WO2011163250A1 - Dispersions aqueuses de polyuréthane - Google Patents

Dispersions aqueuses de polyuréthane Download PDF

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Publication number
WO2011163250A1
WO2011163250A1 PCT/US2011/041276 US2011041276W WO2011163250A1 WO 2011163250 A1 WO2011163250 A1 WO 2011163250A1 US 2011041276 W US2011041276 W US 2011041276W WO 2011163250 A1 WO2011163250 A1 WO 2011163250A1
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certain embodiments
composition
group
groups
matter
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PCT/US2011/041276
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Dean C. Webster
Mohammed J. Nasrullah
Richard R. Roesler
Scott D. Allen
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Ndsu Research Foundation
Novomer, Inc.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives

Definitions

  • This invention pertains to novel aqueous polyurethane dispersions incorporating aliphatic polycarbonate polyols, as well as methods of making, formulating and using the novel materials in the fields of coatings and adhesives. Also provided are films and coatings made from the novel PUD, as well as surfaces and articles coated with said films and coatings.
  • Aqueous polyurethane dispersions have recently emerged to replace their solvent-based counterparts for a number of applications due to increasing health and environmental awareness.
  • Waterborne PUDs are an important class of polymer dispersion that can be used in many industrial applications such as coatings for wood fimshing; glass fiber sizing; adhesives; automotive topcoats and other applications.
  • Research in the area of polyurethane technology has already spanned many decades and the uses of polyurethanes for coatings applications and efforts to enhance knowledge pertaining to their structure- property relationships continue to expand due to the high performance characteristics of polyurethanes.
  • the present invention encompasses aqueous polyurethane dispersions (PUDs) comprising aliphatic polycarbonate polyols.
  • PUDs aqueous polyurethane dispersions
  • the inventive PUDs are derived from prepolymers which are constructed from an aliphatic polycarbonate polyol.
  • the present invention encompasses coating compositions and adhesive compositions derived from the inventive aqueous polyurethane dispersions.
  • the present invention encompasses isocyanate-terminated prepolymers having a plurality of epoxide-C0 2 -derived polyol segments linked via urethane bonds formed from reaction with polyisocyanate compounds.
  • prepolymers are useful for the manufacture of higher polymers and/or for the formulation of aqueous polyurethane dispersions.
  • inventive compositions of the invention include isocyanate- functionalized prepolymers of formula:
  • R 1 , R 2 , R 3 , and R 4 are, at each occurrence in the polymer chain, independently selected from the group consisting of -H, fluorine, an optionally substituted C 1-30 aliphatic group, and an optionally substituted C 1-2 o heteroaliphatic group, and an optionally substituted C 6-10 aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4 may optionally be taken together with mtervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;
  • n and n' are each independently an integer from about 3 to about 1,000, and may be the same or different;
  • y" is, at each occurrence, independently 0 or 1;
  • -X- is independently at each occurrence -0-, -S-, or -NR-, where R is an optionally
  • ⁇ ⁇ ⁇ represents the carbon skeleton of a diisocyanate
  • C ZZI> represents a segment comprising the carbon skeleton of an optionally present coreactant having any combination of hydroxyl-, amino-, carboxyl-, or thio-groups; m is an integer greater than zero; and
  • p is zero or greater.
  • prepolymers of the present invention incorporate hydropbilic functional groups that aid in forming stable aqueous dispersions from the prepolymers or higher polymers derived from them.
  • the present invention provides methods of preparing isocyanate- terminated prepolymers, higher polymers, and aqueous polyurethane dispersions
  • methods of the present invention comprise the steps of: a) providing one or more aliphatic polycarbonate polyols of formula PI,
  • each of R 1 , R 2 , R 3 , R 4 , n, and fa_/ is as defined and described in the classes and subclasses herein;
  • Y is, at each occurrence, independently -H or the site of attachment to any of the chain-extending moieties described in the classes and subclasses herein; and x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.
  • Certain compounds of the present invention can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers.
  • inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers.
  • the compounds of the invention are enantiopure compounds.
  • mixtures of enantiomers or diastereomers are provided.
  • certain compounds, as described herein may have one or more double bonds that can exist as either the Z or E isomer, unless otherwise indicated.
  • the invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of enantiomers.
  • this invention also encompasses compositions comprising one or more compounds.
  • isomers includes any and all geometric isomers and stereoisomers.
  • “isomers” include cis- and tr ra-isomers, E- and Z- isomers, R— and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
  • a stereoisomer may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched.”
  • a particular enantiomer may, in some embodiments be provided substantially free of the opposite enantiomer, and may also be referred to as "optically enriched.”
  • “Optically enriched,” as used herein, means that the compound or polymer is made up of a significantly greater proportion of one enantiomer. In certain embodiments the compound is made up of at least about 90% by weight of a preferred enantiomer. In other embodiments the compound is made up of at least about 95%, 98%, or 99% by weight of a preferred enantiomer.
  • Preferred enantiomers may be isolated from racemic mixtures by any method known to those skilled in the art, including chiral high pressure liquid
  • epoxide refers to a substituted or unsubstituted oxirane.
  • substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes.
  • Such epoxides may be further optionally substituted as defined herein.
  • epoxides comprise a single oxirane moiety.
  • epoxides comprise two or more oxirane moieties.
  • polymer refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass.
  • a polymer is comprised of substantially alternating units derived from C0 2 and an epoxide (e.g., poly(ethylene carbonate).
  • epoxide e.g., poly(ethylene carbonate).
  • a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer incorporating two or more different epoxide monomers.
  • halo and "halogen” as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -CI), bromine (bromo, -Br), and iodine (iodo, -I).
  • aliphatic or "aliphatic group”, as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-40 carbon atoms. In certain embodiments, aliphatic groups contain 1-20 carbon atoms. In certain embodiments, aliphatic groups contain 3-20 carbon atoms. In certain embodiments, aliphatic groups contain 1-12 carbon atoms. In certain embodiments, aliphatic groups contain 1-8 carbon atoms.
  • aliphatic groups contain 1-6 carbon atoms. In some embodiments, aliphatic groups contain 1-5 carbon atoms, in some embodiments, aliphatic groups contain 1-4 carbon atoms, in some embodiments aliphatic groups contain 1-3 carbon atoms, and in some embodiments aliphatic groups contain 1 or 2 carbon atoms.
  • Suitable aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as
  • heteroaliphatic refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, or phosphorus. In certain embodiments, one to six carbon atoms are independently replaced by one or more of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated or partially unsaturated groups.
  • bivalent C 1-8 (or Ci -3 ) saturated or unsaturated, straight or branched, hydrocarbon chain refers to bivalent alkyl, alkenyl, and alkynyl, chains that are straight or branched as defined herein.
  • cycloaliphatic used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring systems, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined above and described herein.
  • Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl.
  • the cycloalkyl has 3-6 carbons.
  • cycloaliphatic also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring.
  • the term “3- to 7-membered carbocycle” refers to a 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclic ring.
  • the term “3- to 8-membered carbocycle” refers to a 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring.
  • the terms "3- to 14-membered carbocycle” and “C 3-14 carbocycle” refer to a 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring, or a 7- to 14-membered saturated or partially unsaturated polycyclic carbocyclic ring.
  • alkyl refers to saturated, straight- or branched-chain hydrocarbon radicals derived from an aliphatic moiety containing between one and six carbon atoms by removal of a single hydrogen atom. Unless otherwise specified, alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbon atoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, in some embodiments alkyl groups contain 1-3 carbon atoms, and in some embodiments alkyl groups contain 1-2 carbon atoms.
  • alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec- butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.
  • alkenyl denotes a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2-4 carbon atoms, in some embodiments alkenyl groups contain 2-3 carbon atoms, and in some embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, l-methyl-2-buten-l-yl, and the like.
  • alkynyl refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms. In some embodiments, alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2-4 carbon atoms, in some embodiments alkynyl groups contain 2-3 carbon atoms, and in some embodiments alkynyl groups contain 2 carbon atoms. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.
  • alkoxy refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom.
  • alkoxy include but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy.
  • acyloxy refers to an acyl group attached to the parent molecule through an oxygen atom.
  • aryl used alone or as part of a larger moiety as in “aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members.
  • aryl may be used
  • aryl refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents. Also included within the scope of the term aryl", as it is used herein, is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like.
  • the terms "6- to 10-membered aryl” and “C 6- io aryl” refer to a phenyl or an 8- to 10-membered polycyclic aryl ring.
  • heteroaryl and “heteroar-”, used alone or as part of a larger moiety refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 ⁇ electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms.
  • heteroatom refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.
  • Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl.
  • heteroaryl and “heteroar-”, as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring.
  • Nonlimiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-l,4-oxazin-3(4H)-one.
  • heteroaryl group may be mono- or bicyclic.
  • heteroaryl may be used interchangeably with the terms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any of which terms include rings that are optionally substituted.
  • heteroarylkyl refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.
  • the term "5- to 10-membered heteroaryl” refers to a 5- to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • the term "5- to 12-membered heteroaryl” refers to a 5- to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 12-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • heterocycle As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclic radical”, and
  • heterocyclic ring are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7-14-membered polycyclic heterocyclic moiety that is either saturated or partially unsaturated, and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above.
  • nitrogen includes a substituted nitrogen.
  • the nitrogen in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or " * JR (as in TV-substituted pyrrolidinyl).
  • heterocyclic refers to a 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • the term "3- to 12-membered heterocyclic” refers to a 3- to 8- membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 7- to 12-membered saturated or partially unsaturated polycyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • a heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted.
  • saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahy&ofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl.
  • heterocycle refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions
  • partially unsaturated refers to a ring moiety that includes at least one double or triple bond.
  • partially unsaturated is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as herein defined.
  • substituted moieties.
  • substituted whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent.
  • an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position.
  • Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds.
  • stable refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.
  • independent occurrences of R° together with their intervening atoms are independently halogen, -(CH 2 )o_ 2 R e , -(haloR e ), -(CH 2 )o_ 2 OH, -(CH ⁇ OR*, - ⁇ CH 2 ) 0 _ 2 CH(OR e ) 2 ; - 0(haloR e ), -CN, -N 3 , -CCH 2 )o- 2 C(0)R e , -(CH 2 )o- 2 C(0)OH, -(CH 2 )o- 2 C(0)OR°, -(CH 2 )o_ 4 C(0)N(R°) 2 ; -(CH 2 )o_ 2 SR e , - CH 2 )o_ 2 SH, -(CH 2 )o_ 2 NH 2 , -(CH 2 ) 0 _ 2 NHR*, -CCH 2 )o-2NR*2, -N0 2 ,
  • Suitable divalent substituents that are bound to vicinal substitutable carbons of an "optionally substituted” group include: -0(CR* 2 )2-30- wherein each independent occurrence of R * is selected from hydrogen, d-6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • Suitable substituents on the aliphatic group of R * include halogen, -R e , -(haloR*), - OH, -OR e , -0(haloR e ), -CN, -C(0)OH, -C(0)OR e , -NH 2 , -NHR", -NR e 2 , or -N0 2 , wherein each R 9 is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently Ci ⁇ 4 aliphatic, -CH 2 Ph, -0(CH 2 )o_iPh, or a 5-6- membered saturated, partially unsaturated, or aryl ring having 0 ⁇ heteroatoms
  • Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include -R ⁇ , -NR ⁇ 2 , -C(0)R ⁇ , -C(0)OR ⁇ , -C(0)C(0)R ⁇ , -C(0)CH 2 C(0)R ⁇ , -S(0) 2 R ⁇ , - S(0) 2 NR ⁇ 2 , -C(S)NR ⁇ 2 , -C(NH)NR ⁇ 2 , or -N(R ⁇ )S(0) 2 R ⁇ ; wherein each R ⁇ is independently hydrogen, Ci_6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of R ⁇ , taken together with their intervening atom(s) form an
  • Suitable substituents on the aliphatic group of R ⁇ are independently halogen, -R*, -
  • each R e is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently d- aliphatic, -CH 2 Ph, -O(CH 2 ) 0 - 1 Ph, or a 5-6- membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms
  • radical means a moiety or functional group having an available position for attachment to the structure on which the substituent is bound. In general the point of attachment would bear a hydrogen atom if the substituent were an independent neutral molecule rather than a substituent.
  • radical or “optionally- substituted radical” in this context are thus interchangeable with “group” or “optionally- substituted group”.
  • head-to-tail refers to the regiochemistry of adjacent repeating units in a polymer chain.
  • PPC poly(propylene carbonate)
  • head-to-tail ratio refers to the proportion of head-to-tail linkages to the sum of all other regiochemical possibilities.
  • alkoxylated means that one or more functional groups on a molecule (usually the functional group is an alcohol, amine, or carboxylic acid, but is not strictly limited to these) has appended to it a hydroxy-terminated alkyl chain.
  • Alkoxylated compounds may comprise a single alkyl group or they may be oligomeric moieties such as hydroxyl-terminated polyethers.
  • Alkoxylated materials can be derived from the parent compounds by treatment of the functional groups with epoxides.
  • Figure 1 shows the reduced modulus of PUD films on microscope slide cured at room- temperature followed by an overnight heat treatment at 70 °C.
  • Figure 2 shows the hardness of PUD films on microscope slide cured at room-temperature followed by an overnight heat treatment at 70 °C.
  • Figure 3 shows the Tg from dynamic mechanical analysis (DMA) for the room-temperature cured PUD films.
  • Figure 4 shows the storage modulus from DMA for the room-temperature cured PUD films.
  • Figure 5 shows the MALDI-TOF mass spectrum of PE170HNA.
  • Figure 6 shows the MALDI-TOF mass spectrum of Des C2100.
  • Figure 7 shows the MALDI-TOF mass spectrum of Des C2200.
  • Figure 8 shows the MALDI-TOF mass spectrum of NOV 7E21.
  • Figure 9 shows the MALDI-TOF mass spectrum of NOV 94B0.
  • Figure 10 shows the MALDI-TOF mass spectrum of NOV 7DF1.
  • Figure 11 shows the Tg of the PUD films cured at RT and 70 °C.
  • Figure 12 shows the water and MI contact angles and surface energies for PUD coatings cured at room temperature.
  • Figure 13 shows the water and methylene iodide (MI) contact angles and surface energies for PUD coatings cured at room temperature followed by 70 °C overnight.
  • MI methylene iodide
  • Figure 14 shows the nanoindentation of PUD films on microscope slide cured at room
  • Figure 15 shows the storage modulus at 25 °C from DMA for the room temperature cured PUD films
  • Figure 16 shows the Tg from DMA for the room temperature cured PUD films
  • Figure 17 shows the Konig Pendulum Hardness for the RT and 70 °C cured PUD films on aluminum panel. DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS
  • the present invention provides novel polyurethane dispersions created from aliphatic polycarbonate polyols.
  • the polyurethane dispersions comprise chain-extended compositions formed by reaction of the aliphatic polycarbonate polyols with one or more isocyanate reagents selected from the group consisting of diisocyanates, triisocyanates, higher polyisocyanates, mixtures of any two or more of these, and derivatives or oligomers of any of these including, but not limited to acylurea- isocyanates, biurets, and allophanates.
  • the chain-extended compositions incorporate additional segments derived from coreactants such as other polyols, polyhydric alcohols, amines, thiols, and carboxylic acids or functionalized analogs of any of these.
  • compositions of the present invention encompass
  • prepolymers formed by reaction of aliphatic polycarbonate polyols with reagents comprising di- or poly-isocyanates and, optionally, one or more coreactants are described.
  • compositions of the present invention comprise aliphatic polycarbonate polyols derived from the
  • the aliphatic polycarbonate polyol used have a high percentage of reactive end groups.
  • Such reactive end- groups are typically hydroxyl groups, but other reactive functional groups may be present if the polyols are treated post-polymerization to modify the chemistry of the end groups.
  • at least 90% of the end groups of the polycarbonate polyol used are -OH groups.
  • at least 95%, at least 96%, at least 97% or at least 98% of the end groups of the polycarbonate polyol used are -OH groups.
  • more than 99%, more than 99.5%, more than 99.7%, or more than 99.8% of the end groups of the polycarbonate polyol used are -OH groups. In certain embodiments, more than 99.9% of the end groups of the polycarbonate polyol used are -OH groups.
  • aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and one epoxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and ethylene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclohexene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclopentene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and 3 -vinyl cyclohexane oxide.
  • the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide along with one or more additional epoxides selected from the group consisting of ethylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3 -vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.
  • such terpolymers contain a majority of repeat units derived from propylene oxide with lesser amounts of repeat units derived from one or more additional epoxides.
  • terpolymers contain about 50% to about 99.5% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 60% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 75% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 80% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 85% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 90% propylene oxide- derived repeat units. In certain embodiments, terpolymers contain greater than 95% propylene oxide-derived repeat units.
  • aliphatic polycarbonate chains comprise a terpolymer of carbon dioxide and ethylene oxide along with one or more additional epoxides selected from the group consisting of propylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3 -vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.
  • such terpolymers contain a majority of repeat units derived from ethylene oxide with lesser amounts of repeat units derived from one or more additional epoxides.
  • terpolymers contain about 50% to about 99.5% ethylene oxide-derived repeat units.
  • terpolymers contain greater than about 60% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 75% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 80% ethylene oxide- derived repeat units. In certain embodiments, terpolymers contain greater than 85% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 90% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 95% ethylen oxide-derived repeat units.
  • aliphatic polycarbonate chains have a number average molecular weight (Mschreib) in the range of 500 g/mol to about 250,000 g/mol.
  • aliphatic polycarbonate chains have an M shadow less than about 100,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M consult less than about 70,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M consult less than about 50,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M consult between about 500 g/mol and about 40,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M consult less than about 25,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M consult between about 500 g/mol and about 20,000 g/mol.
  • aliphatic polycarbonate chains have an M bias between about 500 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M distrus between about 500 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M prohibit between about 1,000 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M prohibit between about 5,000 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M consult between about 500 g/mol and about 1 ,000 g/mol.
  • aliphatic polycarbonate chains have an M reckon between about 1,000 g/mol and about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M reckon of about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an Mschreib of about 4,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an Mschreib of about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M remember of about 2,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M remember of about 2,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an Mschreib of about 1,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an Mschreib of about 1,000 g/mol.
  • the aliphatic polycarbonate polyols used are characterized in that they have a narrow molecular weight distribution. This can be indicated by the polydispersity indices (POT) of the aliphatic polycarbonate polymers.
  • POT polydispersity indices
  • aliphatic polycarbonate compositions have a PDI less than 2. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.8. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.5. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.4. In certain embodiments, aliphatic polycarbonate compositions have a PDI between about 1.0 and 1.2. In certain embodiments, aliphatic polycarbonate compositions have a PDI between about 1.0 and 1.1.
  • aliphatic polycarbonate compositions of the present invention comprise substantially alternating polymers containing a high percentage of carbonate linkages and a low content of ether linkages. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the
  • the percentage of carbonate linkages is 85% or greater.
  • aliphatic polycarbonate compositions of the present invention are
  • aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 90% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 91 % or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the
  • aliphatic polycarbonate compositions of the present invention are
  • aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 93% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 94% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the
  • the percentage of carbonate linkages is 95% or greater.
  • aliphatic polycarbonate compositions of the present invention are
  • aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 96% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 97% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the
  • the percentage of carbonate linkages is 98% or greater.
  • aliphatic polycarbonate compositions of the present invention are
  • aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 99.5% or greater.
  • the percentages above exclude ether linkages present in polymerization initiators or chain transfer agents and refer only to the linkages formed during epoxide C0 2 copolymerization.
  • aliphatic polycarbonate compositions of the present invention are characterized in that they contain essentially no ether linkages either within the polymer chains derived from epoxide C0 2 copolymerization or within any polymerization intiators, chain transfer agents or end groups that may be present in the polymer. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that they contain, on average, less than one ether linkage per polymer chain within the composition. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that they contain essentially no ether linkages.
  • an aliphatic polycarbonate is derived from mono- substituted epoxides (e.g. such as propylene oxide, 1,2-butylene oxide, epichlorohydrin, epoxidized alpha olefins, or a glycidol derivative)
  • the aliphatic polycarbonate is derived from mono- substituted epoxides (e.g. such as propylene oxide, 1,2-butylene oxide, epichlorohydrin, epoxidized alpha olefins, or a glycidol derivative)
  • aliphatic polycarbonate chains in the inventive polymer compositions have a head-to-tail content higher than about 80%. In certain embodiments, the head-to-tail content is higher than about 85%. In certain embodiments, the head-to-tail content is higher than about 90%. In certain embodiments, the head-to-tail content is greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, or greater than about 95%. In certain embodiments, the head-to-tail content of the polymer is as determined by proton or carbon- 13 NMR spectroscopy.
  • compositions of the present invention comprise aliphatic polycarbonate polyols having a structure PI:
  • R 1 , R 2 , R 3 , and R 4 are, at each occurrence in the polymer chain, independently selected from the group consisting of -H, fluorine, an optionally substituted C 1-30 aliphatic group, and an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted C 6 - 10 aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;
  • Y is, at each occurrence, independently -H or the site of attachment to any of the chain- extending moieties described in the classes and subclasses herein;
  • n is at each occurrence, independently an integer from about 3 to about 1,000; is a multivalent moiety
  • x and y are each independently an integer from 0 to 6, where the sum of x and > is
  • the multivalent moiety _/ embedded within the aliphatic polycarbonate chain is derived from a polyfunctional chain transfer agent having two or more sites from which epoxide/C0 2 copolymerization can occur.
  • such copolymerizations are performed in the presence of polyfunctional chain transfer agents as exemplified in published PCT application WO 2010/028362.
  • a polyfunctional chain transfer agent has a formula:
  • aliphatic polycarbonate chains in the inventive polymer compositions are derived from the copolymerization of one or more epoxides with carbon dioxide in the presence of such polyfunctional chain transfer agents as shown in Scheme 2:
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with a structure P2:
  • » is derived from a dihydric alcohol.
  • the carbon- containing backbone of the dihydric alcohol while the two oxygen atoms adjacent to G ⁇ —) are derived from the -OH groups of the diol.
  • G_/ would be -CH 2 CH 2 - and P2 would have the following
  • the dihydric alcohol comprises a C 2-40 diol.
  • the dihydric alcohol is selected from the group consisting of: 1 ,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-l,3-diol, 2-butyl-2- ethylpropane-l,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-l,3-hexane diol, 2-methyl-l,3- propane diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,
  • the dihydric alcohol is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.
  • the dihydric alcohol comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid.
  • the alkoxylated derivatives comprise ethoxylated or pro oxylated compounds.
  • the dihydric alcohol comprises a polymeric diol.
  • a polymeric diol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these.
  • the polymeric diol has an average molecular weight less than about 2000 g/mol.
  • -/ is derived from a polyhydric alcohol with more than two hydroxy groups.
  • the aliphatic polycarbonate chains in polymer com ositions of the present invention comprise aliphatic polycarbonate chains where the
  • such aliphatic polycarbonate chains have the structure P3:
  • R , R , R J , R ⁇ Y, and n is as defined above and described in classes and subclasses herein.
  • the triol is selected from the group consisting of: glycerol, 1,2,4-butanetriol, 2-(hydroxymethyl)- 1,3 -propanediol; hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4- cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these.
  • alkoxylated derivatives comprise ethoxylated or ropoxylated compounds.
  • alkoxylated polymeric derivatives are derived from an alkoxylated derivative of a trifunctional carboxylic acid or trifunctional hydroxy acid.
  • alkoxylated polymeric derivatives com rise ethoxylated or propoxylated compounds.
  • the polymeric triol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these.
  • the alkoxylated polymeric triols comprise ethoxylated or pro oxylated compounds.
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise aliphatic polycarbonate chains where the moiety is derived from a tetraol. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure
  • (?) is derived from a polyhydric alcohol with more than four hydroxy groups.
  • ( v —? /) is derived from a polyhydric alcohol with six hydroxy groups.
  • a polyhydric alcohol is dipentaerithrotol or an alkoxylated analog thereof.
  • a polyhydric alcohol is sorbitol or an alkoxylated analog thereof.
  • aliphatic polycarbonate chains in polymer compositions of the resent invention comprise chains with the structure P5:
  • aliphatic polycarbonates of the present invention comprise a combination of bifunctional chains (e.g. polycarbonates of formula P2) in combination with higher functional chains (e.g. one or more polycarbonates of formulae P3 to P5).
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P6:
  • R 1 , R 2 , R 3 , R 4 , Y, v5Jand n is as defined above and described in classes and subclasses herein.
  • Cf) represents the carbon-containing backbone of the hydroxy acid, while ester and carbonate linkages adjacent to ( are derived from the -
  • ⁇ is derived from an optionally substituted C 2- 4o hydroxy acid.
  • _D is derived from a polyester. In certain embodiments, such polyesters have a molecular weight less than about 2000 g/mol.
  • a hydroxy acid is an alpha-hydroxy acid. In certain embodiments, a hydroxy acid is selected from the group consisting of: glycolic acid, DL- lactic acid, D-lactic acid, L-lactic, citric acid, and mandelic acid.
  • a hydroxy acid is a beta-hydroxy acid.
  • a hydroxy acid is selected from the group consisting of: 3-hydroxypropionic acid, DL 3-hydroxybutryic acid, D-3 hydroxybutryic acid, L-3-hydroxybutyric acid, DL-3- hydroxy valeric acid, D-3-hydroxy valeric acid, L-3-hydroxy valeric acid, salicylic acid, and derivatives of salicylic acid.
  • a hydroxy acid is a ⁇ - ⁇ hydroxy acid.
  • a hydroxy acid is selected from the group consisting of: of optionally substituted C 3-2 o aliphatic ⁇ - ⁇ hydroxy acids and oligomeric esters.
  • a hydroxy acid is selected from the group consisting of:
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P7:
  • each of R 1 , R 2 , R 3 , R 4 , Y is as defined above and described in classes and subclasses herein, and y' is an integer from 1 to 5 inclusive.
  • aliphatic polycarbonate chains have a structure P7, represents the carbon-containing backbone (or a bond in the case of oxalic acid) of a polycarboxylic acid, while ester groups adjacent to are derived from -C0 2 H groups of a polycarboxylic acid.
  • ester groups adjacent to are derived from -C0 2 H groups of a polycarboxylic acid.
  • R 1 , R 2 , R 3 , R 4 , Y, and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P8:
  • ⁇ / is selected from the group consisting of: phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adi ic acid, pimelic acid, suberic acid, and azelaic acid.
  • each in the structures hereinabove is a
  • each R x is independently an optionally substituted group selected from the group consisting of C 2-20 aliphatic, C 2-20 heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10-membered aryl, 5- to 10-membered heteroaryl, and 3- to 12-membered heterocyclic.
  • each in the structures herein is independently selected from
  • aliphatic polycarbonate chains comprise:
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise wherein each of f ) , - Y, and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise wherein each of l) ; - Y, and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • each of 0, -Y, R x , and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • each of-Y, R x , and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • P2j, P2I, P2I-a, P2n, P2p, and P2r, ⁇ is selected from the group consisting of: ethylene glycol; diethylene glycol, triethylene glycol, 1,3 propane diol; 1,4 butane diol, hexylene glycol, 1,6 hexane diol, propylene glycol, dipropylene glycol, tripopylene glycol, and alkoxylated derivatives of any of these.
  • polycarbonates comprising repeat units derived from two or more epoxides, such as those represented by structures P2f through P2r, depicted above
  • the structures drawn may represent mixtures of positional isomers or regioisomers that are not explicitly depicted.
  • the polymer repeat unit adjacent to either end groups of the polycarbonate chains can be derived from either one of the two epoxides comprising the copolymers.
  • the terminal repeat units might be derived from either of the two epoxides and a given polymer composition might comprise a mixture of all of the possibilities in varying ratios.
  • the ratio of these end-groups can be influenced by several factors including the ratio of the differ rent epoxides used in the polymerization, the structure of the catalyst used, the reaction conditions used (i.e temperature pressure, etc.) as well as by the timing of addition of reaction components.
  • the drawings above may show a defined regiochemistry for repeat units derived from substituted epoxides, the polymer compositions will, in some cases, contain mixtures of regioisomers.
  • the regioselectivity of a given polymerization can be influenced by numerous factors including the structure of the catalyst used and the reaction conditions employed. To clarify, this means that the composition represented by structure P2r above, may contain a mixture of several compounds as shown in the diagram below.
  • This diagram shows the isomers graphically for polymer P2r, where the structures below the depiction of the chain show each regio- and positional isomer possible for the monomer unit adjacent to the chain transfer agent and the end groups on each side of the main polymer chain.
  • Each end group on the polymer may be independently selected from the groups shown on the left or right while the central portion of the polymer including the chain transfer agent and its two adjacent monomer units may be independently selected from the groups shown.
  • the polymer composition comprises a mixture of all possible combinations of these. In other embodiments, the polymer
  • DPG dipropylene glycol
  • regioisomer for convenience— as in structure Ql, for example— it will be understood by one skilled in the art that the compound may actually contain a mixture of isomeric dipropylene glycol moieties.
  • the aliphatic polycarbonate polyol is selected from the group consisting of l, Q2, Q3, Q4, and mixtures of any of these.
  • the aliphatic polycarbonate polyol is selected from the group consisting of:
  • Poly (propylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98%) -OH end groups;
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95%> carbonate linkages, and at least 98% -OH end groups; Poly (propylene carbonate) of formula Ql having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly (propylene carbonate) of formula Ql having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages,, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.
  • the polyurethane dispersions of the present invention comprise isocyanate reagents.
  • the purpose of these isocyanate reagents is to react with the reactive end groups on the aliphatic polycarbonate polyols to form higher molecular weight structures through chain extension and/or cross-linking.
  • the isocyanate reagents comprise two or more isocyanate groups per molecule.
  • the isocyanate reagents are diisocyanates.
  • the isocyanate reagents are higher polyisocyanates such as
  • the isocyanate reagents are aliphatic polyisocyanates or derivatives or oligomers of aliphatic polyisocyanates.
  • the isocyanates are aromatic polyisocyanates or derivatives or oligomers of aromatic polyisocyanates.
  • the compositions may comprise mixtures of any two or more of the above types of isocyanates.
  • an isocyanate reagent is selected from the group consisting of: 1,6- hexamethylenediisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4' methylene- bis(cyclohexyl isocyanate) (Hi 2 MDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), diphenyhnethane-4,4'-diisocyanate (MDI), diphenylmethane-2,4'- diisocyanate (MDI), xylylene diisocyanate (XDI), l,3-bis(isocyanatomethyl)cyclohexane (H6-XDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate (TMDI), m-tetramethylxylylene diisocyanate (TMXD
  • Isocyanates suitable for certain embodiments of the present invention are available commercially under various trade names.
  • suitable commercially available isocyanates include materials sold under trade names: Desmodur® (Bayer Material Science), Tolonate® (Perstorp), Takenate® (Takeda), Vestanat® (Evonik), Desmotherm® (Bayer Material Science), Bayhydur® (Bayer Material Science), Lupranate® (BASF), Trixene (Baxenden), Hartben® (Benasedo), Ucopol® (Sapici), and Basonat® (BASF).
  • Each of these trade names encompasses a variety of isocyanate materials available in various grades and formulations.
  • isocyanates suitable for certain embodiments of the present invention are sold under the trade name Lupranate® (BASF).
  • BASF isocyanates
  • the isocyanates are selected from the group consisting of the materials shown in Table 1 :
  • isocyanates suitable for certain embodiments of the present invention are sold under the trade name Desmodur® available from Bayer Material Science.
  • the isocyanates are selected from the group consisting of the materials shown in Table 2:
  • Desmodur® E 3370 Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanate
  • Desmodur® E XP 2605 Polyisocyanate prepolymer based on toluene diisocyanate and diphenylmethan diisocyanate
  • Desmodur® E XP 2605 Polyisocyanate prepolymer based on toluene diisocyanate and diphenylmethan diisocyanate
  • Desmodur® E XP 2723 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).
  • Desmodur® E XP 2727 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate.
  • Desmodur® E XP 2762 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).
  • Desmodur® HL Aromatic/aliphatic polyisocyanate based on toluylene diisocyanate/ hexamethylene diisocyanate
  • Desmodur® I Monomeric cycloaliphatic diisocyanate.
  • Desmodur® L 1470 Aromatic polyisocyanate based on toluene diisocyanate
  • Desmodur® L 75 Aromatic polyisocyanate based on tolulene diisocyanate
  • Desmodur® LD Low-functionality isocyanate based on hexamethylene diisocyanate (HDI)
  • Desmodur® N 3400 Aliphatic polyisocyanate (HDI uretdione)
  • Desmodur® PC-N is a modified diphenyl-methane-4,4'-diisocyanate (MDI).
  • Desmodur® PF is a modified diphenyl-methane-4,4'-diisocyanate (MDI).
  • Desmodur® PL 350 Blocked aliphatic polyisocyanate based on HDI
  • Desmodur® RC Solution of a polyisocyanurate of toluene diisocyanate (TDI) in ethyl acetate is a polyisocyanurate of toluene diisocyanate (TDI) in ethyl acetate.
  • Desmodur® RN Solution of a polyisocyanurate with aliphatic and aromatic NCO groups in ethyl acetate Desmodur® RN Solution of a polyisocyanurate with aliphatic and aromatic NCO groups in ethyl acetate.
  • Desmodur® VK Desmodur VK products re mixtures of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues (PMDI).
  • Desmodur® VKP 79 is a modified diphenylmethane-4,4'-diisocyanate (MDI) with isomers and homologues.
  • Desmodur VKS 10 is a mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues (PMDI).
  • Desmodur® VKS 20 is a mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues (PMDI).
  • Desmodur® VKS 20 F is a mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues (PMDI).
  • Desmodur® VKS 70 is a mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and homologues.
  • Desmodur® VP LS 2371 Aliphatic polyisocyanate prepolymer based on isophorone diisocyanate.
  • Desmodur® VP LS 2397 is a linear prepolymer based on polypropylene ether glycol and diphenylmethane diisocyanate (MDI). It contains isocyanate groups.
  • Desmodur® XP 2404 is a mixture of monomeric polyisocyanates
  • Desmodur® XP 2406 Aliphatic polyisocyanate prepolymer based on isophorone diisocyanate
  • Desmodur® XP 2489 Aliphatic polyisocyanate
  • Desmodur® XP 2505 Desmodur XP 2505 is a prepolymer containing ether groups based on
  • MDI diphenylmethane-4,4 '-diisocyanates
  • PMDI isomers and higher functional homologues
  • Desmodur® XP 2565 Low-viscosity, aliphatic polyisocyanate resin based on isophorone diisocyanate.
  • Desmodur® XP 2580 Aliphatic polyisocyanate based on hexamethylene diisocyanate
  • Desmodur® XP 2599 Aliphatic prepolymer containing ether groups and based on hexamethylene-1,6- diisocyanate (HDI)
  • Desmodur® XP 2617 is a largely linear NCO prepolymer based on hexamethylene
  • Desmodur® XP 2665 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).
  • Desmodur® XP 2730 Low-viscosity, aliphatic polyisocyanate (HDI uretdione)
  • Desmodur® XP 2742 Modified aliphatic Polyisocyanate (HDI-Trimer), contains Si02 -nanoparticles
  • isocyanates suitable for certain embodiments of the present invention are sold under the trade name Tolonate® (Perstorp).
  • the isocyanates are selected from the group consisting of the materials shown in Table 3 :
  • Additional isocyanates suitable for certain embodiments of the present invention include water-emulsifiable isocyanates sold under the trade name Easaqua® (Perstorp). Examples include EasaquaTM WAT; EasaquaTM WAT-1; EasaquaTM WT 1000; EasaquaTM WT 2102; EasaquaTM X D 401; EasaquaTM X D 803; EasaquaTM X M 501; EasaquaTM X M 502; EasaquaTM X WAT-3 ; and EasaquaTM X WAT-4.
  • EasaquaTM WAT Water-emulsifiable isocyanates sold under the trade name Easaqua® (Perstorp). Examples include EasaquaTM WAT; EasaquaTM WAT-1; EasaquaTM WT 1000; EasaquaTM WT 2102; EasaquaTM X D 401; Eas
  • compositions of the present invention comprise coreactants.
  • Coreactants can include other types of polyols (e.g. polyether polyols, polyester polyols, acrylics, or other polycarbonate polyols), or small molecules with functional groups reactive toward isocyanates such as hydroxyl groups, amino groups, thiol groups, and the like.
  • coreactants comprise molecules with two or more functional groups reactive toward isocyanates.
  • coreactants comprise functional coreactants defined as coreactants containing, in addition to functional groups reactive toward isocyanates, additional functional groups that impart desired physical properties to the PUDs.
  • functional coreactants comprise molecules that, when incorporated into the chain-extension process, impart hydrophilic characteristics to the resulting chain-extended composition.
  • coreactants comprise molecules that, when incorporated into the chain-extension process, provide sites for cross-liriking of the prepolymer or the PUD.
  • functional coreactants comprise hydrophilic groups, ionic groups, or precursors to ionic groups any of which may act as internal emulsifiers and thereby aid in the formation of stable aqueous dispersions of the inventive compositions.
  • such functional coreactants comprise precursors to ionic groups.
  • functional coreactants comprise precursors to cationic groups.
  • functional coreactants comprise precursors to anionic groups.
  • Another group of water-dispersibility enhancing compounds of particular interest are side chain hydrophilic monomers. Some examples include alkylene oxide oligomers, polymers and copolymers as shown, for example, in published U.S. Patent Application No. 20030195293, the disclosure of which is incorporated herein by reference.
  • a coreactant comprises a polyhydric alcohol.
  • a coreactant comprises a dihydric alcohol.
  • the dihydric alcohol comprises a C 2-40 diol.
  • the dihydric alcohol is selected from the group consisting of: 1,2-ethanediol, 1,2-propanediol, 1,3 -propanediol, 1,2- butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-l,3-diol, 2- butyl-2-ethylpropane-l,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-l,3-hexane diol, 2-methyl- 1,3 -propane diol, 1,5-hexanediol, 1,6-hexane
  • trimethylolpropane monoethers pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.
  • a coreactant comprises a dihydric alcohol selected from the group consisting of: diethylene glycol, Methylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.
  • a coreactant comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid.
  • the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.
  • a coreactant comprises a polymeric diol.
  • a polymeric diol is selected from the group consisting of poly ethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether
  • the polymeric diol has an average molecular weight less than about 2000 g/mol
  • a coreactant comprises a triol or higher polyhydric alcohol.
  • a coreactant is selected from the group consisting of: glycerol, 1,2,4- butanetriol, 2-(hydroxymethyl)-l,3-propanediol; hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4-cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these.
  • alkoxylated derivatives comprise ethoxylated or propoxylated compounds.
  • a coreactant comprises a polyhydric alcohol with four to six hydroxy groups. In certain embodiments, a coreactant comprises dipentaerithrotol or an alkoxylated analog thereof. In certain embodiments, coreactant comprises sorbitol or an alkoxylated analog thereof.
  • a functional coreactant comprises a polyhydric alcohol containing one or more moieties that can be converted to an ionic functional group.
  • the moiety that can be converted to an ionic functional group is selected from the group consisting of: carboxylic acids, esters, anhydrides, sulfonic acids, sulfamic acids, phosphates, and amino groups.
  • a coreactant comprises a hydroxy-carboxylic acid having the general formula (HO) x Q(COOH) j , wherein Q is a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and > are each integers from 1 to 3.
  • a coreactant comprises a diol carboxylic acid.
  • a coreactant comprises a bis(hydroxylalkyl) alkanoic acid.
  • a coreactant comprises a bis(hydroxylmethyl) alkanoic acid.
  • the diol carboxylic acid is selected from the group consisting of 2,2 bis-(hydroxymethyl)-propanoic acid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoic acid
  • a coreactant comprises an N,N- bis(2-hydroxyalkyl)carboxylic acid.
  • a coreactant comprises a polyhydric alcohol containing a sulfonic acid functional group. In certain embodiments, a coreactant comprises a diol sulfonic acid. In certain embodiments, a polyhydric alcohol containing a sulfonic acid is selected from the group consisting of: 2-hydroxymethyl-3-hydroxypropane sulfonic acid, 2- butene-l,4-diol-2-sulfonic acid, and materials disclosed in U.S. Pat. No. 4,108,814 and US Pat. App. Pub. No. 2010/0273029 the entirety of each of which is incorporated herein by reference.
  • a coreactant comprises a polyhydric alcohol containing a sulfamic acid functional group.
  • a polyhydric alcohol containing a sulfamic acid is selected from the group consisting of: [N,N-bis(2-hydroxyalkyl)sulfamic acid (where each alkyl group is independently a C 2-6 straight chain, branched or cyclic aliphatic group) or epoxide adducts thereof (the epoxide being ethylene oxide or propylene oxide for instance, the number of moles of epoxide added being 1 to 6) also epoxide adducts of sulfopolycarboxylic acids [e.g.
  • sulfoisophthalic acid sulfosuccinic acid, etc.
  • aminosulfonic acids e.g. 2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid, etc.
  • a coreactant comprises a polyhydric alcohol containing a phosphate group.
  • a coreactant comprises a bis (2-hydroxalkyl) phosphate (where each alkyl group is independently a C 2-6 straight chain, branched or cyclic aliphatic group).
  • a coreactant comprises bis (2-hydroxethyl) phosphate.
  • a coreactant comprises a polyhydric alcohol comprising one or more amino groups. In certain embodiments, a coreactant comprises an amino diol. In certain embodiments, a coreactant comprises a diol containing a tertiary amino group.
  • an amino diol is selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N-ethyldiethanolamine (EDEA), N- butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a-amino pyridine, dipropanolamine, diisopropanolamine (DIP A), N-methyldiisopropanolamine, Diisopropanol-p-toluidine, N,N- Bis(hydroxyethyl)-3-cUoroaniline, 3-diethylaminopropane- 1,2 -diol, 3- dimethylaminopropane-l,2-diol and N-hydroxyethylpiperidine.
  • DEA diethanolamine
  • MDEA N-methyldiethanolamine
  • EDEA N-ethyldiethanolamine
  • BDEA butyldiethanolamine
  • a coreactant comprises a diol containing a quaternary amino group.
  • a coreactant comprising a quaternary amino group is an acid salt or quaternized derivative of any of the amino alcohols described above.
  • Compounds having at least one crosslinkable functional group can also be incorporated into the prepolymers of the present invention, if desired. Examples of such compounds include those having carbonyl, amine, epoxy, acetoacetoxy, urea-formaldehyde, auto-oxidative groups that crosslink via oxidization, ethylenically unsaturated groups optionally with U.V.
  • this invention encompasses novel prepolymers containing aliphatic polycarbonate polyol segments.
  • these prepolymers are the result of reaction of the aliphatic polycarbonate polyols with di- or poly-isocyanates, optionally in the presence of one or more coreactants.
  • each -XH represents a functional group on the coreactant capable of reacting with an isocyanate group (for example -OH, -NHR, -SH, etc.), and -G represents optionally present hydrophilic functional group, a cross-linkable functional group or a precursor thereof.
  • an isocyanate group for example -OH, -NHR, -SH, etc.
  • -G represents optionally present hydrophilic functional group, a cross-linkable functional group or a precursor thereof.
  • the reaction of the chain extending reagent with the -OH groups of the aliphatic polycarbonate polyol and, if present, the -XH groups on the coreactant leads to an oligomeric prepolymer composition having a plurality of segments joined by urethane (carbamate) linkages.
  • Each prepolymer chain resulting from this reaction may contain a variable number of polyol segments and incorporate a variable number of coreactants.
  • the compositional abundance and average chain length of the prepolymers can be controlled using methods known in the art such as by changing the stoichiometry of the reagents and/or by modifying the reaction conditions employed.
  • Scheme 3 therefore represents a simplification and it is to be understood that the prepolymer compositions described herein may contain a complex mixture of random copolymers comprising a statistical distribution of a vast number of chain compositions.
  • such linear oligomers are represented by structure Ol: wherein each of R 1 , R 2 , R 3 , , n, and n' is as defined above and described in classes and subclasses herein, temm represents the carbon skeleton of any of the diisocyanates defined above and described in classes and subclasses herein,
  • ZZI represents the carbon skeleton of any of the coreactants defined above and described in classes and subclasses herein,
  • -X- is -0-, -NR-, or -S-;
  • y" is, independently at each occurrence, 0 or 1 ;
  • n is an integer greater than zero
  • p is zero or greater.
  • e&c y" is zero (e.g. the aliphatic polycarbonate polyol is one formed from a diol chain transfer agent as described for polyols of formula P2 above).
  • one >" is zero and the other;/" is one (e.g. the aliphatic polycarbonate polyol is one formed from a hydroxyacid chain transfer agent as described for polyols of formula P6 above).
  • eachy" is one (e.g. the aliphatic polycarbonate polyol is one formed from a dicarboxylic acid chain transfer agent as described for polyols of formula P8 above).
  • each -X- is an oxygen atom (e.g. where a coreactant comprises a dihydric alcohol).
  • each -X- is an -NR- group (e.g. where a coreactant comprises a diamine).
  • the -X- groups present represent a mixture of oxygen and nitrogen atoms.
  • the prepolymer comprises branched or cross-linked oligomers of a difunctional aliphatic polycarbonate polyol and a polyisocyanate having more than two isocyanate groups, where the prepolymer optionally contains segments derived from one or more difunctional coreactants.
  • such branched oligomers comprise compounds represented by structure 02: wherein each of R, R 1 , R 2 , R 3 , R 4 , X, ⁇ , ⁇ » ⁇ , and m, n, ⁇ ', ⁇ , and/' is as defined above and described in classes and subclasses herein, and z is an integer greater than 2.
  • the prepolymer comprises branched or cross-linked oligomers of a branched aliphatic polycarbonate polyol having more than two -OH end groups and a polyisocyanate having at least two isocyanate groups, where the prepolymer optionally contains segments derived from one or more difunctional coreactants.
  • such branched oligomers comprise compounds represented by structure 03: wherein each of R 1 , R 2 , R 3 , R 4 , X, ⁇ , and m, n,p, z, and; " is as defined above and described in classes and subclasses herein, and n" is at each occurrence, independently an integer from about 3 to about 1,000, and may be the same as or different from n or n'.
  • the prepolymer comprises branched or cross-linked oligomers of an aliphatic polycarbonate polyol, a polyisocyanate having at least two isocyanate groups, and one or more coreactants having more than two function groups reactive toward isocyanates.
  • such branched oligomers comprise compounds represented by structure 04: wherein each of R 1 , R 2 , R 3 , R 4 , X, ⁇ , , ⁇ Z ⁇ > , and m, n, ri, p, z, and /' is as
  • the prepolymer comprises complex branched oligomers of formula 05 derived from an aliphatic polycarbonate polyol having more than two hydroxyl groups and a polyisocyanate having more than two isocyanate groups, where the prepolymer optionally contains segments derived from one or more difunctional coreactants.
  • the prepolymer comprises complex branched oligomers of formula 06 comprising an aliphatic polycarbonate polyol having more than two hydroxyl groups, a diisocyanate and a polyfunctional coreactant having more than two functional groups reactive toward isocyanates.
  • the prepolymer comprises complex branched oligomers of formula 07 comprising an aliphatic polycarbonate polyol, a polyisocyanate having more than two isocyanate groups, and a polyfunctional coreactant having more than two functional groups reactive toward isocyanates.
  • complex branched oligomers of formula 07 comprising an aliphatic polycarbonate polyol, a polyisocyanate having more than two isocyanate groups, and a polyfunctional coreactant having more than two functional groups reactive toward isocyanates.
  • the prepolymer comprises complex branched oligomers of formula 08 comprising an aliphatic polycarbonate polyol having more than two hydroxyl groups, a polyisocyanate having more than two isocyanate groups, and a polyfunctional coreactant having more than two functional groups reactive toward isocyanates.
  • prepolymers comprise mixtures containing linear oligomers of formula Ol along with smaller amounts of any one or more branched oligomers of formulae 02 through 08. In certain embodiments, prepolymers comprise linear oligomers of formula Ol with essentially no cross-linking or branching.
  • the prepolymer comprises aliphatic polycarbonate segments derived from any of the polyols of formulae P2a through P2r-a as defined above and described in classes and subclasses herein, or from mixtures of any two or more of these.
  • the prepolymer comprises aliphatic polycarbonate segments derived from any of the polyols of formulae Ql through Q4 as defined above and described in classes and subclasses herein, or from mixtures of any two or more of these.
  • the prepolymer further comprises aliphatic polycarbonate segments derived from any of the polyols of formulae P3, P4, or P5 as defined above and described in classes and subclasses herein, or from mixtures of any two or more of these.
  • the prepolymer further comprises segments derived from any one or more of the coreactants described hereinabove.
  • a coreactant comprises an alcohol (e.g. at least one - X- in any of structures 01-04 is -0-).
  • the prepolymer comprises coreactant segments having one or more hydrophilic functional groups.
  • such hydrophilic functional groups are precursors to anionic groups.
  • the precursors to anionic groups present on coreactant segments are selected from the group consisting of: carboxylic acids, esters, anhydrides, sulfonic acids, sulfamic acids, phosphates.
  • the prepolymer comprises coreactant segments having one or more carboxylic acid groups.
  • such coreactant segments are derived from carboxylic acid diols.
  • such coreactant segments are derived from a bis(hydroxylalkyl) alkanoic acid.
  • such coreactant segments are derived from a bis(hydroxylmethyl) alkanoic acid.
  • such coreactant segments are derived from a compound selected from the group consisting of DMPA; DMBA, tartaric acid, and 4,4'- bis(hydroxyphenyl) valeric acid.
  • prepolymers of formulae Ol through 08 contain coreactant segments derived from DMPA.
  • prepolymers of formulae Ol through 08 contain coreactant segments derived from DMBA.
  • the prepolymer comprises coreactant segments bearing one or more carboxylate salts.
  • a coreactant segment comprising a carboxylate salt is derived from any of the carboxylic acid-containing coreactant segments described above by treating them with a base.
  • the base comprises a metal salt.
  • the base comprises an amine.
  • the prepolymer comprises coreactant segments having one or more amino groups.
  • such coreactant segments are derived from amine diols.
  • such coreactant segments are derived from a diol containing a tertiary amino group.
  • such coreactant segments are derived from an amino diol selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N- ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a- amino pyridine, dipropanolamine, diisopropanolamine (DIP A), N- methyldiisopropanolamine, Diisopropanol-p-toluidine, N ⁇ V-Bis(hydroxyethyl)-3 - chloroaniline, 3-diethylaminopropane-l,2-diol, 3-dimethylaminopropane-l,2-diol andN- hydroxyethylpiperidine.
  • DEA diethanolamine
  • MDEA N-methyldiethanolamine
  • EDEA N- ethyldiethanolamine
  • BDEA N,N-bis(hydroxyethy
  • prepolymers of formulae Ol through 08 contain coreactant segments derived from DEA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from MDEA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from EDEA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from BDEA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from DIP A.
  • the prepolymer comprises coreactant segments having one or more quaternary amino groups.
  • a coreactant segment comprising a quaternary amino group is derived from any of the amine-containing coreactant segments described above by creating an acid salt or quaternized derivative of any of the amine-containing coreactant segments described in the previous paragraph.
  • the prepolymer comprises coreactant segments derived from hydrophilic poly ether polyols.
  • such hydrophilic poly ether polyols are oligomers of ethylene oxide and/or propylene oxide.
  • the hydrophilic polyether polyols are rich in EO repeat units.
  • the prepolymers contain a plurality of different coreactant segments derived from two or more different coreactants including mixtures of two or more of any of the coreactants above and described in the classes and subclasses herein.
  • the molar ratio of aliphatic polycarbonate segments to coreactant segments in the prepolymer composition varies from about 10,000:1 to about 1:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 5,000:1 to about 5:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 1,000:1 to about 10:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 500:1 to about 10:1.
  • the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 500:1 to about 20:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 200:1 to about 50:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments is about 200: 1 , about 100: 1 , about 50:1, about 30:1, about 20:1, about 10:1 or about 5:1. In some embodiments, a prepolymer may contain more than one type of coreactant segment, in which case the ratios above may be taken to describe the ratio of the polycarbonate segments to any single coreactant segment.
  • urethane linkages in the prepolymer are derived from aliphatic diisocyanates, aromatic diisocyanates, oligomeric diisocyanates, or difunctional isocyanate prepolymers.
  • the prepolymer comprises urethane linkages derived from one or more aliphatic diisocyanates.
  • the prepolymer comprises urethane linkages derived from diisocyanates selected from the group consisting of: HDI, IPDI, H 12 MDI, H6-XDI, TMDI, 1 ,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, trimethylhexane diisocyanate, and mixtures of any two or more of these.
  • the prepolymer comprises urethane linkages derived from diisocyanates selected from the group consisting of: HDI, IPDI, H 12 MDI and mixtures of two or more of these.
  • the prepolymer comprises urethane linkages derived from HDI.
  • the prepolymer comprises urethane linkages derived from IPDI.
  • the prepolymer comprises urethane linkages derived from H 12 MDI.
  • the prepolymer comprises urethane linkages derived from H6-XDI.
  • the prepolymer comprises urethane linkages derived from TMDI.
  • the prepolymer comprises urethane linkages derived from oligomers or derivatives of any of the above aliphatic isocyanates. In certain embodiments, the prepolymer comprises urethane linkages derived from biurets of any of the above aliphatic isocyanates.
  • the prepolymer comprises urethane linkages derived from one or more aromatic diisocyanates.
  • the prepolymer comprises urethane linkages derived from diisocyanates selected from the group consisting of: 2,4-TDI, 2,6-TDI, MDI, XDI, TMXDI, and mixtures of any two or more of these.
  • the prepolymer comprises urethane linkages derived from TDI or MDI.
  • the prepolymer comprises urethane linkages derived from TDI.
  • the prepolymer comprises urethane linkages derived from 2,4-TDI.
  • the prepolymer comprises urethane linkages derived from 2,6-TDI. In certain embodiments, the prepolymer comprises urethane linkages derived from H6-XDI. In certain embodiments, the prepolymer comprises urethane linkages derived from MDI. In certain embodiments, the prepolymer comprises urethane linkages derived from XDI. In certain embodiments, the prepolymer comprises urethane linkages derived from TMXDI. In certain embodiments, the prepolymer comprises urethane linkages derived from oligomers or derivatives of any of the above aromatic isocyanates. In certain embodiments, the prepolymer comprises urethane linkages derived from biurets of any of the above aromatic isocyanates.
  • the prepolymer comprises covalently-linked isocyanate groups.
  • Compositions having this property may be produced using methods known in the art. In particular, control of the molar ratios of the reagents during prepolymer formation such that there is a molar excess of the polyfunctional isocyanate relative to the isocyanate-reactive groups on the aliphatic polycarbonate polyol and coreactants (if any) will favor oligomers where the chain ends are capped with an isocyanate resulting from partial reaction of a polyisocyanate molecule.
  • a majority of chain ends in prepolymers of the present invention comprise isocyanate groups.
  • at least 60%, at least 70%, at least 80%, at least 85% or at least 90% of chain ends comprise isocyanate groups.
  • at least 92%, at least 95%, at least 96%, at least 97% or at least 98% of chain ends comprise isocyanate groups.
  • at least 99% of chain ends comprise isocyanate groups.
  • essentially all of the chain ends in prepolymers of the present invention comprise isocyanate groups.
  • the present invention provides novel compositions of matter comprising prepolymers of formula Ol comprising poly(propylene carbonate) (PPC) segments.
  • prepolymers of formula Ol contain segments of formula Ol-al
  • the present invention provides novel compositions of matter comprising prepolymers of formula Ol comprising poly(ethylene carbonate) (PEC) segments.
  • prepolymers contain segments of formula 01-a2
  • prepolymers of formula Ol contain segments derived from polyols of formula Ql, Q2, Q3, or Q4, as defined above and described in the classes and subclasses herein, or from mixtures of any two or more of these.
  • the present invention provides novel compositions of matter comprising prepolymers of formula Ol, where the polyol segments are derived from one or more aliphatic polycarbonate polyol compositions selected from the group consisting of:
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98%) -OH end groups
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a
  • polydisperisty index less than about 1.25, at least 95%> carbonate linkages, and at least
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; and
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least
  • the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols.
  • such prepolymers comprise fragments having a structure Ol-bl:
  • the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from 2,2' dimethylolpropionic acid, (DMPA)
  • prepolymers comprise fragments having a structure Ql-b2:
  • the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from 2,2- bis(hydroxymethyl) butanoic acid (DMBA).
  • prepolymers comprise fragments having a structure 01-b3:
  • the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols, and urethane linkages derived from aliphatic isocyanates.
  • the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols, and urethane linkages derived from one or more aliphatic isocyanates selected from the group consisting of: HDI, IPDI, H 12 MDI, H6-XDI, TMDI, 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, and trimethylhexane diisocyanate.
  • the present invention provides prepolymers of formula Ol comprising fragments having any of structures 01-b4 through 01-b8, wherein each of n and is as defined above and described in classes and subclasses herein.
  • the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols, and urethane linkages derived from aromatic isocyanates. In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols, and urethane linkages derived from one or more aromatic isocyanates selected from the group consisting of: TDI, MDI, XDI, and TMXDI.
  • the present invention provides prepolymers of formula Ol comprising fragments having any of structures 01-b9 through 01- 2, wherein each of n and is as defined above and described in classes and subclasses herein.
  • the present invention provides prepolymers of formula Ol comprising PEC segments in combination with coreactant segments derived from carboxylic acid diols.
  • such prepolymers comprise fragments having any of structures Ol-bl through 01-bl2, where the PPC segments are substituted for PEC, or PPC- co-PEC segments: such compounds may be designated 01-bl3 through 01-b25 where the non-polycarbonate segments of 01-bl3 correspond to those in Ol-bl, those in 01-bl4 correspond to 01-b2, and so on.
  • the present invention provides prepolymers analogous to those depicted in formulae Ol-al through 01-b25 but comprising polycarbonate polyol segments derived from chain transfer agents having one or more carboxylic acid groups.
  • the specific structures of these compounds can be ascertained by substituting some or all of the polycarbonate-polyol-derived segments in compounds Ol-al through 01-b25 with poly(propylene carbonate) or poly(ethylene carbonate) conforming to structures P6 or P8.
  • the present invention provides prepolymers comprising carboxylate salts derived from neutralization of the pendant carboxyl groups to convert the carboxyl groups to carboxylate anions, thus having a water-dispersibility enhancing effect.
  • Suitable neutralizing agents include tertiary amines, metal hydroxides, ammonium
  • the present invention provides prepolymers comprising carboxylate salts derived from any of the fragments of formulae Ol-bl through 01-b25.
  • such carboxylate salts are alkali earth metal salts.
  • such salts are sodium salts.
  • such salts are ammonium salts.
  • the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from amino diols.
  • such prepolymers comprise fragments having a structure Ol- cl:
  • Ri and R 2 is independently selected from the group consisting of:
  • Rr and R 2 may be optionally taken together with intervening atoms to form one or more optionally substituted saturated or unsaturated rings optionally containing one or more additional heteroatoms, and where 3 ⁇ 4 and R 2 may constitute part of the oligomeric chain (e.g. as in the case of hydroxyl alkyl amine-derived materials).
  • the amine-bearing segment is derived from an amino diol selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N- ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a- amino pyridine, dipropanolamine, diisopropanolamine (DIP A), N- methyldiisopropanolamine, Diisopropanol-p-toluidine, N,N-Bis(hydroxyethyl)-3 - chloroaniline, 3 -diethylaminopropane- 1 ,2-diol, 3 -dimethylaminopropane- 1 ,2-diol.
  • DEA diethanolamine
  • MDEA N-methyldiethanolamine
  • EDEA N- ethyldiethanolamine
  • BDEA N-butyldiethanolamine
  • such prepolymers comprise fragments having a structure Ol- cl:
  • R k methyl, ethyl, propyl, n-butyl, 2-pyridyl,
  • such prepolymers comprise fragments having a structure Ol- c3:
  • 01-c3 k methyl, ethyl, propyl, rc-butyl, 2-pyridyl,
  • n, (f) phenyl, benzyl, m-chlorophenyl, or p-methylphenyl wherein each of n, (f) , and is as defined above and described in classes and subclasses herein.
  • such prepolymers comprise fragments having a structure Ol- c4:
  • the present invention encompasses compounds of structure
  • Ol-cl comprising any of the urethane linkages shown in structures 01-b4 through 01- 2 these fragment structures may be referred to as fragments 01-c5 through 01-cl3, where the non coreactant segments in 01-c5 correspond to those in 01-b4, those in 01-c6 correspond to 01-b5, and so forth.
  • the present invention provides prepolymers of formula Ol comprising PEC segments in combination with coreactant segments derived from carboxylic acid diols.
  • such prepolymers comprise fragments having any of structures Ol-cl through 01-cl3, where the PPC segments are substituted for PEC, or PPC- co-PEC segments.
  • the present invention provides prepolymers comprising ammonium salts derived from any of the fragments of formulae Ol-cl through 01-cl3 (or from their PEC counterparts).
  • ammonium salts are quaternized ammonium salts formed by treating the amine with alkylating agents such as alkyl halides (e.g. methyl iodide, bromomethane, benzyl chloride, or allyl chloride), alkyl sulfates (e.g. methyl sulfate or ethyl sulfate) and the like.
  • alkylating agents such as alkyl halides (e.g. methyl iodide, bromomethane, benzyl chloride, or allyl chloride), alkyl sulfates (e.g. methyl sulfate or ethyl sulfate) and the like.
  • alkylating agents such as alkyl halides (e.g
  • the present invention provides prepolymers analogous to those depicted in formulae Ol-cl through 01-cl3 but comprising polycarbonate polyol segments derived from chain transfer agents having one or more carboxylic acid groups.
  • the specific structures of these compounds can be ascertained by substituting some or all of the polycarbonate-polyol-derived segments in compounds Ol-cl through 01-cl3 with poly(propylene carbonate) or poly(ethylene carbonate) conforming to structures P6 or P8.
  • the present invention encompasses solutions of any of the above-described prepolymers.
  • such solutions comprise one or more non-protic polar organic solvents.
  • the solvent comprises a ketone.
  • the solvent comprises acetone or 2-butanone.
  • the solvent comprises an amide.
  • the solvent comprises N- methylpyrrolidone (NMP).
  • the present invention encompasses aqueous dispersions comprising any of the above-described prepolymers.
  • aqueous dispersions comprise emulsions of the prepolymers in substantially unmodified form, while in other embodiments, the aqueous dispersions contain higher polymers formed by the reaction of the isocyanate groups present on the prepolymers with chain-extending agents. If such higher polymers are present, they may be formed in situ by inclusion of suitable chain- extending reagents during or after formation of the dispersion, or they may be foraied prior to dispersion.
  • aqueous dispersions of the present invention are formed by one of several methods including:
  • emulsifiers such as surfactants, or internal emulsifiers having anionic and/or cationic groups as part of or pendant to the polyurethane backbone, and/or as end groups on the polyurethane backbone.
  • emulsifiers such as surfactants, or internal emulsifiers having anionic and/or cationic groups as part of or pendant to the polyurethane backbone, and/or as end groups on the polyurethane backbone.
  • acetone process A prepolymer is formed with or without the presence of acetone, MEK, and/or other polar solvents that are non-reactive and easily distilled. The prepolymer is further diluted in said solvents as necessary, and chain extended with an active hydrogen-containing compound. Water is added to the chain-extended polyurethane, and the solvents are distilled off.
  • a variation on this process would be to chain extend the prepolymer after its dispersion into water.
  • Ketazine and ketimine processes Hydrazines or diamines are reacted with ketones to form ketazines or ketimines. These are added to a prepolymer, and remain inert to the isocyanate. As the prepolymer is dispersed in water, the hydrazine or diamine is liberated, and chain extension takes place as the dispersion is taking place.
  • the higher polymers are formed by chain extension with suitable chain-extending agents.
  • Suitable chain-extending agents can contain hydroxyl, thio, or amino groups in any combination. Examples of chain-extending agents can be found, for example, in US Pat. No. 7,342,068, which is incorporated herein by reference. It is also known that chain extension can also be accomplished by permitting the reaction of an isocyanate functional group on the polyurethane prepolymer with water via a mechanism believed to generate amine functional group on the prepolymer which promptly reacts with another isocyanate functional group of the prepolymer to give a self-extended polymer. In certain embodiments, the formation of higher polymers conforms to the reaction shown in Scheme 4:
  • an isocyanate-terminated prepolymer of formula Ol (or any other isocyanate-terminated prepolymer composition described above and in the classes and subclasses herein) is reacted with a chain-extending reagent having two (or more) -ZH groups, where each -ZH is independently selected from the group consisting of -OH, -C(0)OH, -SH, or -NHR to form a higher polymer comprising segments of formula HI.
  • a chain extender is selected from the group consisting of: water, inorganic or organic polyamines having an average of about 2 or more primary and/or secondary amine groups, polyalcohols, ureas, and combinations of any two or more of these.
  • a chain extender is selected from the group consisting of: diethylene triamine (DETA), ethylene diamine (EDA), meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methyl pentane diamine, and the like, and mixtures thereof.
  • a chain extender is selected from the group consisting of: hydrazine, substituted hydrazines, hydrazine reaction products, and the like, and mixtures thereof.
  • a chain extender is a polyalcohol including those having from 2 to 12 carbon atoms, preferably from 2 to 8 carbon atoms, such as ethylene glycol, diethylene glycol, neopentyl glycol, butanediols, hexanediol, and the like, and mixtures thereof.
  • Suitable ureas include urea and its derivatives, and the like, and mixtures thereof.
  • chain-extending agents containing at least one basic nitrogen atom are selected from the group consisting of: mono-, bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, N-methyl diethanolamine, N-ethyl diethanolamine, N-propyl diethanolamine, N-isopropyl diethanolamine, N-butyl
  • diethanolamine ethoxylated coconut oil fatty amine
  • N-allyl diethanolamine N-methyl diisopropanolamine, N-ethyl diisopropanolamine, N-propyl diisopropanolamine, N-butyl diisopropanolamine, cyclohexyl diisopropanolamine, N,N-diethoxylaniline, N,N-diethoxyl toluidine, N,N-diethoxyl-l-aminopyridine, ⁇ , ⁇ '-diethoxyl piperazine, dimethyl-bis-ethoxyl hydrazine, N,N'-bis-(2-hydroxyethyl)-N,N'-diethylhexahydr op-phenylenediamine, N- 12- hydroxyethyl piperazine, polyalkoxylated amines, propoxylated methyl diethanolamine, N- methyl-N,N-bis-3 -amino
  • chain-extending agents are compounds that contain two amino groups.
  • chain-extending agents are selected from the group consisting of: ethylene diamine, 1,6-hexamethylene diamine, and 1,5-diamino-l-methyl-pentane.
  • the higher polymers are formed by chain extension of any of the above-described prepolymers with polyamines, the end result is a higher molecular weight polyurethane/urea dispersion.
  • such polyurethane/urea dispersions comprise polymer chains of structure HI:
  • each - ⁇ group represents any one or more of the prepolymer compositions as defined above and described in the classes and subclasses herein including any of the prepolymer compositions described by structures Ol-al through 01-cl3,
  • each ! chain ExteDder l group represents a structure derived from any one or more of the diamine cross-linking agents described above, and
  • -R is independently at each occurrence, -H or an optionally substituted C 1-8 aliphatic group.
  • inventive PUD's further contain branched structures derived by chain-extension with reagents having three or more groups reactive toward the isocyanate groups of the prepolymers.
  • inventive PUDs contain branched structures resulting from inclusion of any of the branched prepolymer compositions described hereinabove.
  • the aqueous polyurethane dispersions disclosed herein may comprise water and from about 15 to about 75 weight percent solids, wherein the solids comprise a polyurethane polymer or prepolymer as described above and in the classes and subclasses herein.
  • the aqueous polyurethane dispersion contains about 20 to about 60 weight percent solids.
  • the aqueous polyurethane dispersion contains about 30 to about 40 weight percent solids.
  • the aqueous polyurethane dispersion contains about 30, about 40, about 45, about 50 about 55, or about 60 weight percent solids.
  • the aqueous polyurethane dispersions may be further diluted to any proportion.
  • the particle size of the polyurethane polymer phase contained within the aqueous polyurethane dispersion is less than about 3 microns. In certain embodiments, the particle size of the polyurethane polymer phase contained within the aqueous polyurethane dispersion is less than about 2.5, less than about 2, less than about 1.5, or less than about 1 micron. In certain embodiments, the particle size of the polyurethane polymer phase contained within the aqueous polyurethane dispersion is and more preferably less than about 1 micron.
  • the polyurethane polymer contained within the aqueous polyurethane dispersion has a free isocyanate functionality of approximately zero.
  • the viscosity of the aqueous polyurethane dispersion may range from about 40 to about 12,000 cps. In certain embodiments, the viscosity of the aqueous polyurethane dispersion ranges from about 100 to about 4,000 cps. In certain embodiments, the viscosity of the aqueous polyurethane dispersion ranges from about 200 to about 1 ,200 cps.
  • the aqueous polyurethane dispersion will preferably remain storage stable and fully dispersed within the aqueous media for extended periods of time.
  • inventive polyurethane dispersions further comprise additives as are well known in the art.
  • Typical additives include pigments, fillers, stabilizers curing agents and the like.
  • Other additives well known to those skilled in the art can be used to aid in preparation of the dispersions of this invention.
  • Such additives include surfactants, stabilizers, defoamers, antimicrobial agents, antioxidants, UV absorbers, carbodiimides, and the like.
  • Additives such as activators, curing agents, stabilizers such as StabaxolTM P200, colorants, pigments, neutralizing agents, thickeners, non-reactive and reactive plasticizers, coalescing agents such as di(propylene glycol) methyl ether (DPM), waxes, slip and release agents, antimicrobial agents, surfactants such as PluronicTM F68-LF and IGEPALTM CO630 and silicone surfactants, metals, antioxidants, UV stabilizers, antiozonants, and the like, 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 such as activators, curing agents, stabilizers such as StabaxolTM P200, colorants, pigments, neutralizing agents, thickeners, non-reactive and reactive plasticizers, coalescing agents such as di(propylene glycol) methyl ether (DPM), waxes, slip and release agents, antimicrobial agents
  • Additives may be used as appropriate in order to make articles or to treat (such as by impregnation, saturation, spraying, coating, or the like) porous and non-porous substrates such as papers, non- woven materials, textiles, leather, wood, concrete, masonry, metals, house wrap and other building materials, fiberglass, polymeric articles, personal protective equipment (such as hazardous material protective apparel, including face masks, medical drapes and gowns, and firemen's turnout gear), and the like.
  • Applications include papers and non-wovens; fibrous materials; films, sheets, composites, and other articles; inks and printing binders; flock and other adhesives; and personal care products such as skin care, hair care, and nail care products; livestock and seed applications; and the like.
  • Suitable surfactants include a wide variety of nonionic, cationic, anionic, and zwitterionic surfactants, such as those disclosed in McCutcheon's Detergents and
  • Suitable surfactants include silicone esters, alkyl and alkenyl sulfates; alkyl and alkenyl ethoxylated sulfates (preferably having an average degree of ethoxylation from 1 to about 10); succinamate surfactants such as alkylsulfosuccinamates and dialkyl esters of sulfosuccinic acid; neutralized fatty acid esters of isethionic acid; and alkyl and alkenyl sulfonates, such as olefin sulfonates and beta-alkoxy alkane sulfonates; and the like.
  • alkyl and alkenyl sulfates and alkyl and alkenyl ethoxylated sulfates such as the sodium and ammonium salts of C 12 -C 18 sulfates and ethoxylated sulfates with a degree of ethoxylation from 1 to about 6, and more preferably from 1 to about 4, such as lauryl sulfate and laureth (3.0) sulfate sodium 3-dodecylaminopropionate; N-alkyltaurines such as prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No.
  • alkyl preferably C 6 -C 22 and more preferably C 8-12
  • alkyl preferably C 6 -C 22 and more preferably C 8 -C i 2
  • amphopropionates and the like. Mixtures can also be used.
  • Suitable zwitterionic surfactants for use in the present compositions include those broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, wherein which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and another substituent contains an anionic water-dispersibility enhancing group, such as carboxy, sulfonate, sulfate, phosphate, phosphonate, and the like.
  • Classes of zwitterionics include alkyl amino sulfonates, alkyl betaines and alkyl amido betaines, stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N- tallowpropane diamine, ethoxylated (5 moles ethylene oxide) stearylamine, dihydroxy ethyl stearylamine, arachidylbehenylamine, and the like. Mixtures can also be used.
  • Suitable viscosity adjusters include isopropyl alcohol, ethanol, sorbitol, propylene glycol, diethylene glycol, triethylene glycol, dimethyl ether, butylene glycol, and the like, and mixtures thereof.
  • Suitable plasticizers include ester derivatives of such acids and anhydrides as adipic acid, azelaic acid, benzoic acid, citric acid, dimer acids, fumaric acid, isobutyric acid, isophthalic acid, lauric acid, linoleic acid, maleic acid, maleic anyhydride, melissic acid, myristic acid, oleic acid, palmitic acid, phosphoric acid, phthalic acid, ricinoleic acid, sebacic acid, stearic acid, succinic acid, 1,2-benzenedicarboxylic acid, and the like, and mixtures thereof.
  • epoxidized oils glycerol derivatives, paraffin derivatives, sulfonic acid derivatives, and the like, and mixtures thereof and with the aforesaid derivatives.
  • plasticizers include diethylhexyl adipate, heptyl nonyl adipate, diisodecyl adipate, the adipic acid polyesters sold by Solutia as the Santicizer series, dicapryl adipate, dimethyl azelate, diethylene glycol dibenzoate and dipropylene glycol dibenzoate (such as the K-Flex® esters from Noveon, Inc.), polyethylene glycol dibenzoate, 2,2,4- trimethyl- 1 ,3-pentanediol monoisobutyrate benzoate, 2,2,4-trimethyl- 1 ,3-pentanediol diisobutyrate, methyl (or ethyl, or butyl) phthalyl ethyl glycolate, triethyl citrate, dibutyl fumarate, 2,2,4-trimethyl- 1, 3 -pentanediol diisobutyrate,
  • plasticizers known to those skilled in the art include castor oil, sunflower seed oil, soybean oil, aromatic petroleum condensate, partially hydrogenated terphenyls, silicone plasticizers such as dimethicone copolyol esters, dimethiconol esters, silicone carboxylates, guerbet esters, and the like, alone or as mixtures with other plasticizers known to those skilled in the art include castor oil, sunflower seed oil, soybean oil, aromatic petroleum condensate, partially hydrogenated terphenyls, silicone plasticizers such as dimethicone copolyol esters, dimethiconol esters, silicone carboxylates, guerbet esters, and the like, alone or as mixtures with other plasticizers such as dimethicone copolyol esters, dimethiconol esters, silicone carboxylates, guerbet esters, and the like, alone or as mixtures with other plasticizers known to those skilled in the art include castor oil, sunflower seed oil, soybean oil
  • suitable reactive plasticizers include compositions and mixtures having ethylenic unsaturation, such as triallyl trimellitate (TATM), Stepanol PD-200LV (a mixture of (1) unsaturated oil and (2) polyester diol reaction product of o-phthalic acid and diethylene glycol from Stepan Company), and the like, and mixtures thereof.
  • TATM triallyl trimellitate
  • Stepanol PD-200LV a mixture of (1) unsaturated oil and (2) polyester diol reaction product of o-phthalic acid and diethylene glycol from Stepan Company
  • epoxidized plasticizers including certain monofuctional and
  • polyfunctional glycidyl ethers such as Heloxy® Modifier 505 (polyglycidyl ether of castor oil) and Heloxy® Modifier 71 (dimer acid diglycidyl ether) from Shell Chemical Company, and the like, and mixtures thereof.
  • suitable flame retardant plasticizers include phosphorus-based plasticizers such as cyclic phosphates, phosphites, and phosphate esters, exemplified by PliabracTM TCP (tricresyl phosphate), PliabracTM TXP (trixylenyl phosphate), AntiblazeTM N (cyclic phosphate esters), AntiblazeTM TXP (tar acid, cresol, xylyl, phenol phosphates), and AntiblazeTM 524 (trixylyl phosphate) from Albright & Wilson Americas; FiremasterTM BZ 54 (halogenated aryl esters) from Great Lakes Chemicals; chlorinated biphenyl, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, p-t-butylphenyl diphenyl phosphate, triphenyl
  • phosphorus-based plasticizers include chlorinated alkyl phosphate esters such as AntiblazeTM 100 (chloro alkyl diphosphate ester) from Albright & Wilson Americas; alkyl phosphates and phosphites such as tributyl phosphate, tri-2-ethylhexyl phosphate, and triisoctyl phosphite; other organophosphates and organophosphites such as tributoxy ethylphosphate; other phosphates and phosphonates such as chlorinated diphosphate and chlorinated polyphosphonate; and the like. Mixtures can also be used.
  • chlorinated alkyl phosphate esters such as AntiblazeTM 100 (chloro alkyl diphosphate ester) from Albright & Wilson Americas
  • alkyl phosphates and phosphites such as tributyl phosphate, tri-2-ethylhexyl phosphate, and triisoct
  • Suitable wetting, emulsifying, and conditioning plasticizers include alkyloxylated fatty alcohol phosphate esters such as oleth-2 phosphate, oleth-3 phosphate, oleth-4 phosphate, oleth-10 phosphate, oleth-20 phosphate, ceteth-8 phosphate, ceteareth-5 phosphate, ceteareth-10 phosphate, PPG ceteth-10 phosphate, and the like.
  • inventive polyurethane dispersions described herein can also be provided as blends w/ other dispersions. Examples of other dispersions that may be added to
  • compositions of the present invention include those described in US 4,636,546,
  • the present invention encompasses coatings and adhesives containing or derived from the novel materials described hereinabove.
  • the invention encompasses both the formulated coatings and adhesives as applied, and the cured coatings and adhesives.
  • the polyurethane dispersions of the present invention are suitable for use as protective coatings.
  • the polyurethane coatings of this invention which contain the aliphatic polycarbonates as described above have certain advantages over existing materials.
  • the coatings have unexpected and excellent hardness.
  • these coatings can be useful to protect materials such as wood, metal, stone, masonry, plastic, composites, fabrics, and the like.
  • the coatings have excellent UV stability.
  • these coatings can be useful to protect materials such as wood, metal, stone, masonry, plastic, composites, fabrics, and the like.
  • the present invention encompasses such coatings and coated articles.
  • the polyurethane dispersions of the present invention are suitable for use as adhesives.
  • the present invention encompasses polyurethane adhesives containing any of the polyurethane dispersions or prepolymers described hereinabove, as well as articles of manufacture in which parts are joined using the novel adhesives. II. Methods of Making
  • the present invention encompasses methods of making the prepolymer compositions and polyurethane dispersions described above.
  • methods of the present invention include the steps of:
  • R , R , R , R , Y, n, , x andy are at each occurrence as defined above and described in the classes and subclasses herein,
  • the aliphatic polycarbonate polyol provided in step (a), the reagents having a plurality of isocyanate groups provided in step (b), and the optional coreactants utilized in step (b) are independently selected from any of the specific embodiments of those materials defined above and described in the classes and subclasses herein.
  • the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of P2, P3, P4, P5, P6, P7, P8 and mixtures of two or more of these, where P2-P8 are as defined above and described in the classes and subclasses herein.
  • the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of compounds P2a through P2r-a where each P2
  • the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of Ql, Q2, Q3, Q4, and mixtures of any of these.
  • the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of:
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a
  • Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly (propylene carbonate) of formula Q2 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a
  • polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98%) -OH end groups;
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; and Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a
  • polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.
  • the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: aliphatic diisocyanates, aromatic
  • diisocyanates oligomeric diisocyanates, and difunctional isocyanate prepolymers.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises one or more aliphatic diisocyanates.
  • the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: HDI, IPDI, H 12 MDI, H6-XDI, TMDI, 1 ,4-cyclohexyl diisocyanate, 1,4- tetramethylene diisocyanate, trimethylhexane diisocyanate, and mixtures of any two or more of these.
  • the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: HDI, IPDI, H 12 MDI and mixtures of two or more of these.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises HDI.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises IPDI.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises H 12 MDI.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises H6-XDI.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises TMDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises oligomers or derivatives of any of the above aliphatic isocyanates. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises biurets of any of the above aliphatic isocyanates.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises one or more aromatic diisocyanates.
  • the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: 2,4-TDI, 2,6-TDI, MDI, XDI, TMXDI, and mixtures of any two or more of these.
  • the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: TDI and MDI.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises TDI.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises 2,4-TDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises 2,6-TDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises H6-XDI. In certain
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises MDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises XDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises TMXDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises oligomers or derivatives of any of the above aromatic isocyanates. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises biurets of any of the above aromatic isocyanates.
  • the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 1. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 2. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 3. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: EasaquaTM WAT; EasaquaTM WAT-1 ;
  • the method further includes controlling the ratio of the aliphatic polycarbonate polyol and, if present, the one or more coreactants, to the reagents having a plurality of isocyanate groups such that there is a molar excess of isocyanate groups.
  • the step of contacting aliphatic polycarbonate polyol with the reagent having a plurality of isocyanate groups is performed in the presence of a solvent.
  • the step is performed in a non-protic polar organic solvent.
  • the step is performed in acetone.
  • the step is performed in NMP.
  • the method further comprises mixing the solution of prepolymer thus formed with water and then distilling off at least a portion of the organic solvent.
  • step (b) further includes providing one or more catalysts.
  • catalysts provided in step (b) include tin based materials.
  • catalysts provided in step (b) are selected from the group consisting of di-butyl tin dilaurate, dibutylbis(lauryltliio)stannate, dibutyltinbis(isooctylmercapto acetate) and dibutyltinbis(isooctylmaleate), tin octaoate and mixtures of any of these.
  • catalysts provided in step (b) include tertiary amines.
  • catalysts provided in step (b) are selected from the group consisting of: DABCO,
  • one or more coreactants are provided in step (b).
  • the coreactant provided is selected from the group consisting of: other types of polyols (e.g. polyether polyols, polyester polyols, acrylics, or other polycarbonate polyols), and small molecules with functional groups reactive toward isocyanates such as hydroxyl groups, amino groups, thiol groups, and the like.
  • coreactants comprise molecules with two or more functional groups reactive toward isocyanates.
  • a coreactant provided in step (b) comprises a polyhydric alcohol. In certain embodiments, a coreactant provided in step (b) comprises a dihydric alcohol. In certain embodiments, the dihydric alcohol provided in step (b) comprises a C 2-40 diol.
  • the dihydric alcohol provided in step (b) is selected from the group consisting of: 1,2-ethanediol, 1 ,2-propanediol, 1,3 -propanediol, 1,2-butanediol, 1,3- butanediol, 1 ,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-l,3-diol, 2-butyl-2- ethylpropane-l,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-l,3-hexane diol, 2-methyl-l,3- propane diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12- dodecanediol, 2,2,4,4-t
  • a coreactant provided in step (b) comprises a dihydric alcohol selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.
  • a coreactant provided in step (b) comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid.
  • the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.
  • a coreactant provided in step (b) comprises a polymeric diol.
  • the polymeric diol provided in step (b) is selected from the group consisting of polyethers, polyesters, hydroxy-tenninated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these.
  • the polymeric diol has an average molecular weight less than about 2000 g/mol
  • a coreactant provided in step (b) comprises a triol or higher polyhydric alcohol.
  • a coreactant provided in step (b) is selected from the group consisting of: glycerol, 1 ,2,4-butanetriol, 2-(hydroxymethyl)- 1,3 -propanediol; hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4- cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these.
  • alkoxylated derivatives comprise ethoxylated or propoxylated compounds.
  • a coreactant provided in step (b) comprises a polyhydric alcohol with four to six hydroxy groups.
  • a coreactant present in step (b) comprises dipentaerithrotol or an alkoxylated analog thereof.
  • coreactant present in step (b) comprises sorbitol or an alkoxylated analog thereof.
  • a functional coreactant provided in step (b) comprises a polyhydric alcohol containing one or more moieties that can be converted to an ionic functional group.
  • the moiety that can be converted to an ionic functional group is selected from the group consisting of: carboxylic acids, esters, anhydrides, sulfonic acids, sulfamic acids, phosphates, and amino groups.
  • a coreactant provided in step (b) comprises a hydroxy- carboxylic acid having the general formula (HO) x Q(COOH3 ⁇ 4,, wherein Q is a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x andy are each integers from 1 to 3.
  • a coreactant provided in step (b) comprises a diol carboxylic acid.
  • a coreactant provided in step (b) comprises a bis(hydroxylalkyl) alkanoic acid.
  • a coreactant provided in step (b) comprises a bis(hydroxylmethyl) alkanoic acid.
  • the diol carboxylic acid provided in step (b) is selected from the group consisting of 2,2 bis-(hydroxymethyl)- propanoic acid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoic acid (dimethylolbutanoic acid; DMBA), dihydroxysuccinic acid (tartaric acid), and 4,4'- bis(hydroxyphenyl) valeric acid.
  • a coreactant comprises an N,N- bis(2-hydroxyalkyl)carboxylic acid.
  • a coreactant provided in step (b) comprises a polyhydric alcohol containing a sulfonic acid functional group.
  • a coreactant comprises a diol sulfonic acid.
  • a polyhydric alcohol containing a sulfonic acid is selected from the group consisting of: 2-hydroxymethyl-3-hydroxypropane sulfonic acid, 2-Butene-l,4-diol-2-sulfonic acid, and materials disclosed in U.S. Pat. No. 4,108,814 and US Pat. App. Pub. No. 2010/0273029 the entirety of each of which is incorporated herein by reference.
  • a coreactant provided in step (b) comprises a polyhydric alcohol containing a sulfamic acid functional group.
  • a polyhydric alcohol containing a sulfamic acid is selected from the group consisting of: [N,N-bis(2- hydroxyalkyl)sulfamic acid (where each alkyl group is independently a C 2-6 straight chain, branched or cyclic aliphatic group) or epoxide adducts thereof (the epoxide being ethylene oxide or propylene oxide for instance, the number of moles of epoxide added being 1 to 6) also epoxide adducts of sulfopolycarboxylic acids [e.g. sulfoisophthalic acid, sulfosuccinic acid, etc.], and aminosulfonic acids [e.g. 2-aminoethanesulfonic acid, 3- aminopropanesulfonic acid,
  • a coreactant a coreactant provided in step (b) comprises a polyhydric alcohol containing a phosphate group.
  • a coreactant comprises a bis (2-hydroxaikyl) phosphate (where each alkyl group is independently a C 2-6 straight chain, branched or cyclic aliphatic group).
  • a coreactant a coreactant provided in step (b) comprises bis (2-hydroxethyl) phosphate.
  • a coreactant a coreactant provided in step (b) comprises a polyhydric alcohol comprising one or more amino groups. In certain embodiments, a coreactant a coreactant provided in step (b) comprises an amino diol. In certain embodiments,
  • a coreactant a coreactant provided in step (b) comprises a diol containing a tertiary amino group.
  • a coreactant provided in step (b) is selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N- ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a- amino pyridine, dipropanolarnine, diisopropanolamine (DIP A), N- methyldiisopropanolamine, Diisopropanol-p-toluidine, N,N-Bis(hydroxyethyl)-3 - chloroaniline, 3-diethylaminopropane-l,2-diol, 3-dimethylaminopropane-l,2-diol and iV- hydroxyethylpiperidine.
  • DEA diethanolamine
  • MDEA
  • a coreactant a coreactant provided in step (b) comprises a diol containing a quaternary amino group.
  • a coreactant . a coreactant provided in step (b) is an acid salt or quatemized derivative of any of the amino alcohols described above.
  • Compounds having at least one crosslinkable functional group can also be provided in step (b), if desired.
  • examples of such compounds include those having carbonyl, amine, epoxy, acetoacetoxy, urea-formaldehyde, auto-oxidative groups that crosslink via oxidization, ethylenically unsaturated groups optionally with UV light activation, olefinic and hydrazide groups, blocked isocyanates, and the like, and mixtures of such groups and the same groups in protected forms.
  • a functional coreactant is provided in step (b), wherein the functional coreactant provides hydrophilic characteristics to the resulting chain-extended composition.
  • a functional coreactant is provided in step (b) comprises hydrophilic groups, ionic groups, or precursors to ionic groups any of which may act as internal emulsifiers and thereby aid in the formation of stable aqueous dispersions of the inventive compositions.
  • such functional coreactants comprise precursors of ionic groups.
  • functional coreactants comprise precursors of cationic groups.
  • functional coreactants comprise precursors of anionic groups.
  • the method further comprises a step after step (c) of treating the prepolymer with a reagent to convert the precursor of an ionic group into an ionic group.
  • a coreactant provided in step (b) comprises a carboxylic acid moiety and the method further comprises a step of treating the prepolymer with a base to form a carboxylate salt.
  • a coreactant provided in step (b) comprises an amine moiety and the method further comprises a step of treating the prepolymer with an acid or an alkylating agent to form an ammonium salt.
  • methods of the present invention further comprise the step of dispersing the prepolymer from step (c) in water.
  • the step of dispersing the prepolymer is performed in the presence of one or more chain-extending reagents wherein the chain extending reagents have a plurality of functional groups reactive toward isocyanates.
  • the chain extending reagent is dissolved in the aqueous phase prior to or during the step of dispersing the prepolymer.
  • the method includes dispersing the prepolymer from step (c) into water in the presence of a polyamine compound.
  • the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: mono-, bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, N- methyl diethanolamine, N-ethyl diethanolamine, N-propyl diethanolamine, N-isopropyl diethanolamine, N-butyl diethanolamine, N-isobutyl diethanolamine, N-oleyl
  • a compound selected from the group consisting of: mono-, bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, N- methyl diethanolamine, N-ethyl diethanolamine, N-propyl diethanolamine, N-isopropyl diethanolamine, N-butyl diethanolamine, N-isobutyl diethanolamine, N-oleyl
  • diethanolamine N-stearyl diethanolamine, ethoxylated coconut oil fatty amine, N-allyl diethanolamine, N-methyl diisopropanolamine, N-ethyl diisopropanolamine, N-propyl diisopropanolamine, N-butyl diisopropanolamine, cyclohexyl diisopropanolamine, N,N- diethoxylaniline, ⁇ , ⁇ -diethoxyl toluidine, N,N-diethoxyl-l-aminopyridine, N,N'-diethoxyl piperazine, dimethyl-bis-ethoxyl hydrazine, N,N'-bis-(2-hydroxyethyl)-N,N'-diethylhexahydr op-phenylenediamine, N-12-hydroxyethyl piperazine, polyalkoxylated amines, propoxylated methyl diethanolamine, N-methyl-N,N-
  • chain-extending agents are compounds that contain two amino groups.
  • chain-extending agents are selected from the group consisting of: ethylene diamine, 1,6-hexamethylene diamine, and 1,5-diamino-l-methyl-pentane.
  • the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: diethylene triamine (DETA), ethylene diamine (EDA), meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methyl pentane diamine, and mixtures thereof.
  • a compound selected from the group consisting of: diethylene triamine (DETA), ethylene diamine (EDA), meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methyl pentane diamine, and mixtures thereof.
  • the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, 3,3-dichlorobenzidene, 4,4'-methylene-bis-(2-cMoroaniline), 3,3- dichloro-4,4-diamino diphenylmethane, and sulfonated primary and/or secondary amines.
  • a compound selected from the group consisting of: propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, 3,3-dichlorobenzidene, 4,4'-methylene-bis-(2-cMoroaniline), 3,3- dichloro-4,4-diamino diphenylmethane,
  • the method includes dispersing the prepolymer from step (c) into water in the presence of a polyalcohol.
  • the polyalcohol has from 2 to 12 carbon atoms. In certain embodiments, the polyalcohol has from 2 to 8 carbon atoms.
  • the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: ethylene glycol, diethylene glycol, neopentyl glycol, butanediols, hexanediol, and the like, and mixtures thereof.
  • the methods include a step of providing a chain extending reagent that contains blocked functional groups that are liberated on contact with water and which once liberated will react with isocyanates.
  • methods of the present invention include combining the prepolymer with a blocked chain extending reagent.
  • the methods include a step of dispersing the combination of prepolymer and blocked chain extending reagent into water.
  • the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: hydrazine, substituted hydrazines, hydrazine reaction products, and the like, and mixtures thereof.
  • methods of the present invention comprise the step of applying any of the above described polyurethane dispersions to a surface. In certain embodiments, such methods further include the step of allowing the water to evaporate from the dispersion.
  • Aqueous polyurethane dispersions were synthesized using the NMP process incorporating novel polypropylene carbonate polyols for the first time.
  • Aqueous PUDs were also synthesized using three commercial diols as controls. PUD synthesis was successful for all of the polyols, however, the PUDs from the lowest molecular weight polypropylene carbonate polyol were not shelf stable. Particle size, viscosity, percent resin, and pH of the polypropylene carbonate polyol based PUDs were within normal range as compared to commercial controls. Films of the PUDs were prepared for evaluation and cured at ambient conditions for several days as well as force-cured in an oven overnight.
  • Films of the PUDs based on the polypropylene carbonate polyols were generally harder and more brittle than the control PUDs, especially for the samples which were force-cured as characterized by nanoindentation. Overall, the work showed that the polypropylene carbonate based polyols can be used to prepare aqueous PUDs.
  • Aqueous polyurethane dispersions have recently emerged to replace their solvent-based counterparts for a number of applications due to increasing health and environmental awareness.
  • Waterborne PUDs are an important class of polymer dispersion that can be used in many industrial applications such as coatings for wood fmshing; glass fiber sizing; adhesives; automotive topcoats and other applications (see Keyvani, Advances in Polymer Technology, 2003, 22, 218-224).
  • Polyurethanes are generally synthesized from isocyanates and polyols, and while the incorporation of amine functional chain extenders results in the formation of urea groups these tend to be included in the broad category of polyurethanes. Due to a large number of available isocyanates and polyols, it is possible to get a broad spectrum of excellent properties. Recently, Novomer has developed a novel process for the synthesis of low molecular weight polypropylene carbonate polyols from the metal-catalyzed
  • the synthesis involves formation of an isocyanate functional prepolymer followed by dispersion in water and chain extension to obtain the aqueous PUD (see Nasrallah et al., J. Coat. Technol. Res., 2009, 6, 1-10; Nasrallah et al., Polymer Preprints (American Chemical Society, Division of Polymer Chemistry), 2007, 48, 175-176).
  • Viscosity measurements were done using Brookfield DV-II+ Pro viscometer. The viscosity was measured at room temperature around 23 °C with spindle 06 at 100 rpm. The particle size was measured on water-diluted samples using Submicron Particle Sizer, NICOMPTM 380 and both Gaussian and Nicomp methods were used.
  • An automated surface energy (SE) measurement unit manufactured by Symyx Discovery Tools, Inc and First Ten Angstroms was used to measure the SE of PUD coatings. Droplets of water and methylene iodide (MI) were deposited on the PUD coating separately and a CCD camera imaged the droplets and then automated image analysis was used to determine the contact angles (CA). Three droplets of water and MI were used for each measurement. SE was calculated from the CA data using the Owens- Wendt equation. Quasistatic Nanoindentation was performed using Hysitron Triboindenter (Hysitron
  • MICROMASTER ® micrometer The analysis was carried out from -75 °C to 100 °C at a frequency of 1 Hz and a ramp rate of 5 °C m T 1 .
  • the dispersing water is at room temperature and it is added under high agitation, 500 - 2200 rpm, over a 25 min period. Then, EDA and water are combined at ambient temperature at 25 °C, and added to the reaction mixture drop-wise over 10 - 15 min with agitation of 500 rpm. The agitation is continued for another 2 h to complete the water reaction with residual isocyanate and form the dispersion.
  • Table 1 shows all the PUDs synthesized in 400 - 500 g quantities and they are good and stable. It is important to mention that the PUDs based on NOV 7E21-1 and NOV 7E21-2 became paste or solid cake in 2 weeks and 1 week, respectively, hence incomplete characterization was performed on these two PUDs.
  • Polyurethane coating films were also prepared by drawdown over microscope glass slides. Curing was achieved by allowing the coatings to lie horizontally overnight at ambient conditions. The water and MI contact angles and surface energies for PUD coatings cured at room temperature are given in Table 4. Another set of coatings were cured overnight at ambient conditions followed by an overnight heat treatment at 70 °C. These coatings were used for hardness measurements using Nanoindentation. The reduced modulus and hardness for PUD coatings are given in Figures 1 and 2, respectively. Both the reduced modulus and hardness are high for the polypropylene carbonate polyols compared to the control PUDs. PUD coating films were also prepared by drawdown over TEFLON ® sheets glued to aluminum panels and cured at room temperature (RT).
  • RT room temperature
  • Tg was obtained from the maximum peak in the tan ⁇ curves. Additional characterization work such as tensile strength, Konig Pendulum
  • Aqueous PUDs were synthesized using novel polypropylene carbonate diols for the first time. Two of the three PUDs are shelf stable with most of the desired properties of a PUD. It is likely that adjustments to the PUD recipe can improve the stability of the PUD with the lowest MW polypropylene carbonate diol. Overall, the film properties indicate that the PUDs made with the polypropylene carbonate diols polyols are harder and more brittle than the control polyols as characterized by Nanoindentation. Introducing a slight amount of cross-linking into the PUD might help overcome some of these property limitations. More characterization work is in progress and will be discussed in future publication. Example II.
  • Aqueous polyurethane dispersions were synthesized using the NMP process incorporating candidate polycarbonate polyols supplied by Novomer Inc. as well as three commercial controls. PUD synthesis was successful for all of the polyols, however, the PUDs from the lowest molecular weight candidate polyol was not shelf stable. Particle size and viscosity of the PUDs was within normal ranges. Films of the PUDs were prepared for evaluation and cured at ambient conditions for several days as well as force-cured in an oven overnight.
  • Aqueous polyurethane dispersions have recently emerged to replace their solvent-based counterparts for various applications due to increasing health and
  • Novomer has developed an amorphous, colorless thermoplastic polymer i.e., polypropylene carbonate polyols which decomposes into environmentally benign products making it the perfect solution for broad applications in the electronics, brazing and ceramics industries.
  • polypropylene carbonate polyols which decomposes into environmentally benign products making it the perfect solution for broad applications in the electronics, brazing and ceramics industries.
  • These novel polyols are produced from the metal-catalyzed copolymerization of carbon dioxide with epoxides.
  • This example reports the synthesis of aqueous PUD using these polypropylene carbonate polyols by traditional method in the laboratory.
  • the scheme for the synthesis of PUD is shown in Example I (Scheme A). The synthesis involves formation of an isocyanate functional prepolymer followed by dispersion in water and chain extension to obtain the aqueous PUD.
  • Polyurethanes are generally synthesized from isocyanates and polyols, and while the incorporation of amine functional chain extenders results in the formation of urea groups, these tend to be included in the broad category of polyurethanes. Due to a large number of available isocyanates and polyols, it is possible to get a broad spectrum of excellent properties.
  • the primary focus of this example was the synthesis of PUDs using candidate poly(propylene carbonate) diols, and determination of the basic film properties of the PUDs.
  • the synthesized PUDs are compared with the PUDs obtained using Bayer polyols such as polyester and polycarbonate polyester polyols.
  • DMPA dimethylolpropionic acid
  • NMP N-Methyl-2-pyrrolidone
  • DBTDL dibutyltin dilaurate
  • TEA triethylamine
  • EDA ethylenediamine
  • Linear polyester polyol (Polyester PE 170HNA), polycarbonate polyester polyols (DESMOPHEN ® C 2100 and DESMOPHEN ® C 2200) and dicyclohexylmethane diisocyanate ( ⁇ , ⁇ -methylenebis [4-isocyanatocyclohexane]) were obtained from Bayer MaterialScience.
  • a general synthesis procedure was followed for synthesis using the laboratory method.
  • a one liter reactor vessel was fitted with an agitator, nitrogen inlet, and water condenser.
  • the reactor was heated with an oil bath on a hotplate.
  • the polyol, DMPA, diisocyanate, and MP are charged and stirred at 250 rpm until the mixture becomes homogenous.
  • DBTDL catalyst is added, the mixture is heated to 90 °C, and the temperature is controlled so that it does not go above 95 °C to avoid side reactions or exotherm.
  • the theoretical NCO content is reached, the mixture is cooled to 70 °C and TEA is added with an increase agitation to 500 rpm.
  • the dispersing water is at room temperature and it is added under high agitation, 500 - 2200 rpm, over a 25 min period. Then, EDA and water are combined at ambient temperature at 25 °C, and added to the reaction mixture drop- wise over 10 - 15 min with agitation of 500 rpm. The agitation is continued for another 2 h to complete the water reaction with residual isocyanate and form the dispersion.
  • NCO titrations were performed to obtain the free NCO values. A aliquot of prepolymer was drawn from the reactor vessel, weighed, dissolved in toluene and reacted with 0.1 N dibutyl amine and titrated against 0.1 N HCl. Using the blank titer value, sample titer value and weight of prepolymer, free NCO values were calculated at different timings of PUD synthesis and these are listed in Table 5.
  • the polyol starting materials have the following general structure:
  • NOV-7E21 is a polyol of formula Ql, and was characterized by the supplier, Novomer, as having an Mn of 1102 g/mol (i.e. n is, on average in the composition, about 4.8).
  • the polymer has a PDI of 1.13, contains greater than 99% -OH end groups, and has no detectable ether linkages as determined by NMR.
  • NOV-94B0 is a polyol of formula Ql, and was characterized by the supplier,
  • Novomer as having an Mn of 2107 g/mol (i.e. n is, on average in the composition, about
  • the polymer has a PDI of 1.06, contains greater than 99% -OH end groups, and has no detectable ether linkages as determined by NMR.
  • NOV-7DF1 is a polyol of formula Ql, and was characterized by the supplier, Novomer, as having an Mn of 2939 g/mol (i.e. n is, on average in the composition, about
  • the polymer has a PDI of 1.04, contains greater than 99% -OH end groups, and has no detectable ether linkages as determined by NMR.
  • the polyols NOV-7E21, NOV-94B0, and NOV-7DF1 were synthesized according to the following method: propylene oxide, chain transfer agent (CTA), cobalt catalyst E-2 and co-catalyst E-2c were added to a 2 gallon stainless steel autoclave and the polymerization was carried out according to the conditions disclosed in WO 2010028362.
  • the reaction was quenched and the polyol was purified according to the conditions disclosed in WO 2010/033705 and WO 2010/033703, respectively.
  • the ratios of the propylene oxide, catalyst complex and chain transfer agent were modified according to the description in WO 2010028362 to achieve the stated Mn values of the three polyol samples.
  • a low catalyst to chain transfer agent ratio was maintained to produce polyols with a high percentage of -OH end-groups.
  • the polyols were further characterized by GPC to get the molecular weight (Mn) and molecular weight distribution (PDI).
  • Mn molecular weight
  • PDI molecular weight distribution
  • High throughput Symyx Rapid GPC was used for determining polymer Mn and PDI.
  • the GPC system is equipped with 2 x PLgel Mixed-B columns (10 ⁇ particle size) and has high-speed columns and an evaporative light scattering detector (PL-ELS- 1000). Solutions of 1 mg mL "1 sample in THF were prepared before run; calibration was carried out using polystyrene standards and THF was used as eluent at a flow rate of 2.0 mL min "1 .
  • Mn and PDI were determined using EPOCHTM software. Mn and PDI of the control polyols from Bayer and candidate polyols are listed in Table 6.
  • the polyols were also characterized by differential scanning calorimetry (DSC) to get the Tg and the details are listed in Table 6.
  • DSC experiments were performed utilizing a TA Instruments Q2000 DSC with a heat-cool-heat cycle. The sample size ranged from 4 mg to 10 mg. Temperature was ramped from -150 °C to 50 °C at 10 °C m T 1 in nitrogen for polyols.
  • the control polyester polyol showed two transitions. Due to the low molecular weight, the polyol probably consists of hexanediol rich molecules and neopentyl glycol rich molecules. The Tgs of the control polycarbonate polyols are higher than that of the polyester.
  • the candidate polyols exhibit a strong relationship between the molecular weight and the Tg.
  • the highest MW candidate polyol has a Tg similar to the control polycarbonates.
  • the polyols were also characterized using matrix-assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry to obtain the molecular weight (Mri) and their distribution.
  • MALDI-TOF mass spectra were recorded on a Bruker Ultraflex II spectrometer equipped with a 1.85 m linear flight tube and a Smart beam laser. All mass spectra were obtained in positive ion and reflectron mode.
  • the average particle size was measured with water-diluted samples of PUD using Submicron Particle Sizer, NICOMPTM 380, which uses the method of dynamic light scattering (photocorrelation spectroscopy). Both Gaussian and Nicomp methods for calculating particle size averages were used.
  • the particle size obtained for all the PUDs are given in Table 7.
  • the particle sizes obtained for all the PUDs are less than 500 nm in most cases indicating that a stable dispersion is formed.
  • One can notice that the particle size is very broad in the case of NOV 7E21-1 and NOV 94B0-1 in the first attempt of synthesis.
  • PUD coating films were prepared by drawdown over TEFLON sheets glued to aluminum panels. PUD coating films were also prepared by drawdown over microscope glass slides and aluminum Q panels. Curing was achieved by allowing the coatings to lie horizontally for overnight at ambient conditions and is referred as room temperature cured coatings. Another set of coatings were cured for overnight at ambient conditions followed by an overnight heat treatment at 70 °C. Free films were obtained by releasing the coatings from the TEFLON ® sheet using a spatula at one edge of the coating. PUDs were
  • Control PUDs have Tg- below zero degrees and most of the candidate PUD have Tgs close to zero or above zero degrees.
  • Quasistatic Nanoindentation was performed using Hysitron Triboindenter (Hysitron Incorporated) mounted with a Berkovich tip.
  • the indenting was done in load control mode with the following operating parameters: a 5 second loading, a hold time of 5 seconds at the maximum load to allow visco-elastic dissipation, and a 5 second unloading.
  • Maximum load was 300 ⁇ and pre-load was set to 2 ⁇ .
  • Moduli of the samples were obtained from the unloading segment of a resulting force-depth curve using the Oliver and Pharr method.
  • PUD coating films prepared on microscope glass slides were used to obtain reduced modulus and hardness using Nanoindentation.
  • the reduced modulus and hardness for PUD coatings cured at room temperature as well as coating cured at RT followed by 70 °C are given in Figure 14.
  • the room temperature cured PUDs seem to be soft and once they are cured at 70 °C they seem to become much harder. This is in particular applicable to all candidate PUDs.
  • the control PUDs does not seems to change much after curing at 70 °C.
  • Room temperature cured samples are expected to contain residual NMP, which can act as a plasticizer. Curing at 70 °C can drive off residual NMP and yield a film that is not plasticized. Thus the modulus and hardness of the coating is increased.
  • Dynamic mechanical analysis was performed using a TA Instruments Q800 DMA in rectangular tension/compression geometry. Free films of the cured materials were obtained by removing the material from TEFLON ® covered aluminum substrate using a spatula. Sample size was 21 mm x 5 mm and film thickness was measured using a
  • Hardness testing was performed with a BYK Gardener pendulum hardness tester in Konig mode. Test results are reported as the time in seconds for the swing to be damped from a higher to a lower angle i.e. from 6 to 3 degrees. Usually harder coatings give longer times. PUD coatings were made on aluminum panels and they were cured at RT as well as at 70 °C. The results are presented in Figure 17. From the results it is clear that the hardness values of the control coatings do not change upon curing at 70 °C. On the other hand, all the candidate PUDs show a large increase in the hardness values after curing at RT followed by 70 °C curing overnight.
  • Cross-hatch adhesion was done using the ASTM procedure (D3359-97) and the results are given in Table 9.
  • the most widely used specification test is the cross-hatch adhesion test. Usually using a device with 6 or 11 sharp blades, a scratch mark pattern is made across the sample, followed by a 2nd set cut perpendicular to the first. In our case since the device was not enough sharp, 11 cuts were made using a sharp blade and also in perpendicular direction. A strip of pressure-sensitive adhesive tape is pressed over the pattern of squares and pulled off.
  • PUD coatings were subjected to four different chemical solutions such as 10 %
  • aqueous PUDs can be successfully synthesized using polycarbonate diols supplied by Novomer. Two of the three PUDs are stable with most of the desired properties of a PUD. It is likely that adjustments to the PUD recipe (increasing neutralization, acid content) can improve the stability of the PUD with the lowest MW candidate resin.
  • the film properties indicate that the PUDs made with the candidate polyols are harder and more brittle than the control polyols after the NMP is driven off. It is also interesting that there seemed to be little variation in the hardness and Tg of the PUDs made from the candidate polyols considering that the starting polyols had a wide range of Tgs.
  • the candidate polyol-based PUDs also were not able to withstand high humidity. Introducing a slight amount of crosslinking into the PUD might help overcome some of these property limitations.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne, dans un aspect, des dispersions aqueuses de polyuréthane (PUD) contenant des polyols de polycarbonates aliphatiques dérivés d'époxydes et de CO2. Dans un autre aspect, l'invention concerne des compositions de revêtement et des compositions adhésives obtenues à partir des dispersions aqueuses de polyuréthane de l'invention. Dans d'autres aspects, l'invention concerne des prépolymères à terminaison isocyanate contenant une pluralité de segments polyol dérivés d'époxyde-CO2 liés par l'intermédiaire de liaisons uréthanes formées par réaction avec des composés de polyisocyanate. Ces prépolymères sont utiles pour préparer des polymères supérieurs et/ou des dispersions aqueuses de polyuréthane.
PCT/US2011/041276 2010-06-21 2011-06-21 Dispersions aqueuses de polyuréthane WO2011163250A1 (fr)

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WO2013138161A1 (fr) * 2012-03-12 2013-09-19 Novomer, Inc. Compositions de polymère et procédés
WO2013158621A1 (fr) * 2012-04-16 2013-10-24 Novomer, Inc. Compositions adhésives et procédés
WO2013158845A1 (fr) * 2012-04-18 2013-10-24 Ndsu Research Foundation Résines de carbamate de glycidyle (cg) linéaires pour des revêtements très souples
WO2013163442A1 (fr) * 2012-04-25 2013-10-31 Novomer, Inc. Polyols de polycarbonate aliphatiques contenant des groupes silyles
EP2855558A4 (fr) * 2012-05-24 2015-12-16 Novomer Inc Compositions de polycarbonate polyol et procédés associés
CN107177035A (zh) * 2017-07-20 2017-09-19 广东工业大学 一种聚氨酯预聚体及其制备方法和紫外光固化聚氨酯预聚体组合物
WO2019129111A1 (fr) * 2017-12-28 2019-07-04 Covestro Deutschland Ag Dispersion aqueuse
CN109970994A (zh) * 2017-12-28 2019-07-05 科思创德国股份有限公司 水性分散体
EP3546493A1 (fr) 2018-03-28 2019-10-02 Covestro Deutschland AG Dispersion aqueuse
CN110511350A (zh) * 2019-07-25 2019-11-29 华南理工大学 一种聚碳型水性聚氨酯及其制备方法
US10513638B2 (en) 2015-08-03 2019-12-24 Repsol, S.A. Adhesive composition comprising polyether carbonate polyols
WO2020068796A1 (fr) 2018-09-24 2020-04-02 Saudi Aramco Technologies Company Copolymères séquencés de polycarbonate et procédés associés
CN111040426A (zh) * 2019-12-27 2020-04-21 安徽匠星联创新材料科技有限公司 一种纳米氧化锌改性水性聚氨酯乳液及其制备方法
CN113336470A (zh) * 2021-06-23 2021-09-03 宁夏共享化工有限公司 一种无机粘结剂用复合型浆状固化剂及其制备方法
US20230062606A1 (en) * 2021-08-04 2023-03-02 Hyundai Motor Company Polyurethane adhesive composition for carbon emission reduction and method of preparing same
CN116046825A (zh) * 2023-04-03 2023-05-02 中国核动力研究设计院 辐照后弥散燃料纳米压痕试样及其制备方法

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WO2013138161A1 (fr) * 2012-03-12 2013-09-19 Novomer, Inc. Compositions de polymère et procédés
JP2018024893A (ja) * 2012-04-16 2018-02-15 ノボマー， インコーポレイテッド 接着剤組成物および方法
WO2013158621A1 (fr) * 2012-04-16 2013-10-24 Novomer, Inc. Compositions adhésives et procédés
US9834710B2 (en) 2012-04-16 2017-12-05 Saudi Aramco Technologies Company Adhesive compositions and methods
CN110791246B (zh) * 2012-04-16 2022-04-22 沙特阿美技术公司 粘合剂组合物和方法
US20150083326A1 (en) * 2012-04-16 2015-03-26 Novomer, Inc. Adhesive compositions and methods
JP2015514848A (ja) * 2012-04-16 2015-05-21 ノボマー， インコーポレイテッド 接着剤組成物および方法
CN114774053A (zh) * 2012-04-16 2022-07-22 沙特阿美技术公司 粘合剂组合物和方法
CN104428370A (zh) * 2012-04-16 2015-03-18 诺沃梅尔公司 粘合剂组合物和方法
CN110791246A (zh) * 2012-04-16 2020-02-14 沙特阿美技术公司 粘合剂组合物和方法
WO2013158845A1 (fr) * 2012-04-18 2013-10-24 Ndsu Research Foundation Résines de carbamate de glycidyle (cg) linéaires pour des revêtements très souples
WO2013163442A1 (fr) * 2012-04-25 2013-10-31 Novomer, Inc. Polyols de polycarbonate aliphatiques contenant des groupes silyles
US9388277B2 (en) 2012-05-24 2016-07-12 Novomer, Inc. Polycarbonate polyol compositions and methods
EP3486269A1 (fr) 2012-05-24 2019-05-22 Saudi Aramco Technologies Company Système pour la polymérisation de co2 et des époxydes et procédé associé
EP2855558A4 (fr) * 2012-05-24 2015-12-16 Novomer Inc Compositions de polycarbonate polyol et procédés associés
US9850345B2 (en) 2012-05-24 2017-12-26 Saudi Aramco Technologies Company Polycarbonate polyol compositions and methods
US10513638B2 (en) 2015-08-03 2019-12-24 Repsol, S.A. Adhesive composition comprising polyether carbonate polyols
CN107177035B (zh) * 2017-07-20 2019-10-15 广东工业大学 一种聚氨酯预聚体及其制备方法和紫外光固化聚氨酯预聚体组合物
CN107177035A (zh) * 2017-07-20 2017-09-19 广东工业大学 一种聚氨酯预聚体及其制备方法和紫外光固化聚氨酯预聚体组合物
WO2019129111A1 (fr) * 2017-12-28 2019-07-04 Covestro Deutschland Ag Dispersion aqueuse
CN111527118A (zh) * 2017-12-28 2020-08-11 科思创德国股份有限公司 水性分散体
CN109970994A (zh) * 2017-12-28 2019-07-05 科思创德国股份有限公司 水性分散体
EP3546493A1 (fr) 2018-03-28 2019-10-02 Covestro Deutschland AG Dispersion aqueuse
WO2020068796A1 (fr) 2018-09-24 2020-04-02 Saudi Aramco Technologies Company Copolymères séquencés de polycarbonate et procédés associés
CN110511350A (zh) * 2019-07-25 2019-11-29 华南理工大学 一种聚碳型水性聚氨酯及其制备方法
CN110511350B (zh) * 2019-07-25 2021-10-26 华南理工大学 一种聚碳型水性聚氨酯及其制备方法
CN111040426A (zh) * 2019-12-27 2020-04-21 安徽匠星联创新材料科技有限公司 一种纳米氧化锌改性水性聚氨酯乳液及其制备方法
CN113336470A (zh) * 2021-06-23 2021-09-03 宁夏共享化工有限公司 一种无机粘结剂用复合型浆状固化剂及其制备方法
US20230062606A1 (en) * 2021-08-04 2023-03-02 Hyundai Motor Company Polyurethane adhesive composition for carbon emission reduction and method of preparing same
CN116046825A (zh) * 2023-04-03 2023-05-02 中国核动力研究设计院 辐照后弥散燃料纳米压痕试样及其制备方法
CN116046825B (zh) * 2023-04-03 2023-06-27 中国核动力研究设计院 辐照后弥散燃料纳米压痕试样及其制备方法

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