurethane dispersion was prepared by neutralizing the above prepolymer with 31.8 parts of triethylamine at 65°O70°C and dispersing the neutralized prepolymer in water while maintaining the water/dispersion temperature below 28°C. The dispersed prepolymer was extended with an appropriate amount of hydrazine hydrate (35% hydrazine content) after the prepolymer was dispersed. The chain extension was allowed to proceed for 1 hour.

[01181 Hybrid Dispersion. The above polyurethane dispersion was combined with 2-5 of the ingredients below, and mixed for 1 hour. The temperature of the dispersion was adjusted to 32-35°C and 3 parts of a 1% solution Fe-EDTA complex. 40 parts of aqueous 3.5% tert-butyl hydrogen peroxide, and 55 parts of 2.0% aqueous erythorbic acid neutralized with triethylamine was added. An exotherm indicating initiation and polymerization of the acrylic monomer present. This resulted in a polyurethane/poly(acrylate-co-olefϊn) dispersion of 40.8 % solids with low sediment, a viscosity of 330 cps (25 ⁰C) at a pH of 8.0, The particle size was 56.4 nm.

(0119) Hybrid Dispersions 2B-2D. The above procedure was repeated with the ingredients listed below to make hybrid dispersions 2B-2D of different properties.

(0120) Example 3. The following is an example of the preparation of polyυrethane/polyfacrylate-co-olefin) hybrid dispersions using EA with varied PU to acrylate-olefin copolymer ratios and acrylate to olefin ratios. A polyurethane prepolymer was prepared by combining 1-6 of the ingredients below at 70⁰C into a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The reaction below was run under a stream of dry air introduced through the gas inlet on the reactor. The temperature of the reaction mixture was raised to 82°C to 85⁰C and held at this temperature for 2 hours or until the theoretical NCO% was reached as indicated by titration of a small sample.

j012l| A polyurethane dispersion was prepared by neutralizing the above prepolymer with 31.8 parts of triethylamine at 65°C-70°C and dispersing the neutralized prepolymer in water while maintaining the water/dispersion temperature below 28⁰C. The dispersed prepolymer was extended with an appropriate amount of hydrazine hydrate (35% hydrazine content) after the prepolymer was dispersed. The chain extension was allowed to proceed for 1 hour. 101221 Hybrid Dispersion 3A-3D. The same procedure as in the preparation of hybrid dispersion 2A was repeated with the ingredients listed below to make hybrid dispersions 3A-3D of different properties.

[0123] Hybrid Dispersion 3E-3F. The same procedure as in the preparation of hybrid dispersion 2A was repeated with the ingredients listed below to make hybrid dispersions 3E-3F with dodecene and octadecene.

[G124[ Example 4. The following is an example of the preparation of poiyurethane/poly(acrylate-co-olefin) hybrid dispersions using nBA with various olefins. A polyurethane prepolymer was prepared by combining 1 -6 of the ingredients below at 70⁰C into a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The reaction below was run under a stream of dry air introduced through the gas inlet on the reactor. The temperature of the reaction mixture was raised to 82°C to 85°C and held at this temperature for 2 hours or until the theoretical NC0% was reached as indicated by titration of a small sample.

[0125] A polyurethane dispersion was prepared by neutralizing the above prepolymer with 31.8 parts of triethylamine at 65°C-70°C and dispersing the neutralized prepolymer in water while maintaining the water/dispersion temperature below 28°C. The dispersed prepolymer was extended with an appropriate amount υf hydrazine hydrate (35% hydrazine content) after the prepolymer was dispersed. The chain extension was allowed to proceed for 1 hour.

[0126] Hybrid Dispersion 4A. Initiator A was made by dissolving 0.6 grams of erythorbic acid and 0.3 grams of triethylamine in 30.0 grams of water. Initiator B was made by dissolving 2 grams of 30% SLS solution and 8.8 grams of 17% t-butyl hydroperoxide in 30 grams of water. Approximately 510.2 grains of the above polyurethane dispersion, 6 grams of 1 % Fe-EDTA solution and 518.6 grams of water was charged into a 3 L reactor vessel and heated to 6O⁰C. Initiator A was then added into the reactor, followed by proportioning the initiator B into the vessel over a period of 3 hours and 235.7 grams of n-butyl acrylate over a period of 2.5 hours. The reaction was allowed to proceed for 30 minutes after the completion of the addition, and then cooled to 57⁰C. A mixture of 1.8 grams of 17% t-butyl hydroperoxide and 30 grams of water was added into the reactor. After 5 minutes, a mixture of 0.24 grams of erythobic acid, 0, 12 trieihylamine and 30 grams of water was added into the reactor. After 2 hours, the reaction vessel was cooled to room temperature and filtered through lOQ-micro cloth. A polyurethane/poly(acrylate-co-olefui) dispersion of 31.3% solids was obtained with low sediment, a viscosity of 18 cps (25⁰C) at a pH of 8.0. The particle size was 68,7 nm.

[0127] Hybrid dispersion 4B-4D. The same procedure as in the preparation of hybrid dispersion 4A was repeated with the ingredients listed below to make hybrid dispersions 4B-4D of different properties.

[0128] Example 5. The following is an example of the preparation of polyurethane/poly(acrylate-co-olefm) hybrid dispersions using EA and dodecene. A polyurethane prepolymer was prepared by combining 1 -7 of the ingredients below at 70⁰C into a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The reaction below was run under a stream of dry air introduced through the gas inlet on the reactor. The temperature of the reaction mixture was raised to 82°C to 85°C and held at this temperature for 2 hours or until the theoretical NCO% was reached as indicated by titration of a small sample.

[0129J A polyurethane dispersion was prepared by neutralizing the above prepoiyrner with 17.1 parts of triethylamine at 65^oC-70°C and dispersing the neutralized prepolymcr in water while maintaining the water/dispersion temperature below 28°C. The dispersed prepolymer was extended with an appropriate amount of hydrazine hydrate (35% hydrazine content) after the prepolymer was dispersed. The chain extension was allowed to proceed for I hour.

(013G] Hybrid Dispersion 5A. The above polyurethane dispersion was combined with 2-3 of the ingredients below, and mixed for 1 hour. The temperature of the dispersion was adjusted to 32-35⁰C and 3 parts of a 1% solution Fe-EDTA complex, 40 parts of aqueous 3.5% lert-butyl hydrogen peroxide, and 55 parts of 2.0% aqueous erythorbic acid neutralized with triethylamine was added. An exotheπn resulted, which indicated initiation and polymerization of the acrylic monomer present. This resulted in a polyurethane/poly(acrylate-co~olefm) dispersion of 36.0% solids with low sediment, a viscosity of 75 cps (25°C) at a pH of 7.6. The particle size was 79,6 nm.

(0131] Hybrid Dispersion 5B. Initiator A was made by dissolving 0.6 grams of crythorbic acid and 0.3 grams of rriethylamine in 30.0 grams of water. Initiator B was made by dissolving 2 grams of 30% SLS solution and 8.8 grams of 17% t-butyl hydroperoxide in 30 grams of water. Approximately 450.0 grams of the above polyurethane dispersion, 18.2 grams of dodcccne, o grams of 1 % Fe-EDTA solution and 438.0 grams of water was charged into a 3L reactor vessel and heated to 6O⁰C. Initiator A was then added into the reactor, followed by proportioning the initiator B into the vessel over a period of 3 hours and 189.7 grams of ethyl acryiate over a period of 2.5 hours. The reaction was allowed to proceed for 30 minutes after the completion of the addition, and then cooled to 57⁰C. A mixture of 1.8 grams of 17% t-butyl hydroperoxide and 30 grams of water was. added into the reactor. After 5 minutes, a mixture of 0.24 grams of erythobic acid, 0.12 triethylamine and 30 grams of water was added into the reactor. After 2 hours, the reaction vessel was cooled to room temperature and filtered through 100-miciO cloth. A polyurethane/poiytacrylate-co-olefm) dispersion of 30.0% solids was obtained with low sediment, a viscosity of 18 cps (25"C) at a pH of 7.9. The particle si/e was 68.5 run.

[0132] Hybrid Dispersion 5C. Initiator A was made by dissolving 0.6 grams of eryfhorbic acid and 0.3 grains of triethylamine in 30.0 grams of water. Initiator B was made by dissolving 2 grams of 30% SLS solution and 8.8 grams of 17% t-butyl hydroperoxide in 30 grams of water. Approximately 450.0 grams of the above polyurethane dispersion (Example 5). 6 grams of 1% Fe-EDTA solution and 438.0 grams of water was charged into a 3 L reactor vessel and heated to 60¹¹C. Initiator A was then added into the reactor, followed by proportioning the initiator B into the vessel over a period of 3 hours and 207.9 grams of ethyl acryiate over a period of 2.5 hours. The reaction was allowed to proceed for 30 minutes after the completion of the addition, and then cooled to 57⁰C. A mixture of 1.8 grams of 17% t-butyl hydroperoxide and 30 grams of water was added into the reactor. After 5 minutes, a mixture of 0.24 grams of erythobic acid. 0.12 triethylamine and 30 grams of water was added into the reactor. After 2 hours, the reaction vessel was cooled to room temperature and filtered through 100-micro cloth. A polyurethane/poly(acrylate-co-olefin) dispersion of 30.5% solids w as obtained with low sediment, a viscosity of 18 cps (25"^'C) at a pH of 8,0, The particle size was 68,7 ran.

[0133] Example 6. The following is an example of the preparation υf poiyurethane/poiyfacrylale-co-olefin) hybrid dispersions using nBA in presence of surfactant. A monomer premix was made by mixing 75 grams of water, 10 grams of 30% SLS solution, 210 grams of nBA, 7,5 grams of MAA, and 82.5 grams of MMA. Initiator A was made by dissolving 0,6 grams of erythorbic acid in 30.0 grams of water. ^"Initiator B was made by dissolving 2 grams of 30% SLS solution and 8.8 grains of 17% t-butyl hydroperoxide in 30 grams of water. Approximately 468.8 grams of the seed polyurethane polymer Permax 230, 485 grains of water, 20 grams of 30% SLS solution, and 6 grams of 1 % Fe-EiDTA solution and was charged into a 3 L reactor vessel and heated to 6O⁰C. Initiator A was then added into the reactor, followed by proportioning the initiator B into the vessel over a period of 3 hours and the monomer premix over a period of 2.5 hours. The reaction was allowed to proceed for 30 minutes after the completion of the addition, and then cooled to 57"C. A mixture of 1.8 grams of 17% t- butyl hydroperoxide and 30 grams of water was added into the reactor. After 5 minutes, a mixture of 0.24 grams of erythobic acid, and 30 grams of water was added into the reactor. After 2 hours, the reaction vessel was cooled to room temperature and filtered through 100-micro cloth. A polyurethane/poly(acrylate-eo-olefin) dispersion of 28.9% solids was obtained with low sediment, a viscosity of 75 cps (25⁰C) at a pH of 5.8. The particle size was 160.8 run.

J 0134 J Example 7. The following is an example of the preparation of po!yurethane/poly(acrylate-co-olefin) hybrid dispersions using nBA and TMP-I in presence of surfactant. A monomer premix was made by mixing 75 grams of water, 10 grams of 30% SLS solution, 210 grams of nBA, 15 grams of TMP- L 7.5 grams of MAA, and 82.5 grams of MMA. Initiator A was made by dissolving 0.6 grams of erythorbic acid in 30,0 grams of water. Initiator B was made by dissolving 2 grains of 30% SLS solution and 8.8 grams of 17% t-butyl hydroperoxide in 30 grams of water. Approximately 468.8 grams of the seed polyurethane polymer Permax 230, 485 grams of water, 20 grams of 30% SLS solution, and 6 grams of 1% Fe-EDTA solution was charged into a 3 L reactor vessel and heated to 60⁰C. Initiator A was then added into the reactor, followed by proportioning the initiator B into the vessel over a period of 3 hours and the monomer premix over a period of 2,5 hours. The reaction was allowed to proceed for 30 minutes after the completion of the addition, and then cooled to 57^C'C. A mixture of 1.8 grams of 1 7% t-butyl hydroperoxide and 30 grams of water was added into the reactor. After 5 minutes, a mixture of 0.24 grams of erythobic acid, and 30 grams of water was added into the reactor. After 2 hours, the reaction vessel was cooled to room temperature and filtered through 100-micro cloth. A polyuremaπe/poly(acrylate-co-olefm) dispersion of 28.7% solids was obtained with low sediment, a viscosity of 78 cps (25°C) at a pH of 5.7. The particle size was 154.3 run.

Abbreviations of the Chemicals Used in Examples;

MMA: methyl methacrytate

EA: ethyl acrylate nBA: n-butyl acrylate

TMP- 1 : 2,4,4-trimethyi- 1 -pentene

BHT: 2,6-Di-tert-butyl-4-methyiphenol

SLS: sodium lauryl sulfate

Piothane 67-3000 HNA^S: polyester diol reaction product of hexane diol, neopentyl glycol, and adipic acid (average MW = 3000) from Panolam Industries

Fe-EDTA: mixture of ferrous sulfate and 2-[2-(Bis(carboxymethyl)amino)ethyl-

(carboxymethyl)aminojacetic acid

Perm ax 23(f ; polyurethane dispersion available from Lubrizol Advanced Materials,

PU; polyurethane Appendϊx; Compositions of the Hybrid Dispersions

[0135] The above samples are currently undergoing evaluation for property composition relationships. Based on separate analysis of the alpha-olefhi-acrylic portion of the blend, we expect lower surface tension on the resulting films attributable to the alpha-olefm monomer's low surface tension. The alpha-olefin is also expected to make to blends more hydrophobic meaning that water and other polar materials will have a higher contact angle (i.e., they will not wet the surface well) when they forms drops on a surface or film from the blend. It is also anticipated that due to the hydrophobic low surface energy of the blend that it will more effectively wet a variety of equivalent or higher surface energy substrates, e.g., thermoplastic olefins, polyolefins, etc. It is also anticipated that the solid articles and films from the blends will have lower swelling factors and absorb less polar solvents that equivalent blends of polymers where an alpha- olefiπ component has not been copolymerized into the acrylic copolymer (this is sometimes call solvent resistance, especially resistance to polar solvents such as C 1-C3 alcohols, glycols, di glycols, diglycol ethers, and alky] ketones such as methylethylketone). Due to better wetting of non-polar hydrophobic surfaces it is anticipated that the blends of this disclosure will develop better adhesion to such non- polar substrates than compositionally similar urethane-acrylic blends that lack repeating units derived from polymerizing alpha-olefins. The alpha-olefin monomer's contribution to these properties is slightly different than a similarly sized (same number of carbon atoms in the hydrocarbon group) alkyl group on an acrylate (e.g., ethylhexyl acrylate has a large C8 alkyl group). Thus, the benefits of the alpha-olefin go beyond just changing the hydrophobicity of the copolymer.

[0136] While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

1. A urethane-olefin-acrylic polymeric reaction product as a polymeric dispersion in aqueous media comprising", a) a urethane prepυlymer derived from reacting at least polyisocyaπates with one or more active-hydrogen containing compounds, b) an olefin-acrylic copolymer derived from free radically polymerizing bl ) at least one ethylenically unsaturated aliphatic olefin with 2 to 30 carbon atoms with b2) at least one ethylenically unsaturated monomer containing an electron withdrawing group, and b3) optionally with other ethylenically unsaturated monomers, wherein said bl), b2), and optional b3) form a aliphatic olefin-acrylic copolymer comprising repeating units within the same copolymer from said olefin and said monomer containing an electron withdrawing group, optionally in the presence of a Lewis or Brδnsted acid.

2. The urethane-olefm-acrylic polymeric reaction product according to claim 1. wherein said ethyienically unsaturated olefin has from 4 to 20 carbon atoms.

3. The urethane-oiefin-acrylic polymeric reaction product according to claims 1 or 2 wherein said ethylenically unsaturated olefin has from 5 to 20 carbon atoms.

4. The urethane-olefin-acrylic polymeric reaction product according to claims 1 , 2, or 3. wherein said aliphatic olefm-acrylic copolymer and said urethane prepolymer form a hybrid copolymer dispersion,

5. The urethane-olefin-acrylic polymeric reaction product according to any of claims 1-4, wherein said ethylenically unsaturated aliphatic olefin is incorporated into said aliphatic olefin-acrylic copolymer to an extent such that 5-50 wt.% of the resulting oiefin-aciylic copolymer comprises repeating units derived from said ethylenically unsaturated aliphatic olefin.

6. The urethane-olefin-acrylic polymeric reaction product according to any of claims 1-5, wherein said urethane prepolymer is chain extended with a difunctional or higher amine prior to copolymerizing said a) at least one ethylenically unsaturated aliphatic olefin with 2 to 30 carbon atoms with b) at least one ethylenically unsaturated monomer containing an electron withdrawing group.

7. The urethantj-olefϊn-acrylic polymeric reaction product according to any of claims 1 -6, wherein said aqueous polyurethane dispersion is chain extended with a difunctional or higher amine subsequent to copolymerizing said a) at least one ethylenically unsaturated aliphatic olefin with 2 to 30 carbon atoms with b) at least one ethylenically unsaturated monomer containing an electron withdrawing group.

8. The urethane-olefin-acryϋc polymeric reaction product according to any of claims 1 to 5, wherein at least 10 weight percent of said olefin-acrylic copolymer has a) at least 3 weight percent polymeric units derived from said at least one ethylenically unsaturated olefin with 4 to 30 carbon atoms and b) at least 10 weight percent repeating units derived from said at least one ethylenically unsaturated monomer containing an electron withdrawing group,

9. A process for copolymerizing ethylenically unsaturated aliphatic olefin with ethylenically unsaturated monomer containing an electron withdrawing groups into an alpha-olefin-acrylic copolymer comprising: a) copolymerizing in lhe presence of an aqueous polyurethane dispersion at least one ethylenically unsaturated aliphatic olefin monomer with 2 to 30 carbon atoms with at least one polar monomer, optionally utilizing a Lewis or Brόnsted acid to increase the incorporation rate of said olefin into said copolymer.

10. The process according to claim 9, wherein said copolymcrization involves a free radical as at least part of the propagating species and wherein said at least one ethylenically unsaturated olefin monomer has 4 to 30 carbon atoms.

1 1. The process according to claim 10, wherein polymeric units from said at least one ethyl enieally unsaturated aliphatic olefin monomers has from 4 to 30 carbon atoms comprises at least 3wt. % of the resulting alpha-olefin-acrylic copolymer.

12. The process according to claim 1 !, wherein said at least one ethyl enieally unsaturated aliphatic olefin monomers comprises at least 5 wt.% of said alpha-olefm- acryhc copolymer.

13. The process according to claim 1 1, wherein at least 50 wt.% of said at least one cthylenically unsaturated aliphatic olefin monomers are ethylenscaily unsaturated aliphatic olefin monomers having from 6 to 15 carbon atoms.

14. The process according to claim 10, wherein said alpha-olefm-acrylic copolymer is generally characterized by a number average molecular weight in excess of 10,000 grams/mole as determined by GPC.

15. The process according to claim 10, wherein said olefin-acrylic copolymer is generated in the form of a stable emulsion or dispersion in an aqueous media.

16. The process according to claim 10₁ wherein said emulsion or dispersion is characterized by a volume average particle size of less than 200 nanometers in diameter.

17. An adhesion promoter for adhesives, coatings, and inks, comprising: a reaction product according to claim 1 , wherein said reaction product of olefin and acrylic monomers or olefin-acrylic copolymer is characterized by a number average molecular weight as determined by GPC is at least 10,000 grams/mole.

18. A process according to claim 17, further including a step of removing the any volatile organic content (such as residual monomer, organic diluents, and low molecular weight organic degradation products) to a level of less than 500 ppm.

19. The polymeric reaction product according to claim 1 from polymerizing a) at least one cthylenically unsaturated aliphatic olefin with 2 to 30 carbon atoms with b) at least one cthylenically unsaturated monomer containing an electron withdrawing group in the presence of an aqueous polyurethane dispersion, forming a alpha-olefin-acrylic copolymer comprising repeating units within the same copolymer from said olefin and said monomer containing an electron withdrawing group.

20. The polymeric reaction product according to claim 1, derived from reacting at least polyisυcyanates with one or more active-hydrogen containing compounds, and dispersing the resulting urcthane prepolymer in an olefϊn-acrylic emulsion formed by emulsion copolymerization of said at least one ethylenically unsaturated aliphatic olefin and at least said at least one ethylenically unsaturated monomer containing an electron withdrawing group.

2 i . The polymeric reaction product according to claim 1. in the form of an alpha- olefin-acrylic emulsion further comprising a separately manufactured polyurethane dispersion derived from reacting at least polyisocyanates with one or more active- hydrogen containing compounds forming a prepolymer and dispersing said prepolymer into water and blending the polyurethane dispersion with an emulsion of said alpha- olefin-acrylic copolymer.

22. The polymeric reaction product of damn 19. wherein at least 25 wt.% of the total ethylenically unsaturated aliphatic olefin monomer with 2 to 30 carbon atoms is added to urethane forming components and subsequently to the addition of said ethylenically unsaturated aliphatic olefin said urethane forming components are reacted to for a prepolymer, which is subsequently dispersed in water to foπn said aqueous polyurethane dispersion.