WO2013138161A1

WO2013138161A1 - Polymer compositions and methods

Info

Publication number: WO2013138161A1
Application number: PCT/US2013/029682
Authority: WO
Inventors: Scott D. Allen; Vahid Sendijarevic; Aisa Sendijarevic
Original assignee: Novomer, Inc.
Priority date: 2012-03-12
Filing date: 2013-03-07
Publication date: 2013-09-19

Abstract

The present invention encompasses thermoplastic polyurethane compositions comprising aliphatic polycarbonate chains. In one aspect, the present invention encompasses thermoplastic polyurethanes derived from aliphatic polycarbonate polyols and polyisocyanates wherein the polyol chains contain a primary repeating unit having a structure, In another aspect, the invention provides articles comprising the inventive TPU compositions as well as methods of making such compositions.

Description

POLYMER COMPOSITIONS AND METHODS

PRIORITY CLAIM

This application claims priority to US Application Serial Nos. 61/609,923, filed March 12, 2012, and 61/678, 135, filed August 1, 2012, each of which is incorporated herein by reference in its entirety.

GOVERNMENT SUPPORT

The invention was made in part with United States Government support under grants DE-FE0002474 awarded by the Department of Energy. The United States Government has certain rights in the invention.

FIELD OF THE INVENTION

This invention pertains to the field of polymers. More particularly, the invention pertains to thermoplastic polyurethanes (TPUs) incorporating aliphatic polycarbonate polyols having a high percentage of -OH end groups.

BACKGROUND OF THE INVENTION

Significant effort has been expended in recent years in the pursuit of more renewable and sustainable materials for polyurethanes. Much of this work has been focused on biomass-based polyols, or "natural oil polyols" from sources such as soy and castor oils. The present invention describes an entirely different approach to sustainable polyols in which waste carbon dioxide is used as a raw material and sequestered in a useful polyol product.

In recent years a number of companies have explored renewable alternatives to petroleum-based polyols such as soy and castor oil polyols for various polyurethane applications. Novomer has developed a unique route to high performance renewable polyurethanes using a proprietary catalyst system to transform waste carbon dioxide (C0₂) into valuable polyols. This technology delivers high performance, renewable polycarbonate polyols that are up to 50% CO2 by weight, have a 3-9x carbon footprint advantage vs.

existing petroleum-based materials, and can be cost competitive with existing polyether and polyester polyols at scale. The polymer structure and molecular weight of these polyols can be tailored to meet the demands of specific applications.

Thermoplastic polyurethanes (TPUs) are a unique urethanes product group in that they are supplied as fully-reacted products so that the processor/customer only has to reshape it into the final form required. Nearly all other polyurethane products are supplied as reactive liquids. TPUs can either be designed to be processed on conventional thermoplastic equipment or by solvent processing in a range of solvents. In the former case they are used in injection molding or extrusion processes to create solid components. In solvent-based applications, TPUs are typically used as adhesives or coatings.

TPUs can be used to produce a wide range of products with different properties by varying their chemical building blocks. Recently, Novomer has developed a novel process for the synthesis of low molecular weight aliphatic polycarbonate polyols from the metal- catalyzed copolymerization of carbon dioxide with epoxides (US 8,247,520). These polyols have an improved carbon footprint relative to existing materials and also have a unique polycarbonate backbone which delivers significant "renewable" content and improved and unexpected performance properties of finished TPU systems.

SUMMARY OF THE INVENTION

In one aspect, the present invention encompasses thermoplastic polyurethanes derived from polyisocyanates and aliphatic polycarbonate polyols derived from the copolymerization of CO2 with one or more epoxides. In one embodiment, the aliphatic polycarbonate polyol chains contain a primary repeating unit having a structure:

where R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain, independently selected from the group consisting of -H, fluorine, an optionally substituted C_1-4o aliphatic group, an optionally substituted C_1-2o heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R¹, R², R³, and R⁴ may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

In certain embodiments, such aliphatic polycarbonate chains are derived from the copolymerization of carbon dioxide with one or more epoxide substrates. Such

copolymerizations are exemplified in published PCT application WO/2010/028362 the entirety of which is incorporated herein by reference. In some embodiments, the aliphatic polycarbonate chains are derived from ethylene oxide, propylene oxide, or optionally substituted C3-30 aliphatic epoxides, or mixtures of two or more of these. In certain embodiments, the aliphatic polycarbonate chains have a number average molecular weight (M») less than about 20,000 g/mol. In certain embodiments, the aliphatic polycarbonate polyols have a functional number between about 1.8 and about 6.

In another aspect, the present invention encompasses urethane compositions comprising aliphatic polycarbonate polyols derived from the alternating copolymerization of one or more epoxides and carbon dioxide. In certain embodiments, the inventive urethane compositions comprise thermoplastic polyurethanes (TPUs). In certain embodiments, the inventive urethanes comprise TPUs for injection molding applications. In certain embodiments, the inventive urethanes comprise TPUs to be used in extrusion-processed applications. In certain embodiments, the inventive urethanes comprise TPUs for blow molding, slush molding, thermoforming or calendaring.

In another aspect, the present invention encompasses methods of making thermoplastic polyurethane compositions. In certain embodiments, the methods comprise a step of contacting the aliphatic polycarbonate polyol with one or more isocyanate compounds under conditions to promote the chain extension of the polyol chains by formation of urethane linkages. In certain embodiments, this contacting step occurs in a batch process using either hand mixing and/or an agitated vessel. In certain embodiments, this contacting step occurs via a band casting process in which the raw materials are individually fed to a mixing head which is fitted with a spreader system to deliver a precise stream of mixed material onto a continuous conveyor belt. In certain embodiments, this contacting process occurs via reactive extrusion in which all components are metered in one step into a twin- screw extruder where they mix and react during transfer to a die or pelletizer. In another aspect, the present invention encompasses isocyanate-terminated prepolymers comprisinig a plurality of epoxide-CC -derived polyol segments linked via urethane bonds formed from reaction with polyisocyanate compounds. Such prepolymers can be useful for the manufacture of higher TPU polymers.

DEFINITIONS

Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75^th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March 's Advanced Organic Chemistry, 5^th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3^rd Edition, Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.

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. Thus, 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. In certain embodiments, the compounds of the invention are enantiopure compounds. In certain embodiments, mixtures of enantiomers or diastereomers are provided.

Furthermore, 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. In addition to the above-mentioned compounds per se, this invention also encompasses compositions comprising one or more compounds. As used herein, the term "isomers" includes any and all geometric isomers and stereoisomers. For example, "isomers" include cis- and ira«s-isomers, E- and Z- isomers, R- and 5-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention. For instance, 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."

Where a particular enantiomer is preferred, it 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

chromatography (HPLC) and the formation and crystallization of chiral salts or prepared by asymmetric syntheses. See, for example, Jacques, et al, Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981); Wilen, S.H., et al., Tetrahedron 33:2725 (1977); Eliel, E.L. Stereochemistty of Carbon Compounds (McGraw-Hill, NY, 1962); Wilen, S.H. Tables of Resolving Agents and Optical Resolutions p. 268 (E.L. Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, IN 1972).

The term "epoxide", as used herein, refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. Such epoxides may be further optionally substituted as defined herein. In certain embodiments, epoxides comprise a single oxirane moiety. In certain embodiments, epoxides comprise two or more oxirane moieties.

The term "polymer", as used herein, 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. In certain embodiments, a polymer is comprised of substantially alternating units derived from C0₂ and an epoxide (e.g., poly(ethylene carbonate). In certain embodiments, a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer incorporating two or more different epoxide monomers. With respect to the structural depiction of such higher polymers, the convention of showing enchainment of different monomer units separated by a slash may be used herein

. These structures are to be interpreted to encompass copolymers incorporating any ratio of the different monomer units depicted unless otherwise specified. This depiction is also meant to represent random, tapered, block co-polymers, and combinations of any two or more of these and all of these are implied unless otherwise specified.

The terms "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).

The term "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. In certain embodiments, 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

(cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term "heteroaliphatic," as used herein, 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. As used herein, the term "bivalent Ci_8 (or C1-3) saturated or unsaturated, straight or branched, hydrocarbon chain", refers to bivalent alkyl, alkenyl, and alkynyl, chains that are straight or branched as defined herein.

The term "unsaturated", as used herein, means that a moiety has one or more double or triple bonds.

The terms "cycloaliphatic", "carbocycle", or "carbocyclic", 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. In some embodiments, the cycloalkyl has 3-6 carbons. The terms "cycloaliphatic", "carbocycle" or "carbocyclic" 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. In certain embodiments, the term "3- to 7-membered carbocycle" refers to a 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclic ring. In certain embodiments, the term "3- to 8-membered carbocycle" refers to a 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring. In certain embodiments, the terms "3- to 14-membered carbocycle" and "C3-14 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.

The term "alkyl," as used herein, 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. Examples of 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.

The term "alkenyl," as used herein, 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.

The term "alkynyl," as used herein, 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.

The term "alkoxy", as used herein refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom. Examples of alkoxy, include but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy.

The term "acyl", as used herein, refers to a carbonyl -containing functionality, e.g., - C(=0)R , wherein R is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl group, or is a substituted (e.g., with hydrogen or aliphatic, heteroaliphatic, aryl, or heteroaryl moieties) oxygen or nitrogen containing functionality (e.g., forming a carboxylic acid, ester, or amide functionality). The term "acyloxy", as used here, refers to an acyl group attached to the parent molecule through an oxygen atom. The term "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. The term "aryl" may be used interchangeably with the term "aryl ring". In certain embodiments of the present invention, "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. In certain embodiments, the terms "6- to 10-membered aryl" and "Ce-ιο aryl" refer to a phenyl or an 8- to 10-membered polycyclic aryl ring.

The terms "heteroaryl" and "heteroar-", used alone or as part of a larger moiety, e.g., "heteroaralkyl", or "heteroaralkoxy", refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 π electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms. The term "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. The terms "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. A heteroaryl group may be mono- or bicyclic. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring", "heteroaryl group", or "heteroaromatic", any of which terms include rings that are optionally substituted. The term "heteroaralkyl" refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted. In certain embodiments, 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. In certain

embodiments, 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.

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. When used in reference to a ring atom of a heterocycle, the term "nitrogen" includes a substituted nitrogen. As an example, 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 ⁺NR (as in N-substituted pyrrolidinyl). In some embodiments, the term "3- to 7-membered 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. In some embodiments, 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. Examples of such saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms "heterocycle", "heterocyclyl", "heterocyclyl ring", "heterocyclic group", "heterocyclic moiety", and "heterocyclic radical", are used interchangeably herein, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, where the radical or point of attachment is on the heterocyclyl ring. A heterocyclyl group may be mono- or bicyclic. The term "heterocyclylalkyl" refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions

independently are optionally substituted.

As used herein, the term "partially unsaturated" refers to a ring moiety that includes at least one double or triple bond. The term "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.

As described herein, compounds of the invention may contain "optionally substituted" moieties. In general, the term "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. Unless otherwise indicated, 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. The term "stable", as used herein, 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.

Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH₂)₀^R°; -(CH₂)CMOR⁰; -0-(CH₂)O- ₄C(0)OR °; -(CH₂)o-4CH(OR⁰)₂; -(CH₂) -4SR⁰; -(ΟΗ₂)(ΜΡ¾ which may be substituted with R°; -(CH₂)a 0(CH₂)o-iPh which may be substituted with R°; -CH=CHPh, which may be substituted with R°; -N0₂; -CN; -N₃; -(CH₂)C N(R⁰)₂; -(CH₂)<MN(R^O)C(0)R°; - N(R°)C(S)R°; -(CH₂)o N(R⁰)C(0)NR°₂; -N(R°)C(S)NR°₂; -(CH₂)₀^N(R^o)C(O)OR°; - N(R°)N(R°)C(0)R°; -N(R°)N(R°)C(0)NR°₂; -N(R°)N(R°)C(0)OR°; -(CH₂)CMC(0)R°; - C(S)R°; -(CH₂)o-4C(0)OR°; -(C¾)(MC(0)N(R⁰)₂; -(CH₂)<MC(0)SR°; -(CH₂)₀_

4C(0)OSiR°₃; -(CH₂)o-40C(0)R°; -0C(0)(CH₂)o SR- SC(S)SR°; -(CH₂)₀-4SC(O)R°; - (CH₂)C C(0)NR°₂; -C(S)NR°₂; -C(S)SR°; -SC(S)SR°, -(CH₂)₀^OC(O)NR°₂; - C(0)N(OR°)R°; -C(0)C(0)R°; -C(0)CH₂C(0)R°; -C(NOR°)R°; -(CH₂)CMSSR⁰; -(C¾V ₄S(0)₂R°; -(CH₂)o^S(0)₂OR°; -(CH₂)₀^OS(O)₂R°; -S(0)₂NR°₂; -(CH₂)₀-₄S(O)R°; - N(R°)S(0)₂NR°₂; -N(R°)S(0)₂R°; -N(OR°)R°; -C(NH)NR°₂; -P(0)₂R°; -P(0)R°₂; - OP(0)R°₂; -OP(0)(OR°)₂; SiR°₃; -(Ci^ straight or branched alkylene)0-N(R°)₂; or -(C1-4 straight or branched alkylene)C(0)0-N(R°)₂, wherein each R° may be substituted as defined below and is independently hydrogen, Ci_g aliphatic, -CH₂Ph, -0(CH₂)o-iPh, or a 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 a 3—12— membered saturated, partially unsaturated, or aryl mono- or polycyclic ring having 0^4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, which may be substituted as defined below.

Suitable monovalent substituents on R° (or the ring formed by taking two independent occurrences of R° together with their intervening atoms), are independently halogen, - (CH_{2 2}R^e, -(haloR*), -(CH₂y₂OH, -(CH₂y₂OR^e -(CH₂y₂CH(OR')₂; -O(haloR'), -CN, -N₃₎ -(CHzjo-zCCOi *, -(CH₂y₂C(0)OH, -(CH₂)o-₂C(0)OR^, _> -(CH₂)₀^C(O)N(R°)₂; - (CH₂y₂SR^#, -(CH₂y₂SH, -(CH₂y₂NH₂, -(CH₂y₂NHR*, -(CH₂y₂NR*₂, -N0₂, -SiR\ - OSiR*₃, -C(0)SR* -(Ci-4 straight or branched alkylene)C(0)OR', or -SSR* wherein each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently selected from Ci^ aliphatic, -CH₂Ph, -0(CH₂)o_iPh, or a 5- 6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. Suitable divalent substituents on a saturated carbon atom of R° include =0 and =S.

Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include the following: =0, =S, =NNR^* ₂, =NNHC(0)R^*, =NNHC(0)OR", =NNHS(0)₂R*, =NR*, =NOR*, -0(C(R*₂))₂-₃0- or -S(C(R*₂))₂-₃S- wherein each independent occurrence of R is selected from hydrogen, Ci_6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having heteroatoms independently selected from nitrogen, oxygen, or sulfur. 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, Ci_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*, -O(haloR'), -CN, -C(0)OH, -C(0)OR', -NH₂, -NHR', -NR'₂, or -N0₂, wherein each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently Ci_^t aliphatic, -CH2PI1, -0(CH₂)o_iPh, or a 5-6- membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

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)CH₂C(0)R^†, -S(0)₂R^†, - S(0)₂NR^† ₂, -C(S)NR^† ₂, -C(NH)NR^† ₂, or -N(R^†)S(0)₂R^†; 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 unsubstituted 3-12-membered saturated, partially unsaturated, or aryl mono- or bicyclic ring having 0^1 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R^† are independently halogen, -R", - (haloR*), -OH, -OR", -O(haloR'), -CN, -C(0)OH, -C(0)OR', -NH₂, -NHR*, -NR*₂, or - N0₂, wherein each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently C1-4 aliphatic, -CH₂Ph, -O(CH₂)₀-iPh, or a 5-6- membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. When substituents are described herein, the term "radical" or "optionally substituted radical" is sometimes used. In this context, "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. The terms "radical" or "optionally- substituted radical" in this context are thus interchangeable with "group" or "optionally- substituted group".

As used herein, the "term head-to-tail" or "HT", refers to the regiochemistry of adjacent repeating units in a polymer chain. For example, in the context of poly(propylene carbonate) (PPC), the term head-to-tail based on the three regiochemical possibilities depicted below:

The term head-to-tail ratio (H:T) refers to the proportion of head-to-tail linkages to the sum of all other regiochemical possibilities. With respect to the depiction of polymer structures, while a specific regiochemical orientation of monomer units may be shown in the representations of polymer structures herein, this is not intended to limit the polymer structures to the regiochemical arrangement shown but is to be interpreted to encompass all regiochemical arrangements including that depicted, the opposite regiochemistry, random mixtures, isotactic materials, syndiotactic materials, racemic materials, and/or

enantioenriched materials and combinations of any of these unless otherwise specified.

As used herein the term "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 such as ethylene oxide, propolyene oxide, butylene oxide and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 shows the optical clarity of a TPU of the present invention relative to a prior art TPU. Fig. 2 shows a Loss Modulus Overlay for three elastomers from Example 6 (line with highest storage modulus at -80°C: inventive elastomer; line with arrow at 73.72°C: UH-50 elastomer; and line peaking at approximately 85°C: Fomrez 44-160 elastomer).

Fig. 3 shows a DMA Graph for an elastomer of the present invention from Example 6 (solid line: inventive elastomer; dashed line: UH-50 elastomer; and dash dot line: Fomrez 44-

160 elastomer).

Fig. 4 shows the effect of temperature on tensile strength at yield (psi) of elastomers of

Example 6; left bar: UH-50 50% HS, center bar: Fomrez 44-160 50% HS, right bar:

Novomer 58-076 50% HS.

Fig. 5 shows Resistance of an inventive TPU of Example 6 to various solvents measured as a weight change after immersion; left bar: UH-50, center bar: Fomrez 44-160, right bar:

Novomer 58-076.

Fig. 6 shows the retention of tensile strength at yield of inventive TPUs from Example 6 after immersion in different solvents (Retention of properties in water was measured by exposing TPU samples to 100% RH at 50°C; in all other solvents samples were immersed at RT for one week, except for hydrogen peroxide in which samples were immersed for 2 weeks at 37°C).

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

In one aspect, the present invention encompasses polymer compositions comprising aliphatic polycarbonate chains cross-linked or chain extended through urethane linkages. In certain embodiments, these polymer compositions comprise thermoplastic polyurethanes (TPUs). The field of thermoplastic polyurethane manufacture and formulation is well advanced. In some embodiments, the novel materials presented herein are formulated, processed, and/or used according to methods well known in the art. Combining knowledge of the art with the disclosure and teachings herein, the skilled artisan will readily apprehend variations, modifications and applications of the compositions and such variations are specifically encompassed herein. The following references contain information on the formulation, manufacture and uses of thermoplastic polyurethanes, the entire content of each of these references is incorporated herein by reference.

Handbook of Thermoplastic Elastomers, William Andrew Publishers, 2007 (ISBN 978-0815515494)

The Polyurethanes Book. J. Wiley & Sons, 2003 (ISBN 978-0470850411)

Szvcher's Handbook of Polyurethanes. CRT Press LLC, 1999 (ISBN 0-8493-0602-7) Poyurethane Elastomers: From Morphology to Mechanical Aspects. Springer- Verlag/Wein, 2011 (ISBN 978-3-7091-0 13-9)

Szvcher's Handbook of Polyurethanes. CRT Press LLC, 1999 (ISBN 0-8493-0602-7) Polyurethane Handbook, Hanser, 1994 (ISBN 1569901570)

In certain embodiments, the polyurethane compositions of the present invention are derived by combining two compositions: a first composition comprising one or more isocyanate compounds optionally containing diluents, solvents, coreactants and the like, and a second composition comprising one or more aliphatic polycarbonate polyols optionally with additional reactants, diluents, solvents, catalysts, or additives. These compositions may be formulated separately and then combined or all components of the finished polyurethane composition may be combined in a single step. Before fully describing these compositions, the polyols and isocyanates from which they are formulated will be more fully described.

I. Aliphatic Polycarbonate Polyols

This section describes some of the aliphatic polycarbonate polyols that have utility in making compositions of the present invention. In certain embodiments, compositions of the present invention comprise aliphatic polycarbonate polyols derived from the

copolymerization of one or more epoxides and carbon dioxide. Examples of suitable polyols, as well as methods of making them are disclosed in PCT publications WO 2010/028362, WO WO 2012/071505, and WO 2013/016331 the entirety of each of which is incorporated herein by reference.

As thermoplastic polyurethanes (TPUs) allow for the production of polyurethanes by conventional thermoplastic processing techniques, they must not thermally degrade when repeatedly plasticized by the influence of temperature. Therefore the TPU macromolecules are typically largely linear and not branched macromolecules since the latter cannot easily be thermoformed. Thus, Afunctional or nearly bifunctional polyols are typically used to make TPUs.

It is advantageous for many of the embodiments described herein that the aliphatic polycarbonate polyols 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 to modify the chemistry of the end groups, such modified materials may terminate in amino groups, thiol groups, alkene groups, carboxylate groups, isocyanate groups and the like, suitable methods for such end-group modifications are disclosed in WO WO/2012/027725, 2012/094619, and WO/2012/154849, the entirety of each of which is incorporated herein by reference. For purposes of this invention, the term 'aliphatic polycarbonate polyol' includes both traditional hydroxy-terminated materials as well as these end-group modified compositions as long as the modified end groups are competent substrates for the TPU formulation.

In certain embodiments, at least 90% of the end groups of the polycarbonate polyol used are reactive end groups. In certain embodiments, at least 95%, at least 96%, at least 97% or at least 98% of the end groups of the polycarbonate polyol used are reactive end groups. In certain embodiments, 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 reactive end groups. In certain embodiments, more than 99.9% of the end groups of the polycarbonate polyol used are reactive end groups.

In certain embodiments, at least 90% of the end groups of the polycarbonate polyol used are -OH groups. In certain embodiments, at least 95%, at least 96%, at least 97% or at least 98%o of the end groups of the polycarbonate polyol used are -OH groups. In certain embodiments, 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.

Another way of expressing the -OH end-group content of a polyol composition is by reporting its OH# which is measured using methods well known in the art. In certain embodiments, the aliphatic polycarbonate polyols used in the present invention have an OH# greater than about 20. In certain embodiments, the aliphatic polycarbonate polyols utilized in the present invention have an OH# greater than about 40. In certain embodiments, the aliphatic polycarbonate polyols have an OH# greater than about 50, greater than about 75, greater than about 100, greater than about 120, greater than about 140, greater than about 160, greater than about 180, or greater than about 200. In certain embodiments, the aliphatic polycarbonate polyols utilized in the present invention have an OH# between about 40 and 120, between about 60 and 120, between about 40 and 100, between about 60 and 80, between about 40 and 60, between about 60 and 80, or between about 80 and 100. In certain embodiments, the aliphatic polycarbonate polyols utilized in the present invention have an OH# between about 100 and 250, between about 100 and 150, between about 150 and 200, or between about 200 and 250.

In certain embodiments, it is advantageous if the aliphatic polycarbonate polyol compositions have a substantial proportion of primary hydroxyl end groups. These are the norm for compositions comprising poly(ethylene carbonate), but for polyols derived copolymerization of substituted epoxides with CO2, it is common for some or most of the chain ends to consist of secondary hydroxyl groups. In certain embodiments, such polyols are treated to increase the proportion of primary -OH end groups. This may be accomplished by reacting the secondary hydroxyl groups with reagents such as ethylene oxide, reactive lactones, and the like. In certain embodiments, the aliphatic polycarbonate polyols are treated with beta lactones, caprolactone and the like to introduce primary hydroxyl end groups. In certain embodiments, the aliphatic polycarbonate polyols are treated with ethylene oxide to introduce primary hydroxyl end groups.

In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and one or more epoxides. 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 propylene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and 1,2-butene oxide and/or 1,2-hexene 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 cyclohexene oxide.

In certain embodiments, 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, cyclopentene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins. In certain embodiments, 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. In certain

embodiments, terpolymers contain about 50% to about 99.5% ethylene oxide-derived repeat units. In certain embodiments, 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% ethylene oxide-derived repeat units.

In some embodiments, 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, cyclopentene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins. In certain embodiments, 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. In certain

embodiments, 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.

In certain embodiments, in the polymer compositions described hereinabove, aliphatic polycarbonate chains have a number average molecular weight (M„) in the range of 400 g/mol to about 250,000 g/mol.

In certain embodiments, aliphatic polycarbonate chains have an M„ less than about 100,000 g mol. In certain embodiments, aliphatic polycarbonate chains have an M„ less than about 70,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M_H less than about 50,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M_n between about 500 g/mol and about 40,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M_K less than about 25,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 500 g/mol and about 20,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 500 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M_H between about 500 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 500 g/mol and about 2,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 1,000 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M_K between about 5,000 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M_K between about 500 g/mol and about 1,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 1,000 g/mol and about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M_K of about 4,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 2,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 2,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 1,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 1 ,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 750 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 500 g/mol.

In certain embodiments, the aliphatic polycarbonate polyols used are characterized in that they have a narrow molecular weight distribution. This can be indicated by the polydispersity indices (PDI) of the aliphatic polycarbonate polymers. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 3. In certain embodiments, 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.

In certain embodiments, 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

composition, the percentage of carbonate linkages is 85% 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 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 composition, the percentage of carbonate linkages is 92% 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 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 composition, the percentage of carbonate linkages is 95% 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 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 composition, the percentage of carbonate linkages is 98% 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 99% 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 99.5% or greater. In certain embodiments, the percentages above exclude ether linkages present in polymerization initiators or chain transfer agents and refer only to the linkages formed during epoxide CO2 copolymerization.

In certain embodiments, 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 CO₂ 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.

In certain embodiments where 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

characterized in that it is regioregular. Regioregularity may be expressed as the percentage of adjacent monomer units that are oriented in a head-to-tail arrangement within the polymer chain. In certain embodiments, 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.

In certain embodiments, aliphatic polycarbonate polyols useful for the present invention have a viscosity controlled to be within a particular range. The preferred range may depend upon a particular application and may be controlled to be within the normal range for a particular application.

In certain embodiments, the aliphatic polycarbonate polyol used in the formulation of a TPU has a viscosity of less than about 1,000,000 centipoise at ambient temperatures. In certain embodiments, such polyols have a viscosity of less than 250,000 centipoise. In certain embodiments, such polyols have a viscosity of less than 100,000 centipoise. In certain embodiments, such polyols have a viscosity of less than 25,000 centipoise. In certain embodiments, such polyols have a viscosity of less than 10,000 centipoise.

In certain embodiments, it is preferred that the aliphic polycarbonate polyols used in the formulation of TPUs have a functionality between 1.8 and 2.5. In certain embodiments, it is preferred that the polyols have a functionality of 1.9 to 2.3. In certain embodiments, it is preferred that the polyols have a functionality of 1.9 to 2.2. In certain embodiments, it is preferred that the polyols have a functionality of 1.95 to 2.1.

In certain embodiments, aliphatic polycarbonate polyols useful for the present invention have a glass transition temperature (Tg) within a particular range. The desired Tg will vary with the application and may be controlled to be within the known normal range for a particular application. In certain embodiments, where the polyol is used in the formulation of a more flexible thermoplastic polyurethane, the polyol has a Tg less than about 20 °C. In certain embodiments, such polyols have Tg less than about 15 °C, less than about 10 °C, less than about 5 °C, less than about 0 °C, less than about -10 °C, less than about -20 °C, or less than about -40 °C. In certain embodiments, such polyols have a Tg between about -30 °C and about -20 °C. In certain embodiments, such polyols have a Tg between about -30 °C and about -20 °C.

In certain embodiments, where the aliphatic polycarbonate polyol is used in the formulation of a more rigid thermoplastic polyurethane, the polyol has a Tg greater than about -30 °C. In certain embodiments, such polyols have Tg greater than about -20 °C, greater than about -10 °C, greater than about 0 °C, greater than about 10 °C, greater than about 15 °C, or greater than about 25 °C. In certain embodiments, such polyols have a Tg between about -10 °C and about 30 °C. In certain embodiments, such polyols have a Tg between about 0 °C and about 20 °C. In certain embodiments, such polyols have a Tg between about 10 °C and about 40 °C.

In certain embodiments, compositions of the present invention comprise aliphatic polycarbonate polyols having a structure PI:

wherein,

R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain, independently selected from the group consisting of -H, fluorine, an optionally substituted C1.30 aliphatic group, and an optionally substituted Ci.₂o heteroaliphatic group, and an optionally substituted C₆-io aryl group, where any two or more of R¹, R², R³, and R⁴ 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 a site of attachment to any of the chain- extending moieties or isocyanates described in the classes and subclasses herein;

n is at each occurrence, independently an integer from about 3 to about 1,000; ft .

— ' is a multivalent moiety; and

x and j are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

. ft]

In certain embodiments, 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/COz copolymerization can occur. In certain embodiments, such copolymerizations are performed in the presence of polyfunctional chain transfer agents as exemplified in published PCT application WO 2010/028362. In certain embodiments, such copolymerizations are performed as exemplified in US 2011/0245424. In certain embodiments, such copolymerizations are performed as exemplified in US 2011/0245424. In certain embodiments, such copolymerizations are performed as exemplified in Green Chem. 2011, 13, 3469-3475.

In certain embodiments, a polyfunctional chain transfer agent has a formula:

wherein each of

x, and y is as defined above and described in classes and subclasses herein.

In certain embodiments, 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:

In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with a structure P2:

P2

wherein each of R¹, R², R³, R⁴, Y,

n is as defined above and described in the classes and subclasses herein.

In certain embodiments where aliphatic polycarbon chains have a structure P2, ^v— ' is derived from a dihydric alcohol. In such instances

represents the carbon- containing backbone of the dihydric alcohol, while the two oxygen atoms adjacent to

are derived from the -OH groups of the diol. For example, if the polyiunctional chain transfer agent were ethylene glycol, then V-/ would be -CH2CH2- and P2 would have the following structure:

In certain embodiments, where

derived from a dihydric alcohol, the dihydric alcohol comprises a C2-40 diol. In certain embodiments, 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, 10-decanediol, 1,12- dodecanediol, 2,2,4,4-tetramethylcyclobutane-l,3-diol, 1,3-cyclopentanediol, 1,2- cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1 ,2-cyclohexanedimethanol, 1,3- cyclohexanedimethanol, l,4-cycloher°— A ^_n* _n„^ ¹ A— ¹-¹— anediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters,

trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.

In certain embodiments, where

is derived from a dihydric alcohol, 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 polypropylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol, polytetramethylene glycol such as those having molecular weights from about 150 to about 2000 /mol.

In certain embodiments, where

derived from a dihydric alcohol, the dihydric alcohol comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid. In certain embodiments, the alkoxylated derivatives comprise ethoxylated or pro oxylated compounds.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol comprises a polymeric diol. In certain embodiments, a polymeric diol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters,

polyoxymethylene polymers, and alkoxylated analogs of any of these. In certain

embodiments, the polymeric diol has an average molecular weight less than about 2000 g/mol.

In certain embodiments,

is derived from a polyhydric alcohol with more than two hydroxy groups. In certain embodiments where / is derived from a polyhydric alcohol with more than two hydroxyl groups, these >2 functional polyols are a component of a polyol mixture containing predominantly polyols with two hydroxyl groups. In certain embodiments, these >2 functional polyols comprise less than 20% of the total polyol mixture by weight. In certain embodiments, these >2 functional polyols comprise less than 10% of the total polyol mixture. In certain embodiments, these >2 functional polyols comprise less than 5% of the total polyol mixture. In certain embodiments, these >2 functional polyols comprise less than 2% of the total polyol mixture. In certain embodiments, the aliphatic polycarbonate chains in polymer compositions of the present invention comprise aliphatic polycarbonate chains where the moiety

is derived from a triol. In certain embodiments, such aliphatic polycarbonate ch

wherein e

ach of R , RR²,, RR^3j,, RR⁴⁴,, YY,, aanndd nn iiss as defined above and described in classes and subclasses herein.

In certain embodiments where

derived from a triol, 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. In certain embodiments, alkoxylated derivatives comprise ethoxylated or propox lated compounds.

In certain embodiments,

is derived from an alkoxylated derivative of a trifunctional carboxylic acid or trifunctional hydroxy acid. In certain embodiments, alkoxylated derivatives comprise ethox lated or propoxylated compounds.

In certain embodiments,

derived from a polymeric triol. In certain embodiments, the polymeric triol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefms, polyether-copolyesters, polyether

polycarbonates, polyoxymethylene polymers, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, the alkoxylated polymeric triols comprise ethoxylated or propoxylated com ounds.

In certain embodiments,

is derived from a polyhydric alcohol with four hydroxy groups. In certain embodiments, aliphatic polycarbonate chains in polymer com ositions 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 P4:

wherein each of R

nn iiss as defined above and described in classes and subclasses herein.

In certain embodiments,

is derived from a polyhydric alcohol with more than four hydroxy groups. In certain embodiments, 0,) is derived from a polyhydric alcohol with six hydroxy groups. In certain embodiments, a polyhydric alcohol is dipentaerithrotol or an alkoxylated analog thereof. In certain embodiments, a polyhydric alcohol is sorbitol or an alkoxylated analog thereof. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P5:

wherein each of R¹, R R²,, RR³\, RR⁴⁴,, YY,, aanndd nn iis as defined above and described in classes and subclasses herein.

In certain embodiments, 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).

In certain embodiments,

is derived from a hydroxy acid. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P6:

wherein each of R¹, R², R³, R⁴, Y, 0 and n is as defined above and described m classes and subclasses herein. In such instances, © represents the carbon-containing backbone of the hydroxy acid, while ester and carbonate linkages adjacent to are derived from the -CO2H group and the hydroxy group of the hydroxy acid. For example, if © were derived from 3 -hydroxy propanoic acid, then (_ would be -CH2CH2- and P6 would have the following structure:

In certain embodiments,

is derived from an optionally substituted C2-40 hydroxy acid. In certain embodiments, © is derived from a polyester. In certain embodiments, such polyesters have a molecular weight less than about 2000 g mol.

In certain embodiments, 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.

In certain embodiments, a hydroxy acid is a beta-hydroxy acid. In certain embodiments, 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.

In certain embodiments, a hydroxy acid is a α-ω hydroxy acid. In certain embodiments, a hydroxy acid is selected from the group consisting of: of optionally substituted C3.2₀ aliphatic α-ω hydroxy acids and oligomeric esters.

In certain embodiments, a hydroxy acid is selected from the group consisting of:

In certain embodiments, © is derived from a polycarboxylic acid. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P7:

wherein each of R RR^2z,, RR³, RR⁴\, YY,, Θ-^ aanndd «« iiss as defined above and described in classes and subclasses herein, and y' is an integer from 1 to 5 inclusive.

In embodiments where the 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 Θ are derived from-C02H groups of the polycarboxylic acid. For example 2,, if ft./ were derived from succinic acid (HO₂CCH₂CH₂CO₂H), then would be -CH₂CH₂- and P7 would have the following structure:

wherein each of R¹, R², R³, R⁴, Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments,

derived from a dicarboxylic acid. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P8:

In certain embodiments,

from the group consisting of: phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.

In certain embodiments, is derived from a diacid selected from the group consisti

IYI ^«>^J^Y i_H -<^« . ^" HO¾_jC^^^ . V,H ^H¾CT ,Η

In certain embodiments, © is derived from a phosphorous-containing molecule. In certain embodiments, © has a formula -P(0)(OR)i- where each R is independently an optionally substituted C_1-2o aliphatic group or an optionally substituted aryl group and k is 0, l, or 2.

For example, if _/ were derived from phenyl phosphite (PhO-P(0)(OH)2), then ft» would be -P(0)(OPh)- and P7 would have the following structure:

In certain embodiments, © is derived from a phosphorous-containing molecule selected from the group consisting of:

In certain embodiments, © has a formula -P(0)(R)- where R is an optionally substituted C_1-2o aliphatic group or an nntionallv ub tituted arvl ^proup and is 0, 1, or 2. In certain embodiments, ^ is derived from a phosphorous-containing molecule selected from the group consisting of:

where R^d is halogen, NO2, CN, or an optionally substituted moiety selected from the group consisting of C_1-2o aliphatic, C_1-2o heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10- membered aryl, 5- to 10-membered heteroaryl, and 3- to 12-membered heterocyclic.

In certain embodiments, each

in the structures herein is independently selected from the group consisting of:

wherein each R^x is independently an optionally substituted group selected from the group consisting of C_1-2o aliphatic, C_1-2o heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10-membered aryl, 5- to 10-membered heteroaryl, and 3- to 12-membered heterocyclic.

In certain embodiments, each

wherein R^x is as defined above and described in classes and subclasses herein. In certain embodiments, aliphatic polycarbonate chains comprise:

wherein each of , -Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y and « is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y and n is as defined above and described in classes and subclasses herein, and φ = 2-20.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y, n, and φ is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each

-Y, and n is as defined above and described in classes and

subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of , -Y, and n is as defined above and described in classes and

subclasses herein.

In certain embodiments aliphatic polycarbonate chains comprise

wherein each of -Y and n are is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y, and n is as defined above and described in classes and

subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y and n is as defined above and described in classes and subclasses herein. In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of ©, -Y, and n is as defined above and described in classes and

subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of ©, -Y, R^x, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y, R^x, and n is as defined above and described in classes and

subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of ©_; -Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of 0, -Y, and n are is as defined above and described in classes and subclasses herein; and each ^==z independently represents a single or double bond.

In certain embodiments, aliphatic polycarbonate chains comprise

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y, ^====z , and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of ©, R^x, -Y and n is as defined above and described in classes and subclasses herein. In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y, R^x, and n is as defined above and described in classes and

subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y, , and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y, ^===: , and n is as defined above and described in classes and

subclasses herein.

In certain embodiments, ali hatic polycarbonate chains comprise

wherein each of 0, -Y, and n is as defined above and described in classes and

subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

In certain embodiments, in polycarbonates of structures P2a, P2c, P2d, P2f, P2h,

P2j, P21, P21-a, P2n, P2p, and P2r, © i_s selected from the group consisting of: ethylene glycol; diethylene glycol, triethylene glycol, higher ethylene glycol, 1,3 propane diol; 1,4 butane diol, hexylene glycol, neopentyl glycol, 1,6 hexane diol, propylene glycol, dipropylene glycol, tripopylene glycol, higher propylene glycol, polytetramethylene glycol, and alkoxylated derivatives of any of these.

For polycarbonates comprising repeat units derived from two or more epoxides, such as those represented by structures P2f through P2r, depicted above, it is to be understood that the structures drawn may represent mixtures of positional isomers or regioisomers that are not explicitly depicted. For example, the polymer repeat unit adjacent to either end group of the polycarbonate chains can be derived from either one of the two epoxides comprising the copolymers. Thus, while the polymers may be drawn with a particular repeat unit attached to an end group, 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 different 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. Similarly, while 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. In certain embodiments, the polymer composition comprises a mixture of all possible combinations of these. In other embodiments, the polymer composition is enriched in one or more of these.

In certain embodiments, the aliphatic polycarbonate polyol is selected from the group

Q5, Q6, Q7', Q8', and mixtures of any two or more of these.

where κ is as defined above and in the classes and subclasses herein, t is an integer from 1 to 12 inclusive, and R^l is independently at each occurrence -H, or -CH₃. In certain embodiments, the aliphatic polycarbonate polyol is selected from the group consisting of: Poly(ethylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, 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 Ql having an average molecular weight number of about 500 g/mol, 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 Ql having an average molecular weight number of about 1,000 g/mol, 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 Ql having an average molecular weight number of about 2,000 g/mol, 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 Ql having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% 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, 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, 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, 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, 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, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene 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 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol, 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 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 95% 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, 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, 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, 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, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.

Poly(propylene carbonate) of formula Q5 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, 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 Q5 having an average molecular weight number of about 500 g/mol, 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 Q5 having an average molecular weight number of about 1,000 g/mol, 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 Q5 having an average molecular weight number of about 2,000 g/mol, 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 Q5 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of between about 500 g/mol and about 3,000 g mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 500 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 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 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 3,000 g/mol, 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 Q7' having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, 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 Q7' having an average molecular weight number of about 500 g/mol, 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 Q7' having an average molecular weight number of about 1,000 g/mol, 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 Q7' having an average molecular weight number of about 2,000 g/mol, 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 Q7' having an average molecular weight number of about 3,000 g/mol, 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 Q8' having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, 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 Q8' having an average molecular weight number of about 500 g/mol, 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 Q8' having an average molecular weight number of about 1,000 g/mol, 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 Q8' having an average molecular weight number of about 2,000 g/mol, 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 Q8' having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; and

mixtures of any two or more of these.

(7)

In certain embodiments, the embedded chain transfer agent ^ is a moiety derived from a polymeric diol or higher polyhydric alcohol. In certain embodiments, such polymeric

(7)

alcohols are polyether or polyester polyols. In certain embodiments — ' is a polyether polyol comprising ethylene glycol or propylene glycol repeating units (-OCH₂CH₂0-, or

-OCH2CH(C¾)0-) or combinations of these. In certain embodiments, ^ is a polyester polyol comprising the reaction product of a diol and a diacid, or a material derived from ring- opening polymerization of one or more lactones.

(z )

In certain embodiments where ^ com rises a ol ether diol the aliphatic polyc

wherein,

R^q is at each occurrence in the polymer chain independently -H or -C¾;

R^a is -H, or -CH₃;

q and q' are independently an integer from about 2 to about 40; and

and n is as defined above and in the examples and embodiments herein.

In certain embodiments, an aliphatic polycarbonate polyol is selected from the consisting of:

In certain embodiments, where aliphatic polycarbonate polyols comprise compounds conforming to structure Q7, the moiety ^ is derived from a commercially available polyether polyol such as those typically used in the formulation of polyurethane

compositions.

(z )

In certain embodiments where ^ comprises a polyether diol, the aliphatic polycarbonate polyol has a structure Q8:

wherein,

c is at each occurrence in the polymer chain independently an integer from 0 to 6; d is at each occurrence in the polymer chain independently an integer from 1 to 1 1; and

each of R^q, n, and q and is as defined above and in the examples and embodiments herein. In certain embodiments, an aliphatic polycarbonate polyol is selected from the group consisting of:

In certain embodiments, where aliphatic polycarbonate polyols comprise compounds conforming to structure Q8, the moiety ( ^?) is derived from a commercially available polyester polyol such as those typically used in the formulation of polyurethane compositions.

II. Isocyanate Reagents

As described above, the compositions of the present invention comprise higher polymers derived from reactions with isocyanate reagents, this section describes the isocyanates in more detail.

The purpose of the isocyanate reagents is to react with the reactive end groups on the aliphatic polycarbonate polyols (and any other reactive hydrogen compounds present) to form higher molecular weight structures through chain extension and/or cross-linking.

The art of polyurethane synthesis is well advanced and a very large number of isocyanates and related polyurethane precursors are known in the art. While this section of the specification describes isocyanates suitable for use in certain embodiments of the present invention, it is to be understood that it is within the capabilities of one skilled in the art of polyurethane formulation to use alternative isocyanates along with the teachings of this disclosure to formulate additional compositions of matter within the scope of the present invention. Descriptions of suitable isocyanate compounds and related methods can be found in: Chemistry and Technology of Polyols for Polyurethanes Ionescu, Mihail 2005 (ISBN 978- 1-84735-035-0), and H. Ulrich, "Urethane Polymers," Kirk-Othmer Encyclopedia of Chemical Technology, 1997 the entirety of each of which is incorporated herein by reference.

In certain embodiments, the isocyanate reagents comprise two or more isocyanate groups per molecule. In certain embodiments, the isocyanate reagents are diisocyanates. hi other embodiments, the isocyanate reagents are higher polyisocyanates such as triisocyanates, tetraisocyanates, isocyanate polymers or oligomers, and the like, which are typically a minority component of a mix of predominanetly diisocyanates. In certain embodiments, the isocyanate reagents are aliphatic polyisocyanates or derivatives or oligomers of aliphatic polyisocyanates. In other embodiments, the isocyanates are aromatic polyisocyanates or derivatives or oligomers of aromatic polyisocyanates. In certain embodiments, the compositions may comprise mixtures of any two or more of the above types of isocyanates.

In certain embodiments, isocyanate reagents usable for the production of the thermoplastic polyurethane include aliphatic, cycloaliphatic, and aromatic diisocyanate compounds.

Suitable aliphatic and cycloaliphatic isocyanate compounds include, for example, 1,3- trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9- nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4,'-dicyclohexylmethane diisocyanate, 2,2'- diethylether diisocyanate, hydrogenated xylylene diisocyanate, and hexamethylene diisocyanate-biuret.

The aromatic isocyanate compounds include, for example, p-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4'- diphenylmethane diisocyanate, 1,5-napthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-methyleneditolylene-4,4'-diisocyanate, tolylenediisocyanate- trimethylolpropane adduct, triphenylmethane triisocyanate, 4,4'-diphenylether diisocyanate, tetrachlorophenylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, and triisocyanate phenylthiophosphate. In certain embodiments, the isocyanate compound employed comprise one or more of: 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene hexamethylene diisocyanate and isophorone diisocyanate. In certain embodiments, the isocyanate compound employed is 4,4'- diphenylmethane diisocyanate. The above-mentioned diisocyanate compounds may be employed alone or in mixtures of two or more thereof.

In certain embodiments, the isocyanate component used in the formulation of the novel materials of the present invention have a functionality of 2 or more. In certain embodiments, the isocyanate component of the inventive materials comprise a mixture of diisocyanates and higher isocyanates formulated to achieve a particular functionality number for a given application. In certain embodiments, where the inventive composition is a typical TPU processed in standard equipment and used in common applications, the isocyanate employed has a functionality of about 2. In certain embodiments, such as those requiring a more rigid TPU and/or using non-standard processing equipment, isocyanates are selected to have a functionality between about 2 and about 2.7. In certain embodiments, such isocyanates have a functionality between about 2 and about 2.5. In certain embodiments, such isocyanates have a functionality between about 2 and about 2.3. In certain embodiments, such isocyanates have a functionality between about 2 and about 2.2.

In certain embodiments, an isocyanate reagent is selected from the group consisting of: 1,6-hexamethylaminediisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4' methylene- bis(cyclohexyl isocyanate) (Hi₂MDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI), diphenylmefhane-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 (TMXDI), p-tetramethylxylylene diisocyanate (TMXDI), isocyanatomethyl-l,8-ictane diisocyanate (TIN), triphenylmethane- 4,4',4"triisocyanate, Tris(p-isocyanatomethyl)thiosulfate, 1,3- Bis(isocyanatomethyl)benzene, 1 ,4-tetramethylene diisocyanate, trimethylhexane diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, lysine diisocyanate, and mixtures of any two or more of these.

In certain embodiments, an isocyanate reagent is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate and isophorone diisocyanate. In certain embodiments, an isocyanate reagent is 4,4'-diphenylmethane diisocyanate. In certain embodiments, an isocyanate reagent is 1 ,6-hexamethylene diisocyanate. certain embodiments, an isocyanate reagent is isophorone diisocyanate.

Isocyanates suitable for certain embodiments of the present invention are available commercially under various trade names. Examples of 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), Mondur (Bayer Material Science), Suprasec (Huntsman Inc.), 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. The selection of suitable commercially-available isocyanate materials as reagents to produce polyurethane compositions for a particular application is within the capability of one skilled in the art of polyurethane coating technology using the teachings and disclosure of this patent application along with the information provided in the product data sheets supplied by the above- mentioned suppliers.

Additional isocyanates suitable for certain embodiments of the present invention are sold under the trade name Lupranate® (BASF). In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 1, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:

Lupranate M 4,4' MDI 33.5 2

Lupranate MS 4,4' MDI 33.5 2

Lupranate Ml 2,4' and 4,4' MDI Blend 33.5 2

Lupranate LP30 Liquid Pure 4,4' MDI 33.1 2

Lupranate 227 Monomeric/Modified MDI Blend 32.1 2

Lupranate 5143 Carbodiimide Modified 4,4' MDI 29.2 2.2

Lupranate R2500U Polymeric MDI Variant 31.5 2.7

Lupranate M205 Mid-Functionality Polymeric 31.5 2.7

Lupranate M20FB Mid-Functionality Polymeric 31.5 2.7

Lupranate M70L High-Functionality Polymeric 31 3

Lupranate M200 IHigh-FuMTrtion 30 3.1

Lupranate 241 Low Functionality Polymeric 32.6 2.3

Lupranate 230 Low Viscosity Polymeric 32.5 2.3

Lupranate 245 Low Viscosity Polymeric 32.3 2.3

Lupranate TF2115 Mid Functionality Polymeric 32.3 2.4

Lupranate 78 Mid Functionality Polymeric 32 2.3

Lupranate 234 Low Functionality Polymeric 32 2.4

Lupranate 273 Low Viscosity Polymeric 32 2.5

Lupranate 266 Low Viscosity Polymeric 32 2.5

Lupranate 261 Low Viscosity Polymeric 32 2.5

Lupranate 255 Low Viscosity Polymeric 31.9 2.5

Lupranate 268 Low Viscosity Polymeric 30.6 2.4

Lupranate 5010 Higher Functional Prepolymer 28.6 2.3

Lupranate 223 Low Vise. Derivative of Pure MDI 27.5 2.2

Lupranate 5040 Mid Functional, Low Viscosity 26.3 2.1

Lupranate 5110 Polymeric MDI Prepolymer 25.4 2.3

Lupranate MP102 4,4' MDI Prepolymer 23 2

Lupranate 5090 Special 4,4' MDI Prepolymer 23 2.1

Lupranate 5050 Mid Functional, Mid NCO Prepol 21.5 2.1

Lupranate 5030 Special MDI Prepolymer 18.9 NA

Lupranate 5080 2,4'-MDI Enhanced Prepolymer 15.9 2

Lupranate 5060 Low Funct, Higher MW Prepol 15.5 2

Lupranate 279 Low Funct, Special Prepolymer 14 2

Lupranate 5070 Special MDI Prepolymer 13 2

Lupranate 5020 ^^^^ff.i ¹.³.¹.'.^' ^{Low NC0 9,5 2}

m

Lupranate T80- 80/20 :2,4/2,6TDI 48.3 2

Lupranate T80- High Acidity TDI 48.3 2

Lupranate 8020 80/20:TDI/Polymeric MDI 44.6 2.1

TABLE 1

Other isocyanates suitable for certain embodiments of the present invention are sold under the trade name Desmodur¾> available from Bayer Material Science. In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 2, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:

Desmodur^® E 15 Aromatic polyisocyanate prepolymer based on toluene diisocyanate.

Desmodur^® E 1660 Aromatic polyisocyanate prepolymer based on toluene diisocyanate.

Desmodur^® E 1750 PR Polyisocyanate prepolymer based on toluene diisocyanate

Desmodur^® E 20100 Modified polyisocyanate prepolymer based on

diphenylmethane diisocyanate.

Desmodur^® E 21 Aromatic polyisocyanate prepolymer based on

diphenylmethane diisocyanate ( DI).

Desmodur^® E 2190 X Aromatic polyisocyanate prepolymer based on

diphenylmethane diisocyanate (MDI)

Desmodur^® E 22 Aromatic polyisocyanate prepolymer based on

diphenylmethane diisocyanate.

Desmodur^® E 2200/76 Desmodur E 2200/76 is a prepolymer based on (MDI) with isomers.

Desmodur^® E 23 Aromatic polyisocyanate prepolymer based on

diphenylmethane diisocyanate (MDI).

Desmodur^® E 29 Polyisocyanate prepolymer based on diphenylmethane diisocyanate.

Desmodur^® E 305 Desmodur E 305 is a largely linear aliphatic NCO prepolymer based on hexamethylene diisocyanate.

Desmodur^® E 3255 PA/SN Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanate (HDI)

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 2715 Aromatic polyisocyanate prepolymer based on 2,4'- diphenylmethane diisocyanate (2,4'-MDI) and a hexanediol

Desmodur^® E XP 2723 Aromatic polyisocyanate prepolymer based on

diphenylmethane diisocyanate (MDI).

Desmodur^® E XP 2726 Aromatic polyisocyanate prepolymer based on 2,4'- diphenylmethane diisocyanate (2,4'-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^® H Monomeric aliphatic diisocyanate

Desmodur^® HL Aromatic/aliphatic polyisocyanate based on toluylene

diisocyanate/ hexamethylene diisocyanate

Desmodur^® 1 Monomeric cycloaliphatic diisocyanate.

Desmodur^® IL 1351 Aromatic polyisocyanate based on toluene diisocyanate Desmodur^® IL 1451 Aromatic polyisocyanate based on toluene diisocyanate

Desmodur^® IL BA Aromatic polyisocyanate based on toluene diisocyanate

Desmodur^® IL EA Aromatic polyisocyante resin based on toluylene diisocyanate

Desmodur^® L 1470 Aromatic polyisocyanate based on toluene diisocyanate

Desmodur^® L 67 BA Aromatic polyisocyanate based on tolulene diisocyanate

Desmodur^® L 67 MPA/X Aromatic polyisocyanate based on tolulene diisocyanate

Desmodur^® L 75 Aromatic polyisocyanate based on tolulene diisocyanate

Desmodur^® LD Low-functionality isocyanate based on hexamethylene diisocyanatG (HDI)

Desmodur^® LS 2424 Monomeric diphenylmethane diisocyanate with high 2,4'- isomer content

Desmodur^® T Polyisocyanate prepolymer based on diphenylmethane diisocyanate

Desmodur^® N 100 Aliphatic polyisocyanate (HDI biuret)

Desmodur^® N 3200 Aliphatic polyisocyanate (low-viscosity HDI biuret)

Desmodur^® N 3300 Aliphatic polyisocyanate (HDI trimer)

Desmodur^® N 3368 BA/SN Aliphatic polyisocyanate (HDI trimer)

Desmodur^® N 3368 SN Aliphatic polyisocyanate (HDI trimer)

Desmodur^® N 3386 BA/SN Aliphatic polyisocyanate (HDI trimer)

Desmodur^® N 3390 BA Aliphatic polyisocyanate (HDI trimer)

Desmodur^® N 3390 BA/SN Aliphatic polyisocyanate (HDI trimer)

Desmodur^® N 3400 Aliphatic polyisocyanate (HDI uretdione)

Desmodur^® N 3600 Aliphatic polyisocyanate (low-viscosity HDI trimer)

Desmodur^® N 3790 BA Aliphatic polyisocyanate (high functional HDI trimer)

Desmodur^® N 3800 Aliphatic polyisocyanate (flexibilizing HDI trimer)

Desmodur^® N 3900 Low-viscosity, aliphatic polyisocyanate resin based on hexamethylene diisocyanate

Desmodur^® N 50 BA/ PA Aliphatic polyisocyanate (HDI biuret) Desmodur^® N 75 BA Aliphatic polyisocyanate (HDI biuret)

Desmodur^® N 75 MPA Aliphatic polyisocyanate (HDI biuret)

Desmodur^® N 75 MPA/X Aliphatic polyisocyanate (HDI biuret)

Desmodur^® NZ 1 Aliphatic polyisocyanate

Desmodur^® PC-N Desmodur PC-N is a modified diphenyl-methane-4,4'- diisocyanate ( DI).

Desmodur^® PF Desmodur PF is a modified diphenyl-methane-4,4'-diisocyanate

(MDI).

Desmodur^® PL 340, 60 % BA/SN Blocked aliphatic polyisocyanate based on IPDI

Desmodur^® PL 350 Blocked aliphatic polyisocyanate based on HDI

Desmodur^® RC Solution of a polyisocyanurate of toluene diisocyanate (TDI) in ethyl acetate.

Desmodur^® RE Solution of triphenylmethane-4,4',4"-tnisocyanate in ethyl acetate

Desmodur^® RFE Solution of tris(p-isocyanatophenyl) thiophosphate in ethyl acetate

Desmodur^® RN Solution of a polyisocyanurate with aliphatic and aromatic NCO groups in ethyl acetate.

Desmodur^® T 100 Pure 2,4 '-toluene diisocyanate (TDI)

Desmodur^® T 65 N 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 67 : 33

Desmodur^® T 80 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 80 : 20

Desmodur^® T 80 P 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 80 : 20 with an increased content of hydrolysable chlorine

Desmodur^® VH 20 N Polyisocyanate based on diphenylmethane diisocyanate

Desmodur^® VK Desmodur VK products re mixtures of diphenylmethane-4,4'- diisocyanate (MDI) with isomers and higher functional

Desmodur^® VKP 79 Desmodur VKP 79 is a modified diphenylmethane-4,4'- diisocyanate (MDI) with isomers and homologues.

Desmodur^® VKS 10 Desmodur VKS 10 is a mixture of diphenylmethane-4,4'- diisocyanate (MDI) with isomers and higher functional

Desmodur^® VKS 20 Desmodur VKS 20 is a mixture of diphenylmethane-4,4'- diisocyanate (MDI) with isomers and higher functional

Desmodur^® VKS 20 F Desmodur VKS 20 F is a mixture of diphenylmethane-4,4'- diisocyanate (MDI) with isomers and higher functional

Desmodur^® VKS 70 Desmodur VKS 70 is a mixture of diphenylmethane-4,4'- diisocyanate (MDI) with isomers and homologues.

Desmodur^® VL Aromatic polyisocyanate based on diphenylmethane

diisocyanate Desmodur^® VP LS 2078/2 Blocked aliphatic polyisocyanate based on IPDI

Desmodur^® VP LS 2086 Aromatic polyisocyanate prepolymer based on

diphenylmethane diisocyanate

Desmodur^® VP LS 2257 Blocked aliphatic polyisocyanate based on HDI

Desmodur^® VP LS 2371 Aliphatic polyisocyanate prepolymer based on isophorone diisocyanate.

Desmodur^® VP LS 2397 Desmodur VP LS 2397 is a linear prepolymer based on

polypropylene ether glycol and diphenylmethane diisocyanate

Desmodur^® W Monomeric cycloaliphatic diisocyanate

Desmodur^® W/l Monomeric cycloaliphatic diisocyanate

Desmodur^® XP 2404 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 diphenylm9thane-4,4 '-diisocyanates (MDI) with

Desmodur^® XP 2551 Aromatic polyisocyanate based on diphenylmethane

diisocyanate

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-l,6-diisocyanate (HDI)

Desmodur^® XP 2617 Desmodur XP 2617 is a largely linear NCO prepolymer based on hexamethylene diisocyanate.

Desmodur^® XP 2665 Aromatic polyisocyanate prepolymer based on

diphenylmethane diisocyanate (MDI).

Desmodur^® XP 2675 Aliphatic polyisocyanate (highly functional HDI trimer)

Desmodur^® XP 2679 Aliphatic polyisocyanate (HDI allophanate trimer)

Desmodur^® XP 2714 Silane-functional aliphatic polyisocyanate based on

hexamethylene diisocyanate

Desmodur^® XP 2730 Low-viscosity, aliphatic polyisocyanate (HDI uretdione)

Desmodur^® XP 2731 Aliphatic polyisocyanate (HDI allophanate trimer)

Desmodur^® XP 2742 Modified aliphatic Polyisocyanate (HDI-Trimer), contains Si02 - nanoparticles

TABLE 2 Additional isocyanates suitable for certain embodiments of the present invention are sold under the trade name Tolonate® (Perstorp). In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 3, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:

TABLE 3

Other isocyanates suitable for certain embodiments of the present invention are sold under the trade name Mondur ® available from Bayer Material Science. In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 4, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:

MONDUR MA-2903 modified monomelic MDI; isocyanate-terminated (MDI) prepolymer; NCO weight 19.0%; viscosity 400 mPa-s @ 25°C; equivalent weight 221; functionality 2.0

MONDUR MA-2904 Allophanate-modified MDI polyether prepolymer; NCO weight 12.0%; viscosity 1,800 mPa- ■s @ 25°C; equivalent weight 350; functionality of 2.0

high-purity grade difunctional isocyanante, diphenylmethane 4,4'-diiscocyanate; used in production of polyurethane elastomers, adhesives, coatings and intermediate

MONDUR MB

polyurethane products; appearance colorless solid or liquid; specific gravity @ 50°C+15.5 1.19; flash point 202°C PMCC; viscosity (in molten form) 4.1 mPa-S; bult density 10 lb/gal (fused) or 9.93 lb/gal (molten); freezing temperature 39°C

monomeric diphenylmethan diisocyanate; used in a foams, cast elastomers, coatings and

MONDUR MLQ

ahdesives; appearance light yellow clear liquid, NCO 33.4% wt; 1.19 specific gravity at 25°C, 196°C flash point, DIN 51758; 11-15°C freezing temperature high-purity-grade difunctional isocyanate, diphenylmethane 4,4'-diisocyanate (MDI); used in production of solid polyurethane elastomers, adhesives, coatings and in intermediate

MONDUR MQ

polyurethane products; appearance colorless solid or liquid; specific gravity 1.19 @ 50°C; flash point 202°C PMCC; viscosity 4.1 mPa-S; bulk density 10 Ib./gal (fused) or 9.93 Ib./gal (molten); freezing temperature 39°C

MONDUR MR polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa-s

@ 25°C; equivalent weight 133; functionality 2.8

MONDUR MR LIGHT polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa-s

@ 25°C; equivalent weight 133; functionality 2.8

MONDUR MR-5 polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.5%; viscosity 50 mPa-s @

25°C; equivalent weight 129; functionality 2.4

MONDUR MRS 2,4' rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity

200 mPa-s @ 25°C; equivalent weight 133; functionality2.6

MONDUR MRS 2 2,4' rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 33.0%; viscosity 25 mPa-s @ 25°C; equivalent weight 127; functionality2.2

MONDUR MRS-4 2,4' rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.5%; viscosity 40 mPa-s @ 25°C; equivalent weight 129; functionality 2.4

MONDUR MRS-5 2,4' rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.3%; viscosity 55 mPa-s @ 25°C; equivalent weight 130; functionality 2.4

MONDUR PC modified 4,4' diphenylmethane diisocyanate (mMDI); NCO weight 25.8%; viscosity 145 mPa-s @ 25°C; equivalent weight 163; functionality 2.1

MONDUR PF modified 4,4' diphenylmethane diisocyanate (mMDI) prepolymer; NCO weight 22.9%;

viscosity 650 mPa-s @ 25°C; equivalent weight 183; functionality 2

MONDUR TD-65 monomeric toluene diisocyanate (TDI); 65/35 mixture of 2,4 and 2.6 TDI; NCO weight 48%;

viscosity 3 mPa-s @ 25°C; equivalent weight 87.5; functionality 2

MONDUR TD-80 GRADE

monomeric toluene diisocyanate (TDI); 80/20 mixture of the 2,4 and 2,6 isomer; NCO A

weight 48%; viscosity 5 mPa-s @ 25°C; equivalent weight 87.5; functionality 2

MONDUR TD-80 GRADE

monomeric toluene diisocyanate (TDI); 80/20 mixture of the 2,4 and 2,6 isomer; NCO A/GRADE B

weight 48%; viscosity 5 mPa-s @ 25°C; equivalent weight 87.5; functionality 2

TABLE 4

In certain embodiments, one or more of the above-described isocyanate compositions is provided in a formulation typical of a mixture known in the art of thermoplastic

polyurethane manufacture. Such mixtures may comprise prepolymers formed by the reaction of a molar excess of one or more isocyanates with reactive molecules comprising reactive functional groups such as alcohols, amines, thiols, carboxylates and the like. These mixtures may also comprise solvents, surfactants, stabilizers, and other additives known in the art.

III. Pre-Polymers

In another aspect, the present invention encompasses prepolymers comprising isocyanate-terminated epoxide C0₂-derived polyols. In certain embodiments, such isocyanate-terminated prepolymers comprise a plurality of epoxide-C0₂-derived polyol segments linked via urethane bonds formed from reaction with polyisocyanate compounds. Such prepolymers can be useful for the manufacture of higher TPU polymers.

In certain embodiments, a prepolymer of the present invention is the result of a reaction between one or more of the aliphatic polycarbonate polyols described above with a stoichiometric excess of any one or more of the diisocyanates described herein. The degree of polymerization of these prepolymers (i.e. the average number of polyol segments contained in the prepolymer chains) can be manipulated by controlling the relative amount of isocyanate, as well as the order of reagent addition and the reaction conditions.

In certain embodiments, prepolymers comprise compounds conforming to a formula:

black rectangles ^β represent the carbon skeleton of the diisocyanate, ¹, R², R³, R⁴, n, x, and y, are as defined above and in the classes and subclasses herein.

In certain embodiments, prepolymers comprise compounds conforming to a formula:

wherein Q is 0 or an integer between 1 and about 20, each open rectangle, t 1 , represents a polyol moiety each of which may be the same or different, and · , R¹, R², R³, R⁴, n, x, and y, are as defined above and in the classes and subclasses herein. In certain of these embodiments, some of the polyol moieties are derived from one or more of the aliphatic polycarbonate polyols as defined herein, while other of the polyol moieties may be derived from other polyols such as polyether or polyester polyols as described herein. In certain embodiments, prepolymers comprise chains conforming to the formula:

wherein, and Q, R¹, R², R³, R⁴, n, x, andj, are as defined above and in the classes and subclasses herein.

In other embodiments, a prepolymer may be formed by reacting a stoichiometric excess of polyol with a limited amount of isocyanate. In such embodiments, the inventive prepolymer has -OH end groups and contains two or more polyol units connected by urethane linkages. In certain embodiments, such prepolymers conform to a structure:

wherein ■ , and Q, are as defined above and in the classes and subclasses herein.

In certain embodiments, such prepolymers have structures conforming to:

wherein,

□ and Q, R¹, R², R³, R⁴, «, x, and , are as defined above and in the classes and subclasses herein.

IV. Other co-reactants and additives

As described above, in some embodiments, compositions of the present invention can include one or more of the aliphatic polycarbonate polyols described in Section I above. Additional aliphatic polycarbonate polyols suitable for the formulation of such mixtures of the present invention are disclosed in WO 2010/028362.

In certain embodiments, these mixtures comprise the aliphatic polycarbonate polyols in combination with one or more additional polyols and/or one or more additives. In certain embodiments, the additional polyols are selected from the group consisting of: polyester polyols, in some cases based on adipic acid and various diols; polyether polyols; and/or polycaprolactone polyols. In certain embodiments, the mixtures comprise additional reactive small molecules known as chain extenders such as amines, alcohols, thiols or carboxylic acids that participate in bond-forming reactions with isocyanates. In certain embodiments, additives are selected from the group consisting of: solvents, water, catalysts, surfactants, blowing agents, colorants, UV stabilizers, flame retardants, antimicrobials, plasticizers, cell- openers, antistatic compositions, compatibilizers, and the like.

A. Additional Polyols

In certain embodiments, the mixtures of the present invention comprise aliphatic polycarbonate polyols as described above in combination with one or more additional polyols such as are traditionally used in thermoplastic polyurethane compositions. In embodiments where additional polyols are present, they may comprise up to about 95 weight percent of the total polyol content with the balance of the polyol mixture made up of one or more aliphatic polycarbonate polyols described in Section I above and in the examples and specific embodiments herein.

In embodiments where mixtures of the present invention comprise or derived from a mixture of one or more aliphatic polycarbonate polyols and one or more additional polyols, the additional polyols are selected from the group consisting of polyether polyols, polyester polyols, polystyrene polyols, polyether-carbonate polyols, polyether-ester carbonates, butane diol adipate polyols, ethylene glocol adipate polyols, hexane diol adipate polyols, polycaprolactone polyols, polycarbonate polyols, polytetramethylene ether glycol (PTMEG) polyols, EO/PO polyether polyols, and mixtures of any two or more of these. In certain embodiments, mixtures of the present invention comprise or derived from a mixture of one or more aliphatic polycarbonate polyols as described herein and one or more other polyols selected from the group consisting of materials available commercially under the trade names: Voranol® (Dow), SpecFlex® (Dow), Tercarol® (Dow), Caradol® (Shell),

Hyperliter®, Acclaim® (Bayer Material Science), Ultracel® (Bayer Material Science), Desmophen® (Bayer Material Science), and Arcol® (Bayer Material Science).

In certain embodiments, the mixtures of the present invention contain polyether polyols, polyester polyols, and/or polycaprolactone polyols in combination with one or more aliphatic polycarbonate polyols as described herein. In certain embodiments, such polyols are characterized in that they have an Mn between about 500 and about 10,000 g/mol. In certain embodiments, such polyols have an Mn between about 500 and about 5,000 g mol. In certain embodiments, such polyols have an Mn between about 1,500 and about 25,000 g/mol.

In certain embodiments, mixtures of the present invention contain polyether polyols, polyester polyols, and/or polycaprolactone polyols in combination with one or more aliphatic polycarbonate polyols as described herein. In certain embodiments, such polyols are characterized in that they have a functionality between 1.9 and 2.5. In certain embodiments, such polyols are characterized in that they have a functionality between 1.95 and 2.2. In certain embodiments, such polyols have a functionality greater than 2.5, in which cases such high-functionality polyols typically compromise a minority of the overall polyol formulation. Polyester polyols that may be present include those which can be obtained by known methods, for example, polyester polyols can be based on the reaction of adipic acid with various diols including butanediol (BDO), hexanediol (HDO), and ethylene glycol (EG).

Polyether polyols that may be present include those which can be obtained by known methods, for example, polyether polyols can be produced by anionic polymerization with alkali hydroxides such as sodium hydroxide or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium ethylate, or potassium ethylate or potassium isopropylate as catalysts and with the addition of at least one initiator molecule containing 2 to 8, preferably 2, reactive hydrogens or by cationic polymerization with Lewis acids such as antimony pentachloride, boron trifhioride etherate, etc., or bleaching earth as catalysts from one or more alkylene oxides with 2 to 4 carbons in the alkylene radical. Any suitable alkylene oxide may be used such as 1,3 -propylene oxide, 1,2- and 2,3 butylene oxide, amylene oxides, styrene oxide, and preferably ethylene oxide and 1,2-propylene oxide and mixtures of these oxides. The polyalkylene polyether polyols may be prepared from other starting materials such as tetrahydrofuran and alkylene oxide-tetrahydrofuran mixtures; epihalohydrins such as epichlorohydrin; as well as aralkylene oxides such as styrene oxide. The polyalkylene polyether polyols may have either primary or secondary hydroxyl groups, preferably secondary hydroxyl groups from the addition of propylene oxide onto an initiator because these groups are slower to react. Included among the polyether polyols are polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combinations of polyoxypropylene and polyoxyethylene glycols, poly-l,2-oxybutylene and polyoxyethylene glycols, poly-l,4-tetramefhylene and

polyoxyethylene glycols, and copolymer glycols prepared from blends or sequential addition of two or more alkylene oxides. The polyalkylene polyether polyols may be prepared by any known process such as, for example, the process disclosed by Wurtz in Encyclopedia of Chemical Technology, Vol. 7, pp. 257-262, published by Interscience Publishers, Inc. (1951) or in U.S. Pat. No. 1,922,459. Polyethers which are preferred include the alkylene oxide addition products of polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,2- butanediol, 1,5-pentanediol, l,6hexanediol, 1,7- heptanediol, hydroquinone, resorcinol glycerol, glycerine, 1,1,1-trimethylol-propane, l,l, ltrimethylolethane, pentaerythritol, 1,2,6-hexanetriol, a-methyl glucoside, sucrose, and sorbitol. Also included within the term "polyhydric alcohol" are compounds derived from phenol such as 2,2-bis(4-hydroxyphenyl)-propane, commonly known as Bisphenol A.

Suitable organic amine initiators which may be condensed with alkylene oxides include aromatic amines-such as aniline, N-alkylphenylene-diamines, 2,4'-, 2,2'-, and 4,4'- methylenedianiline, 2,6- or 2,4-toluenediamine, vicinal toluenediamines, o-chloroaniline, p- aminoaniline, 1,5-diaminonaphthalene, methylene dianiline, the various condensation products of aniline and formaldehyde, and the isomeric diaminotoluenes; and aliphatic amines such as mono-, di-, and trialkanolamines, ethylene diamine, propylene diamine, diethylenetriamine, methylamine, triisopropanolamine, 1,3-diaminopropane, 1,3- diaminobutane, and 1,4-diaminobutane. Preferable amines include monoethanolamine, vicinal toluenediamines, ethylenediamines, and propylenediamine. Yet another class of aromatic polyether polyols contemplated for use in this invention are the Mannich-based polyol an alkylene oxide adduct of phenol/formaldehyde/alkanolamine resin, frequently called a "Mannich" polyol such as disclosed in U.S. Pat. Nos. 4,883,826; 4,939,182; and 5,120, 815. In certain embodiments where additional polyols are present, they comprise from about 5 weight percent to about 95 weight percent of the total polyol content with the balance of the polyol mixture made up of one or more aliphatic polycarbonate polyols described in Section I above and in the examples and specific embodiments herein. In certain embodiments, up to about 75 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, up to about 50 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, up to about 40 weight percent, up to about 30 weight percent, up to about 25 weight percent, up to about 20 weight percent, up to about 15 weight percent, or up to about 10 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 5 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 10 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 15 weight percent, at least about 20 weight percent, at least about 25 weight percent, at least about 40 weight percent, or at least about 50 weight percent, of the total polyol content of the mixture is aliphatic polycarbonate polyol.

B. Chain Extenders

In certain embodiments, the mixtures of the present invention include one or more small molecules reactive toward isocyanates. In certain embodiments, reactive small molecules included in the inventive mixtures comprise low molecular weight organic molecules having one or more functional groups selected from the group consisting of alcohols, amines, carboxylic acids, thiols, and combinations of any two or more of these.

In certain embodiments, the mixtures of the present invention include one or more alcohols. In certain embodiments, the mixtures include polyhydric alcohols.

In certain embodiments, reactive small molecules included in the inventive mixtures comprise dihydric alcohols. In certain embodiments, the dihydric alcohol comprises a C2-40 diol. The polyol compound is selected from aliphatic and cycloaliphatic polyol compounds, for example, ethylene glycol, 1 ,2-ethanediol, 1,2-propanediol, 1,3 -propanediol, 1,2- butanediol, 1,2-propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6- hexane diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, neopentyl glycol, 3-methyl- 1,5-pentane diol, 3,3-dimethylolheptane, 1,4-cyclohexane diol, 1,4-cyclohexanedimethanol and 1,4-dihydroxyethyl cyclohexane; and aliphatic and aromatic polyamine compounds, for example, ethylene diamine, 1,2-propylene diamine, 1,6-hexamethylene diamine, isophorone diamine bis(4-aminocyclohexyl)methane, piperazine and meta- or para-xylene diamine; aliphatic, cycloaliphatic and aromatic aminoalcohol compounds, for example, 2- ethanolamine, N-methyldiethanolamine, N-phenyldipropanolamine; hydroxyalkyl sulfamides, for example, hydroxyethyl sulfamide and hydroxyethylaminoethyl sulfamide; urea and water. Among the above-mentioned chain extending compounds, preferably 1,4- butane diol, 2-ethanolamine, and 1,2-propylenediamine are employed. In certain embodiments, the chain extender is selected from the group consisting of: 1,4- cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers,

trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these. The above-mentioned chain-extending compounds may be used alone or in a mixture of two or more thereof.

In certain embodiments, a reactive small molecule included in the inventive mixtures 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.

In certain embodiments, a reactive small molecule included in the inventive mixtures comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid. In certain embodiments, the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

In certain embodiments, a reactive small molecule included in the inventive mixtures comprises a polymeric diol. In certain embodiments, 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. In certain embodiments, the polymeric diol has an average molecular weight less than about 2000 g/mol.

In certain embodiments, a reactive small molecule comprises a hydroxy-carboxylic acid having the general formula (HO)_xQ'(COOi¾,, wherein Q' is a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y are each integers from 1 to 3. In certain embodiments, a coreactant comprises a diol carboxylic acid. In certain embodiments, a coreactant comprises a bis(hydroxylalkyl) alkanoic acid. In certain embodiments, a coreactant comprises a bis(hydroxylmet yl) alkanoic acid. In certain embodiments 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 (dimethylolbiitanoic acid; DMBA), dihydroxysuccinic acid (tartaric acid), and 4,4'-bis(hydroxyphenyl) valeric acid. In certain embodiments, a coreactant comprises an N,N- bis(2-hydroxyalkyl)carboxylic acid.

In certain embodiments, a reactive small molecule comprises a polyhydric alcohol comprising one or more amino groups. In certain embodiments, a reactive small molecule comprises an amino diol. In certain embodiments, a reactive small molecule comprises a diol containing a tertiary amino group. In certain embodiments, 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-chloroaniline, 3-diethylaminopropane- 1,2-diol, 3-dimethylaminopropane-l,2-diol and N-hydroxyethylpiperidine. In certain embodiments, a coreactant comprises a diol containing a quaternary amino group. In certain embodiments, a coreactant comprising a quaternary amino group is an acid salt or quaternized derivative of any of the amino alcohols described above.

In certain embodiments, a reactive small molecule is selected from the group consisting of: 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. In certain embodiments, a reactive small molecule 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. Also suitable for practice in the present invention are propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, 3,3-dichlorobenzidene, 4,4'-methylene-bis-(2-chloroaniline), 3,3-dichloro- 4,4-diamino diphenylmethane, and sulfonated primary and/or secondary amines. In certain embodiments, reactive small molecule is selected from the group consisting of: hydrazine, substituted hydrazines, hydrazine reaction products, and the like, and mixtures thereof. In certain embodiments, a reactive small molecule 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.

In certain embodiments, reactive small molecules 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, 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, Ν,Ν-diethoxylaniline, N,N-diethoxyl toluidine, N,N-diethoxyl-l-aminopyridine, Ν,Ν'-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-aminopropylamine, N-(3-aminopropyl)-N,N'-dimethyl ethylenediamine, N-(3-aminopropyl)-N-methyl ethanolamine, N,N'-bis-(3-aminopropyl)-N,N'-dimethyl ethylenediamine, N,N'-bis-(3-aminopropyl)-piperazine, N-(2-aminoethyl)-piperazine, N, N'- bisoxyethyl propylenediamine, 2,6-diaminopyridine, diethanolaminoacetamide, diethanolamidopropionamide, Ν,Ν-bisoxyethylphenyl thiosemicarbazide, N,N-bis- oxyethylmethyl semicarbazide, ρ,ρ'-bis-aminomethyl dibenzyl methylamine, 2,6- diaminopyridine, 2-dimethylaminomethyl-2-methylpropanel, 3-diol. In certain embodiments, chain-extending agents are compounds that contain two amino groups. In certain embodiments, chain-extending agents are selected from the group consisting of: ethylene diamine, 1,6-hexamethylene diamine, and 1,5-diamino-l-methyl-pentane.

C. Catalysts

In certain embodiments, no catalysts are used in the mixtures. In certain

embodiments, in the polymerization reaction for the polyurethane, a conventional catalyst comprising an amine compound or tin compound can be employed to promote the reaction. These embodiments are most commonly found in reactive extrusion methods of TPU production. Any suitable urethane catalyst may be used, including tertiary amine compounds, guanidines, amidines, and organometallic compounds. Exemplary tertiary amine compounds include triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, 1 -methyl-4- dimethylaminoethylpiperazine, 3 -methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine, N,N-dimefhyl- Ν',Ν'-dimethyl

isopropylpropylenediamine, N,N-diethyl-3-diethylaminopropylamine and

dimethylbenzylamine. Exemplary guanidine compounds include triaza bicyclo 4.4.0 dec-5- ene (TBD), A^-methyl triaza bicyclo 4.4.0 dec-5-ene (MTBD), and pentamethyl guanidine. Exemplary amidine compounds include N- methyl imidizole, and 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU). Exemplary organometallic catalysts include organomercury, organolead, organoferric and organotin catalysts, with organotin catalysts being preferred among these. Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyltin dilaurate, as well as other organometallic compounds such as are disclosed in U.S. Pat. No. 2,846,408. A catalyst for the trimerization of

polyisocyanates, resulting in a polyisocyanurate, such as an alkali metal alkoxide may also optionally be employed herein. Such catalysts are used in an amount which measurably increases the rate of polyurethane or polyisocyanurate formation.

In certain embodiments, where mixtures of the present invention comprise catalysts, the catalysts comprise tin-based materials. In certain embodiments, tin catalysts included in the B-side mixtures are selected from the group consisting of: di-butyl tin dilaurate, dibutylbis(laurylthio)stannate, dibutyltinbis(isooctylmercapto acetate) and

dibutyltinbis(isooctylmaleate), tin octanoate and mixtures of any two or more of these.

In certain embodiments, catalysts included in the B-side mixtures comprise tertiary amines. In certain embodiments, catalysts included in the B-side mixtures are selected from the group consisting of: DABCO, pentametyldipropylenetriamine, bis(dimethylamino ethyl ether), pentamethyldiethylenetriamine, DBU phenol salt, dimethylcyclohexylamine, 2,4,6- tris(N,N-dimethylaminomethyl)phenol (DMT-30), l,3,5-tris(3- dimethylaminopropyl)hexahydro-s-triazine, ammonium salts and combinations or formulations of any of these.

Typical amounts of catalyst are 0.001 to 10 parts of catalyst per 100 parts by weight of total polyol in the mixture. In certain embodiments, catalyst levels in the formulation, when used, range between about 0.001 pph (weight parts per hundred) and about 3 pph based on the amount of polyol present in the mixture. In certain embodiments, catalyst levels range between about 0.05 pph and about 1 pph, or between about 0.1 pph and about 0.5 pph.

D. Mono-functional Materials

In certain embodiments, monofunctional components are added. A monofunctional alcohol will serve as a chain termination which can be used to limit molecular weight or crosslinking if higher functionality species are used. U.S. Patent 5,545,706 illustrates the use of a monofunctional alcohol in a substantially linear polyurethane. The monofunctional alcohol can be any compound with one alcohol available for reaction with isocyanate such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, phenol and the like. Additionally, the monofunctional component can be added as a low molecular weight polymer that has been initiated by or reacted with the monofunctional alcohol. The monofunctional alcohol can be a polyether such as polypropylene oxide or polyethylene oxide initiated with any of the monofunctional alcohols listed. The monofunctional alcohol can be a polyester polymer where the monofunctional alcohol is added to the recipe. The monofunctional alcohol can be a polycarbonate polymer such as polyethylene carbonate or polypropylene carbonate initiated with a monfunctional anion, such as halide, nitrate, azide, carboxylate, or a monohydric alcohol.

Similarly, the monofunctional component could be an isocyanate. Any

monofunctional isocyanate could be added for this same function. Possible materials include phenyl isocyanate, naphthyl isocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, octyl isocyanate and the like.

E. Blowing Agents

In certain embodiments, no blowing agents are used in mixtures and compositions of the present invention. In certain embodiments, mixtures of the present invention contain blowing agents: although these compositions are less common they are used in certain specialty thermoplastic polyurethane applications such as microcellular footwear TPU elastomers. Blowing agents may be chemical blowing agents (typically molecules that react with components to liberate C0₂ or other volatile compounds) or they may be physical blowing agents (typically molecules with a low^r boiling point that vaporize during the foam formation. Many blowing agents are known in the art and may be applied to compositions of the present invention according to conventional methodology. The choice of blowing agent and the amounts added can be a matter of routine experimentation.

In certain embodiments, the blowing agent comprises a chemical blowing agent. In certain embodiments, water is present as a blowing agent. Water functions as a blowing agent by reacting with a portion of the isocyanate in the mixture to produce carbon dioxide gas. Similarly, formic acid can be included as a blowing agent. Formic acid functions as a blowing agent by reacting with a portion of the isocyanate to produce carbon dioxide and carbon monoxide gas.

In certain embodiments, water is present in an amount of from 0.5 to 20 parts per 100 parts by weight of the polyol in the composition. In certain embodiments, water is present from about 1 to 10 parts, from about 2 to 8 parts, or from about 4 to 6 parts per 100 parts by weight of polyol in the composition. In certain embodiments, it is advantageous not to exceed 2 parts of water, not-to exceed 1.5 parts of water, or not to exceed 0.75 parts of water. In certain embodiments, it is advantageous to have water absent.

In certain embodiments, formic acid is present in an amount of from 0.5 to 20 parts per 100 parts by weight of the polyol in the composition. In certain embodiments, formic acid is present from about 1 to 10 parts, from about 2 to 8 parts, or from about 4 to 6 parts per 100 parts by weight of polyol in the composition.

In certain embodiments physical blowing agents can be used. Suitable physical blowing agents include hydrocarbons, fluorine-containing organic molecules hydrocarbons, chlorocarbons, acetone, methyl formate and carbon dioxide. In some embodiments, fluorine- containing organic molecules comprise perfluorinated compounds, chlorofluorocarbons, hydrochlorofluorocarbons, and hydrofluorocarbons. Suitable hydrofluoroalkanes are C1.4 compounds including difiuoromethane (R-32), 1,1,1,2-tetrafluoroethane (R-134a), 1, 1- difluoroethane (R-152a), difiuorochloroethane (R-142b), trifiuoromethane (R-23), heptafluoropropane (R-227a), hexafluoropropane (R136), 1,1,1-trifluoroefhane (R-133), fluoroethane (R-161), 1,1,1,2,2-pentafluoropropane (R-245fa), pentafluoropropylene (R2125a), 1, 1, 1,3-tetrafiuoropropane, tetrafhioropropylene (R-2134a), 1,1,2,3,3- pentafluoropropane and 1,1,1,3,3-pentafiuoro-H-butane. In certain embodiments, when a hydrofiuorocarbon blowing agent is present in the mixture, it is selected from the group consisting of: tetrafluoroethane (R-134a),

pentafluoropropane (R-245fa) and pentafluorobutane (R-365).

Suitable hydrocarbons for use as blowing agent include nonhalogenated hydrocarbons such as butane, isobutane, 2,3-dimethylbutane, n- and /-pentane isomers, hexane isomers, heptane isomers and cycloalkanes including cyclopentane, cyclohexane and cycloheptane. Preferred hydrocarbons for use as blowing agents include cyclopentane and notably n- pentane an iso-pentane. In a certain embodiments the composition comprises a physical blowing agent selected from the group consisting of tetrafluoroethane (R-134a), pentafluoropropane (R-245fa), pentafluorobutane (R-365), cyclopentane, n-pentane and iso- pentane.

In certain embodiments where a physical blowing agent is present, it is used in an amount of from about 1 to about 20 parts per 100 parts by weight of the polyol in the composition. In certain embodiments, the physical blowing agent is present from 2 to 15 parts, or from 4 to 10 parts per 100 parts by weight of the polyol in the composition.

F. Additives

In addition to the above components, mixtures of the present invention may optionally contain various additives as are known in the art of thermoplastic polyurethane technology. Such additives may include, but are not limited to compatibilizers, colorants, surfactants, flame retardants, antistatic compounds, antimicrobials, UV stabilizers, plasticizers, and cell openers.

1. Colorants

In certain embodiments, the mixtures of the present invention comprise one or more suitable colorants. Many TPU products are color coded during manufacture to identify product grade, to conceal yellowing, or to make a consumer product. The historical method of coloring TPUs was to blend in traditional pigments or dyes. Typical inorganic coloring agents included titanium dioxide, iron oxides and chromium oxide. Organic pigments originated from the azo/diazo dyes, phthalocyanines and dioxazines, as well as carbon black. Recent advances in the development of polyol-bound colorants are described in: Miley, J. W.; Moore, P. D. "Reactive Polymeric Colorants For Polyurethane",

Proceedings Of The SPI-26th Annual Technical Conference; Technomic: Lancaster, Pa., 1981 ; 83-86.

Moore, P. D.; Miley, J. W.; Bates, S. H.; "New Uses For Highly Miscible Liquid

Polymeric Colorants In The Manufacture of Colored Urethane Systems"; Proceedings of the SPI-27th Annual Technical/Marketing Conference; Technomic: Lancaster, Pa., 1982; 255-261.

Bates, S. FL; Miley, J. W. "Polyol-Bound Colorants Solve Polyurethane Color Problems";

Proceedings Of The SPI-30th Annual Technical/ Marketing Conference; Technomic:

Lancaster, Pa., 1986; 160-165

Vielee, R. C; Haney, T. V. "Polyurefhanes"; In Coloring of Plastics;Webber, T. G., Ed.,

Wiley-Interscience: New York, 1979, 191-204.

2. UV Stabilizers

In certain embodiments, the mixtures of the present invention comprise one or more suitable UV stabilizers. Polyurefhanes based on aromatic isocyanates will typically turn dark shades of yellow upon aging with exposure to light. A review of polyurethane weathering phenomena is presented in: Davis, A.; Sims, D. Weathering Of Polymers; Applied Science: London, 1983, 222-237. Light protection agents, such as hydroxybenzotriazoles, zinc dibutyl thiocarbamate, 2,6-ditertiary butylcatechol, hydroxybenzophenones, hindered amines and phosphites have been used to improve the light stability of polyurethanes. Color pigments have also been used successfully for UV stabilization.

3. Flame Retardants

In certain embodiments, the mixtures of the present invention comprise one or more suitable flame retardants. Flame retardants are often added to reduce flammability. The choice of flame retardant for any specific TPU often depends upon the intended service application of that TPU and the attendant flammability testing scenario governing that application. Aspects of flammability that may be influenced by additives include the initial ignitability, burning rate and smoke evolution.

The most widely used flame retardants are the chlorinated phosphate esters, chlorinated paraffins and melamine powders. These and many other compositions are available from specialty chemical suppliers. A review of this subject has been given: Kuryla, W. C; Papa, A. J. Flame Retardancy of Polymeric Materials, Vol. 3; Marcel Dekker: New York, 1975, 1-133.

4. Bacteriostats

Under certain conditions of warmth and high humidity, TPUs are susceptible to attack by microorganisms. When this is a concern, additives against bacteria, yeast or fungi are added to the TPU during manufacture. In certain embodiments, the mixtures of the present invention comprise one or more suitable bacteriostats.

5. Plasticizers

In certain embodiments, the mixtures of the present invention comprise one or more suitable plasticizers. Nonreactive liquids have been used to soften a TPU or to reduce viscosity for improved processing. The softening effect can be compensated for by using a polyol of lower equivalent weight. These materials often adversely affect physical properties.

6. Cell-Openers

In certain embodiments, mixtures of the present invention comprise one or more suitable cell openers. In some specialty blown TPUs it is necessary to add cell-openers to obtain a foamed TPU structure of the required properties. Known additives for inducing cell- opening include silicone-based antifoamers, waxes, finely divided solids, liquid

perfluocarbons, paraffin oils, long-chain fatty acids and certain polyether polyols made using high concentrations of ethylene oxide.

7. Anti-Static Agents

In certain embodiments, the mixtures of the present invention comprise one or more suitable antistatic compounds. Some TPUs are used in packaging, clothing and other applications where it is desired to minimize the electrical resistance of the foam so that buildup of static electrical charges is minimized. This has traditionally been accomplished through the addition of ionizable metal salts, carboxylic acid salts, phosphate esters and mixtures thereof. These agents function either by being inherently conductive or by absorbing moisture from the air. The desired net result is orders of magnitude reduction in foam surface resistivity. 8. Compatibilizers

In certain embodiments, the mixtures of the present invention comprise one or more suitable compatibilizers. Compatibilizers are molecules that allow two or more nonmiscible ingredients to come together and give a homogeneous liquid phase. Many such molecules are known to the polyurethane industry, these include: amides, amines, hydrocarbon oils, phthalates, polybutyleneglycols, and ureas.

V. Compositions of Specific Mixtures and Methods of Carrying Out the Invention

In certain embodiments, the present invention encompasses mixtures suitable for the formation of TPUs wherein the mixtures comprise:

10-80 parts by weight of one or more isocyanate components or pre-polymers

based on isocyanate components as described above and in the specific embodiments and examples herein;

20-90 parts by weight of a polyol component or a polyol-based pre-polymer

component, wherein the polyol component comprises from about 5 weight percent to 100 weight percent of one or more of the aliphatic polycarbonate polyols described above and in the specific

embodiments and examples herein;

0.01 to 10 parts by weight of one or more blowing agents as described above

and in the specific embodiments and examples herein;

0 to 1 parts by weight of one or more catalysts as described above and in the

specific embodiments and examples herein;

0 to 20 parts by weight of one or more chain extenders, wherein the chain

extenders molecules are substantially as described above and in the specific embodiments and examples herein; and

0 to 10 parts by weight of one or more additives, wherein the additives are

selected from the group consisting of: compatibilizers, colorants, surfactants, flame retardants, antistatic compounds, antimicrobials, UV stabilizers, plasticizers, and cell openers substantially as described above and in the specific embodiments and examples herein.;

In certain embodiments, the present invention encompasses a mixture denoted PEC- Bl wherein the polyol component comprises 5 to 100 weight percent poly(ethylene carbonate) polyol, said poly(ethylene carbonate) characterized in that it has a functional number of 2, an Mn less than about 7000 g/mol and greater than 99% hydroxyl end groups.

In certain embodiments, mixtures PEC-B1 are characterized in that the poly(ethylene carbonate) polyol has an Mn less than about 5,000 g/mol, less than about 4,000 g/mol, less than about 3,000 g/mol, less than about 2,500 g/mol, or less than about 2,000 g/mol. In certain embodiments, the poly(ethylene carbonate) polyol has an Mn of between about 500g/mol and about 3,000 g/mol. In certain embodiments, the poly(ethylene carbonate) polyol has an Mn of between about 500g mol and about 2,500 g/mol. In certain

embodiments, the poly(ethylene carbonate) polyol has an Mn of between about 500g/mol and about 2,000 g/mol.

In certain embodiments, mixtures PEC-B1 are characterized in that the poly(ethylene carbonate) polyol has greater than 99%, greater than 99.5%, greater than 99.7%, greater than 99.8% or greater than about 99.9% -OH end groups.

In certain embodiments, mixtures PEC-B1 are characterized in that the poly(ethylene carbonate) polyol has a polydispersity index (PDI) less than about 1.8. In certain embodiments, the poly(ethylene carbonate) polyol has a PDI less than about 1.5, less than about 1.4, less than about 1.3, or less than about 1.2. In certain embodiments, the poly(ethylene carbonate) polyol is characterized in that it has a PDI between about 1.05 and about 1.2.

In certain embodiments, mixtures PEC-B1 are characterized in that the poly(ethylene carbonate) polyol contains, on average, greater than about 80% carbonate linkages. In certain embodiments, the poly(ethylene carbonate) polyol contains, on average, greater than about 85%, greater than about 90%, greater than about 92%, greater than about 95%, greater than about 97%, greater than about 98%, or greater than about 99% carbonate linkages. In certain embodiments, the poly(ethylene carbonate) polyol contains, on average, less than about 1 % ether linkages. In certain embodiments, the % carbonate linkage and/or percent ether linkage characteristics are defined as being exclusive of any embedded chain transfer agent that may be embedded in the polycarbonate polyol chain.

In certain embodiments, mixtures PEC-B1 are characterized in that the included poly(ethylene carbonate) polyol has a viscosity below 1,000,000 centipoise at 20 degrees celcius. In certain embodiments, poly(ethylene carbonate) polyol has a viscosity below 150,000 centipoise at 20 degrees celcius. In certain embodiments, the polyethylene carbonate) polyol has a viscosity below 100,000 centipoise, below 60,000 centipoise, or below 40,000 centipoise, all at 20 degrees celcius. In certain embodiments, the poly(ethylene carbonate) poly has a viscosity below 10,000 centipoise at 20 degrees celcius.

In certain embodiments, mixtures PEC-B1 are further characterized in that the poly(ethylene carbonate) polyol has a formula P2c:

wherein each -Y is -OH, and each of

_; and n is as defined above and

described in classes and subclasses herein.

In certain embodiments, mixtures PEC-B1 are characterized in that the poly(ethylene carbonate) polyol has a formula Ql :

wherein t is an integer from 1 to 11 and n is as defined above and in the

specific embodiments and examples herein.

In certain embodiments, where compositions comprise polyols of formula Ql, t is an integer between 1 and 5. In certain embodiments, ί is 1. In certain embodiments, t is 2. In certain embodiments, t is 3. In certain embodiments, t is 4. In certain embodiments, t is 5.

In certain embodiments, mixtures PEC-B1 are characterized in that the poly(ethylene carbonate) polyol has a formula Q4:

wherein R^l is independently at each occurrence -H, or -CH₃, and each of n

and t is as defined above and described in the specific examples and embodiments herein.

In certain embodiments, where compositions comprise polyols of formula Q4, t is an integer between 1 and 3. In certain embodiments, ί is 1. In certain embodiments, t is 2. In certain embodiments, t is 3.

In certain embodiments, the present invention encompasses a mixture denoted PPC-1 containing 100 parts by weight of a polyol component, wherein the polyol component comprises 5 to 100 weight percent poly(propylene carbonate) polyol, said poly(propylene carbonate) characterized in that it has an Mn less than about 7000 g/mol and greater than 99% hydroxy 1 end groups.

In certain embodiments, mixtures PPC-B1 are characterized in that the

poly(propylene carbonate) polyol has an Mn less than about 5,000 g/mol, less than about 4,000 g/mol, less than about 3,000 g/mol, less than about 2,500 g/mol, or less than about 2,000 g/mol. In certain embodiments, the poly(propylene carbonate) polyol has an Mn of between about 500g/mol and about 3,000 g/mol. In certain embodiments, the poly(propylene carbonate) polyol has an Mn of between about 500g/mol and about 2,500 g/mol. In certain embodiments, the poly(propylene carbonate) polyol has an Mn of between about 500g/mol and about 2,000 g/mol.

In certain embodiments, mixtures PPC-B1 are characterized in that the

poly(propylene carbonate) polyol has greater than 99%, greater than 99.5%, greater than 99.7%, greater than 99.8% or greater than about 99.9% -OH end groups.

In certain embodiments, mixtures PPC-B1 are further characterized in that the poly(propylene carbonate) polyol has a polydispersity index (PDI) less than about 1.8. In certain embodiments, the poly(propylene carbonate) polyol has a PDI less than about 1.5, less than about 1.4, less than about 1.3, or less than about 1.2. In certain embodiments, the poly(propylene carbonate) polyol is characterized in that it has a PDI between about 1.05 and about 1.2.

In certain embodiments, mixtures PPC-B1 are further characterized in that the poly(propylene carbonate) polyol contains, on average, greater than about 90% carbonate linkages. In certain embodiments, the poly(ethylene carbonate) polyol contains, on average, greater than about 95%, greater than about 97%, greater than about 98%, greater than about 99%, greater than about 99.5%, or greater than about 99.9%, carbonate linkages. In certain embodiments, the polypropylene carbonate) polyol contains no detectable ether linkages. In certain embodiments, the percent carbonate linkage and/or percent ether linkage

characteristics are defined as being exclusive of any embedded chain transfer agent that may be present within the polycarbonate polyol chain.

In certain embodiments, mixtures PPC-B1 are further characterized in that the included polypropylene carbonate) polyol has a viscosity below about 1,000,000 centipoise at 20 degrees celcius. In certain embodiments, the poly(ethylene carbonate) polyol has a viscosity below 30,000 centipoise, below 15,000 centipoise, or below 12,000 centipoise, all at 20 degrees celcius. In certain embodiments, the poly(ethylene carbonate) poly has a viscosity below 10,000 centipoise, 8,000 centipoise, or 6,000 centipoise at 20 degrees celcius.

In certain embodiments, mixtures PPC-B1 are further characterized in that the polypropylene carbonate) polyol has a formula P2a:

wherein each -Y is -OH, and each of

_; and n is as defined above and

described in classes and subclasses herein.

In certain embodiments, mixtures PPC-B1 are characterized in that the

polypropylene carbonate) polyol has a formula Q2:

wherein each of and n is as defined above and in the specific embodiments and examples herein.

In certain embodiments, where compositions comprise polyols of formula Q2, t is an integer between 1 and 5. In certain embodiments, ί is 1. In certain embodiments, t is 2. In certain embodiments, t is 3. In certain embodiments, t is 4. In certain embodiments, t is 5.

In certain embodiments, mixtures PPC-B1 are characterized in that the

polypropylene carbonate) polyol has a formula Q5:

wherein R¹ is independently at each occurrence -H, or -C¾, and each of n

In certain embodiments, where compositions comprise polyols of formula Q5, t is an integer between 1 and 3. In certain embodiments, f is 1. In certain embodiments, t is 2. In certain embodiments, t is 3.

In certain embodiments mixtures PEC-B1 and PPC-B1 are characterized in that polyol component of the mixtures contain from about 5% to 100% of the described aliphatic polycarbonate polyol, with the balance (if any) comprising one or more polyols typically used for polyurethane thermoplastic formulation.

In certain embodiments where mixtures PEC-B1 and PPC-B1 contain less than 100% aliphatic polycarbonate polyol, the balance comprises a polyol selected from the group consisting of polyether polyols, polyester polyols, and combinations of these. In certain embodiments, the balance comprises a polyether polyol. In certain embodiments, the balance comprises a polyester polyol.

In certain embodiments, the mixtures of the present invention comprise a single aliphatic polycarbonate polyol from the list described above and a single chain extender from the list described above. Such a mixture is often referred to as a "B-side" mixture (although this nomenclature is not common in the area of TPUs), and can be formulated to have attractive processing characteristics such as an optimum viscosity, and can be stored for future reaction with one or more isocyanates or pre-polymers. In certain embodiments, these mixtures comprise an aliphatic polycarbonate polyol and another polyol of the types listed above and a single chain extender. In certain embodiments, these mixtures comprise a single polyol and multiple chain extenders. In certain embodiments, these mixtures comprise multiple polyols and multiple chain extenders. In certain embodiments, these mixtures comprise one or more polyols, one or more chain extenders, and one or more additives as described in the lists above.

The polyurethane producing reaction can be carried out in the absence of a reaction medium, or in the presence of a solvent non-reactive to the diisocyanates. When no reaction medium is used, the polymerization reaction can be carried out (1) by mixing an aliphatic polycarbonate diol with a chain extender, and further mixing the resultant mixture with a diisocyanate to cause all the mixed compounds to be reacted with each other; (2) by reacting the an aliphatic polycarbonate diol with the diisocyanate to produce a prepolymer having isocyanate end groups, mixing the prepolymer-containing mixture with the chain extender to allow the prepolymer to react with the chain extender; or (3) by mixing an aliphatic polycarbonate diol with the chain extender, further mixing a portion of the necessary amount of the diisocyanate to allow the mixed portion of the diisocyanate to react with the aliphatic polycarbonate diol and the chain extender and to produce a prepolymer having hydroxyl groups, still further mixing a remaining portion of the diisocyanate into the prepolymer- containing mixture to allow the mixed portion of the diisocyanate to react with the prepolymer.

The polymerization reaction in the absence of the reaction medium is preferably carried out at a reaction temperature of 80 to 150° C. When the procedure (2) or (3) is carried out, the resultant prepolymer has a low molecular weight, the prepolymer must be further polymerized to increase the molecular weight thereof.

When the reaction medium (solvent) is employed, the polymerization reaction for the thermoplastic polyurethane is carried out (1) by dissolving an aliphatic polycarbonate diol in a solvent, optionally mixing the resultant solution with a chain extender and then with a diisocyanate, and subjecting the resultant reaction mixture to the polymerization reaction; (2) by dissolving the aliphatic polycarbonate diol in a solvent, mixing the resultant solution with the diisocyanate to allow the diisocyanate to react with the aliphatic polycarbonate diol and to prepare a prepolymer having isocyanate end groups, and further mixing the prepolymer- containing mixture with the chain extender to allow the chain extender to react with the prepolymer; or (3) by dissolving the aliphatic polycarbonate diol in the solvent, mixing the resultant solution with the chain extender and a portion of the necessary amount of diisocyanate, to allow the mixed chain extender and diisocyanate to react with the aliphatic polycarbonate diol and to prepare a prepolymer having hydroxyl groups, and further mixing the prepolymer-containing mixture with a remaining portion of the diisocyanate, to allow the diisocyanate to react with the prepolymer. The polymerization reaction in the presence of the reaction medium (solvent) is preferably carried out at a reaction temperature of 20 to 100° C. The solvent for the reaction medium preferably comprises at least one material selected from the group consisting of: methylethyl ketone, ethyl acetate, toluene, dioxane,

dimethylformamide, and dimethylsulfoxide.

The polyurethane components can be mixed in a batch, mixed and dispensed continuously, or mixed continuously in an extruder. For illustration, U.S. Patent 3,642,964 describes the continuous feed and mixing of polyurethane components to an extruder where the components are substantially reacted in the extruder. Output strands of the extruder are then cooled and pelletized. Another illustration of the polyurethane component mixing and reaction is shown in U.S. Patent 6,294,637 where the extruder is a twin screw extruder. U.S. Patent 6,930,163 illustrates a tubular reactor with a mixer to substitute for the extruder. All of these production methods are incorporated by reference.

In certain embodiments of compositions of the present invention produced by the above-mentioned polymerization procedures, the terminal groups of the polyurethane molecules are hydroxyl groups or isocyanate groups. The thermoplastic polyurethane of the present invention can be further polymerized linearly or in three-dimensional network structure by reacting with a compound having at least two hydrogen atoms reactive to isocyanate groups per molecule, or a compound having two isocyanate groups per molecule. Also, by reacting with a compound having a urethane bond and/or a urea bond or a compound having at least three hydrogen atoms reactive to the isocyanate groups, the thermoplastic polyurethane of the present invention can be modified with a cross-linking structure introduced thereinto. Further, the thermoplastic polyurethane of the present invention optionally contains one or more conventional additives unless the additives negatively impact the effect of the present invention.

In the polymerization reaction, the polyurethane the chain extender is preferably employed in an amount in the range of from 0.1 to 10 moles, more preferably 0.5 to 5 moles, per mole of the aliphatic polycarbonate diol. The molar ratio of the chain extender to the polyol diol(s) can be established in response to the target properties of the thermoplastic polyurethane.

Also, the diisocyanate is preferably employed in a molar amount approximately equal to the total molar amount of the polycarbonate diol and the chain extender. Particularly, the diisocyanate is preferably employed in an equivalent weight ratio of total active hydrogen atoms contained in the polycarbonate diol and the chain extender to the isocyanate groups of the diisocyanate of 1:0.8 to 1 :1.2, more preferably 1 :0.95 to 1 : 1.05.

Also, in the polymerization reaction for the polyurethane, a conventional catalyst comprising an amine compound or tin compound can be employed to promote the reaction.

VI. TPU compositions

In another aspect, the present invention encompasses TPUs derived from one or more of aliphatic polycarbonate polyol compositions described above and in the specific embodiments and examples disclosed herein. In certain embodiments, the TPU compositions comprise the reaction product of one or more isocyanates with one or more of the aliphatic polycarbonate polyol compositions defined above. In certain embodiments, the TPU compositions comprise the reaction product of one or more isocyanates and a mixture containing one or more of the aliphatic polycarbonate polyol compositions defined above.

A. MDI-based TPUs

In one aspect, the present invention encompasses MDI-based TPUs. In certain embodiments, such TPU compositions are derived from MDI (or an analog or polymeric derivative thereof) and one or more of the aliphatic polycarbonate polyol compositions as defined above and in the embodiments and examples herein. In certain embodiments the MDI-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric MDI with a B-side mixture of type PEC-B1, described above.

In certain embodiments the MDI-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric MDI with a B-side mixture of type PPC-B1, described above.

In certain embodiments, MDI-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric MDI with a B-side mixture comprising an aliphatic polycarbonate polyol selected from the group consisting of:

Poly(ethylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% 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, 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, 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, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/'mol, a polydisperisty index less than about 1.25, at least 90% 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, 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, 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, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 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 90% carbonate linkages, and at least 98% -OH end groups;

Poly(propylene carbonate) of formula Q7' having an average molecular weight number of about 3,000 g/mol, 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 Q8' having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, 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 Q8' having an average molecular weight number of about 1,000 g/mol, 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 Q8' having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

mixtures of any two or more of these.

In certain embodiments, MDI-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric MDI with a B-side mixture comprising an aliphatic polycarbonate polyol of structure Q7:

wherein,

R^q is at each occurrence in the polymer chain independently -H or -C¾;

R^a is -H, or -CH₃;

q and q' are independently an integer from about 2 to about 40; and

and n is as defined above and in the examples and embodiments herein.

In certain embodiments, MDI-based TPU compositions of the present invention comprise the reaction product of a pure or polymeric MDI with an aliphatic polycarbonate polyol selected from the group consisting of:

where each of n, q, q', and R is as defined above and in the classes and subclasses herein.

In certain embodiments, MDI-based TPU compositions of the present invention comprise the reaction product of a pure or polymeric MDI with an aliphatic polycarbonate polyol derived from a commercially available polyether polyol such as those typically used in the formulation of polyurethane compositions.

In certain embodiments, MDI-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric MDI with a B-side mixture comprising an aliphatic polycarbonate polyol of structure Q8:

wherein,

c is at each occurrence in the polymer chain independently an integer from 0 to 6; d is at each occurrence in the polymer chain independently an integer from 1 to 11; and

each of R^q, n, and q is as defined above and in the examples and embodiments herein. In certain embodiments, MDI-based TPU compositions of the present invention comprise the reaction product of a pure or polymeric MDI with an aliphatic polycarbonate polyol selected from the group consisting of:

where each of n, and q is as defined above and in the classes and subclasses herein.

In certain embodiments, formulations for MDI-based thermoplastic elastomers of the invention have viscosities below 1 ,000,000 centipoise, preferably below 500,000 centipoise at 20 degrees celcius. Preferred polyols have OH numbers between 28 and 224. Preferred polyols have acid numbers below 1. Preferred polyols have functionalities between 1.9 and 2.1. Preferred isocyanates have functionalities between 1.9 and 2.1.

In certain embodiments, MDI-based TPU formulations have MDI concentrations between 15 and 30% by weight, polyol concentrations (one or more of which is/are aliphatic polycarbonate polyols) of 55-80%, chain extender concentrations of 1-10%, and additive concentrations of 0-5%. In certain embodiments, MDI-based TPU formulations have MDI concentrations between 30 and 50% by weight, polyol concentrations (one or more of which is/are aliphatic polycarbonate polyols) of 30 to 60%, chain extender concentrations of 1-20%, and additive concentrations of 0-5%.Preferred finished MDI-based TPUs can have varied properties depending on the specific polyols and additives used. In certain embodiments, the finished TPUs have a shore A hardness of 75-95. In certain embodiments, the finished TPUs have a shore D harness of 50-70. In certain embodiments, the finished TPUs have tensile strength between 10 and 30 MPa. In certain embodiments, the finished TPUs have tensile strength between 30 and 50 MPa. In certain embodiments, the finished TPUs have tensile strength greater than 50 MPa.

B. Aliphatic lsocyanate-based TPUs

In one aspect, the present invention encompasses aliphatic isocyanate-based TPU compositions. In certain embodiments, such TPU compositions are derived from a mixture containing one or more of the aliphatic polycarbonate polyol compositions as defined above and in the embodiments and examples herein.

In certain embodiments the aliphatic isocyanate-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric aliphatic polyisocyanates with a B-side mixture of type PEC-B1, described above.

In certain embodiments the aliphatic isocyanate-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric aliphatic isocyanate with a B-side mixture of type PPC-B1, described above.

In certain embodiments, aliphatic isocyanate-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric aliphatic isocyanate with a B-side mixture comprising an aliphatic polycarbonate polyol selected from the group consisting of:

Poly(ethylene carbonate) of formula Ql having an average molecular weight number of about 500 g/mol, 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 Ql having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene 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

Poly(propylene carbonate) of formula Q5 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, 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 Q5 having an average molecular weight number of about 500 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of between about 500 g/mol and about 3,000 g/'mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 1 ,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 1 1), a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 3,000 g/mol, 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 Q7' having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

mixtures of any two or more of these. In certain embodiments, aliphatic isocyanate-based TPU compositions of the present invention comprise the reaction product of an A-side composition comprising a pure or polymeric aliphatic isocyanate with a B-side mixture comprising an aliphatic polycarbonate polyol o

wherein,

R^q is at each occurrence in the polymer chain independently -H or -C¾;

R^a is -H, or -CH₃;

q and q' are independently an integer from about 2 to about 40; and

and n is as defined above and in the examples and embodiments herein.

In certain embodiments, aliphatic isocyanate-based TPU compositions of the present invention comprise the reaction product of aliphatic isocyanate with an aliphatic polycarbonate polyol selected from the group consisting of:

where each of n, q, q', and R is as defined above and in the classes and subclasses herein. In certain embodiments, aliphatic isocyanate-based TPU compositions of the present invention comprise the reaction product of an aliphatic isocyanate with an aliphatic polycarbonate polyol derived from a commercially available polyether polyol such as those typically used in the formulation of polyuretliane compositions.

In certain embodiments, aliphatic isocyanate-based TPU composition of the present invention comprises the reaction product of an A-side composition comprising a pure or polymeric aliphatic isocyanate with a B-side mixture comprising an aliphatic polycarbonate polyol o

wherein,

each of R^q, n, and q is as defined above and in the examples and embodiments herein.

In certain embodiments, aliphatic isocyanate-based TPU compositions of the present invention comprise a reaction product of an aliphatic isocyanate with an aliphatic polycarbonate polyol selected from the group consisting of:

In certain embodiments, formulations for aliphatic isocyanate-based thermoplastic elastomers of the invention have viscosities below 1,000,000 centipoise, preferably below 500,000 centipoise at 20 degrees celcius. Preferred polyols have OH numbers between 28 and 224. Preferred polyols have acid numbers below 1. Preferred polyols have

functionalities between 1.9 and 2.1. Preferred isocyanates have functionalities between 1.9 and 2.1.

In certain embodiments, aliphatic-based TPU formulations have isocyanate concentrations between 20 and 40% by weight, polyol concentrations (one or more of which is/are aliphatic polycarbonate polyols) of 50 to 70%, chain extender concentrations of 1-10%, and additive concentrations of 0-5%. In certain embodiments, aliphatic-based TPU formulations have isocyanate concentrations between 35 and 55% by weight, polyol concentrations (one or more of which is/are aliphatic polycarbonate polyols) of 35 to 55%, chain extender concentrations of 2-15%, and additive concentrations of 0-5%.Preferred finished aliphatic -based TPUs can have varied properties depending on the specific polyols and additives used. In certain embodiments, the finished TPUs have a shore A hardness of 75-95. In certain embodiments, the finished TPUs have a shore D harness of 40-70. In certain embodiments, the finished TPUs have tensile strength between 10 and 30 MPa. In certain embodiments, the finished TPUs have tensile strength between 30 and 50 MPa. In certain embodiments, the finished TPUs have tensile strength greater than 50 MPa.

In certain embodiments, TPUs provided by the present invention have the unexpected advantage that they are much more transparent than corresponding TPUs formulated from prior art polyols (See Figure 1).

EXAMPLES

The present invention is illustrated by the following examples. It is to be understood that the particular examples, materials, amounts, and procedures are to be interpreted broadly in accordance with the scope and spirit of the invention as set forth herein.

Presented below are the formulations of a variety of thermoplastic polyurethanes. These materials were made using aliphatic polycarbonate polyols as defined hereinabove. Specifically, the aliphatic polycarbonate polyols used and identified in the examples below have the following properties:

NOV-53-053 is a poly(ethylene carbonate) polyol initiated with Fomrez® 1 1-1 12 and having an Mn of 2486 g/mol, a PDI of 1.41, containing greater than 99% -OH end groups and having approximately 85% carbonate linkages (excluding the starter). This material conforms to formula Q8a, where q is, on average in the composition, approximately 4.4, and n is on average in the composition approximately 8.4.

NOV-53-050 is a polyethylene carbonate) polyol initiated with Voranol® 220-1 10N a polyether polyol (polypropylene oxide capped with polyethylene oxide -1,000 g/mol). The polyol has an Mn of 2656 g/mol, a PDI of 1.10, contains greater than 99% -OH end groups and approximately 85% carbonate linkages (excluding the starter). This material conforms to formula Q7b:

are, on average in the composition, approximately 8, and n is on average in the composition approximately 5.3. NOV-53-052 is a poly(ethylene carbonate) polyol initiated with Voranol® 220-1 ION and having an Mn of 1938 g mol, a PDI of 1.11, containing greater than 99% -OH end groups and approximately 85% carbonate linkages (excluding the starter). This material conforms to formula Q7b, where q and q' are, on average in the composition, approximately 8, and n is on average in the composition approximately 9.4.

NOV-58-076 is a polypropylene carbonate) polyol initiated with dipropylene glycol and having an Mn of 816 g/mol, a PDI of 1.15, containing greater than 99% -OH end groups and >99% carbonate linkages (excluding the starter). This material conforms to formula Q5,

s methyl, ί is 2, and n is on average in the composition approximately 3.3.

Example 1: TPU formulations without a prepolymer step

In Example 1, a series of elastomers were formulated and a qualitative assessment of their performance was completed. In all cases, the procedure for making these elastomers is as follows. First, all polyol-side components were dispensed in precise quantities into a cup, including all polyols, catalysts and other additives. They were then hand mixed using a wooden stirring tool at room temperature for a minimum of 30 seconds, until the mixture was uniform. After the polyol side was uniform, the isocyanate side was added and the mixture was again mixed by hand for a minimum of 15 seconds. After the full formulation was well mixed, the mixture was poured into an aluminum mold and cured at 65 degrees celcius for one hour.

Example 2: TPU Formulations via aliphatic polycarbonate polyol-based prepolymer

In Example 2, thermoplastic polyuretfianes were formulated and a quantitative assessment of their physical properties was completed. In all cases, the procedure for making these elastomers is as follows. First, pre-polymers of aliphatic polycarbonate polyol 58-076 were created using a commercial isocyanate Rubinate 44. The polyol was added to the isocyanate in the quantities indicated in Table 3 at 30 minutes, reaction time was 105 minutes, and temperature was 56-80 degrees celcius. After reaction, the properties of the pre- polymers were examined including theoretical and actual % NCO. See bottom of Table 3 for data. Table 3. Formulation of NCO-prepolymers

Novomer

Prepolymer Designation

58-076

Prepolymer Formulation (pbw)

Mondur M -

Rubinate 44 341.40

Eternacoll UH-50 -

Novomer 58-076 392.69

Fomrez 44-160 -

N CO/OH Ratio 2.05/1

Reaction temperature and time

Time of Polyol Addition 30 min.

Time of Reaction 105 min.

Temperature 56-80°C

Properties of prepolymer

NCO% Theoretical 7.36

NCO% Measured 7.40

Consistency at RT Solid

Viscosity at 70°C, mPa.s, cps TBD

As a second step, the polycarbonate polyol-based prepolymers were used to formulate TPUs. The prepolymers were heated to 120 degrees celcius and were combined with 1,4 butane diol as a chain extender (heated to 80 degrees celcius) at at isocyanate index of 1.02 (Table 4). They were mixed at 2200 rpm for 20 seconds. A gel time of 60 seconds was observed. The resulting TPUs were cured for 2 hours at 120 degrees celcius and then for 20 hours at 110 degrees celcius.

After curing, basic physical properties were tested, Table 6.

empera ure

Example 3

In Example 3, thermoplastic polyurethanes are created using the process described above and the formulations described below.

Formulation of NCO-prepolymers Formulation of TPUs

Novomer PPC Polyol Mw 1000 i Formulation

Pre polymer Formulation (pbw) : Novomer polyol-based prepolymer 125

Diphenylmethane 4,4-diisocyanate mmm m l,4 butanediol 9.7

Novomer Polyol 585: ; Isocyanate Index 1.02

Ratio of NCO to OH 2.05! Reaction & curing temperature and time

Reaction temperature and time : Temperature of prepolymer 120

Time of Polyol Addition 30 min. Temperature of 1,4 butanediol 80

Time of Reaction 105 min. iCuring time and temperature 2 @ 120C

Temperature 50-85°Ci ; Post-curing time and temperature 20 @ HOC

Example 4

In Example 4, thermoplastic polyurethanes are created using the process described above and the formulations described below. Formulation of NCO-prepolymers Formulation of TPUs

Novomer PPC Polyol Mw 1500; Formulation

Prepolymer Formulation (pbw) ; Novomer polyol-based prepolymer ; m.

Diphenylmethane 4,4-diisocyanate 300: : l,4 butanediol 7.6

Novomer Polyol 856: : Isocyanate Index 1.05

Ratio of NCO to OH 2.1: Reaction & curing temperature and time

Reaction temperature and time iTemperature of prepolymer 120

Time of Polyol Addition 30 min. iTemperature of 1,4 butanediol 80

Time of Reaction 105 min. :Curing time and temperature 2 @ 120C

Temperature 50-85°C: : Post-curing time and temperature 20 @ HOC

Example 5

In Example 5, thermoplastic polyurethanes are created using the process described above and the formulations described below.

Formulation of NCO-prepolymers i Formulation of TPUs

Novomer PPC Polyol Mw 2000: Formulation

Prepolymer Formulation (pbw) : Novomer polyol-based prepolymer : 150

Diphenylmethane 4,4-diisocyanate mmmmmw 1,4 butanediol 11.1

Novomer Polyol 761 Isocyanate Index m.

Ratio of NCO to OH Reaction & curing temperature and time

Reaction temperature and time iTemperature of prepolymer 120

Time of Polyol Addition 30 min. iTemperature of 1,4 butanediol 80

Time of Reaction 105 min. iCuring time and temperature 2 @ 120C

Temperature 50-85°C : Post-curing time and temperature 20 @ HOC

Example 6

To gain an understanding of the fundamental structure-property relationship of these unique polycarbonate polyols in polyurethane systems, thermoplastic polyurethanes (TPUs) were synthesized and physical properties were evaluated and compared to existing polycarbonate and polyester poyols in equivalent systems. The Novomer C(½-based polyols exhibit unique and favorable performance characteristics vs. these standard polyols, including exceptional hardness, high tensile and flexural strength, excellent heat resistance and very good oil, chemical and water resistance

The objective of this Example was to determine practical performance of CCVbased PPC diol with a molecular weight of 750 g/mol in thermoplastic polyurethanes (TPUs) prepared via a prepolymer method using 1,4-butane diol (1,4-BD) as a chain extender and diphenylmethane-4,4'-diisocyante (MDI) as the isocyanate. These TPUs were compared to the TPUs based on two traditional diols: Fomrez 44-160, a polyester polyol produced by Chemtura; and Eternacall UH-50, a hexanediol-carbonate polyol produced by Ube, with similar molecular weights and at the same hard segment concentration.

Raw materials used in this Example are shown in Tables E6-1 and E6-2. Prior to preparation of NCO-prepolymers, polyols and 1,4-BD were dried for 24 hours at 75°-80°C under vacuum of 1-3 mm Hg and continuous mixing by magnetic stirrer. The water content after drying was checked by Karl Fisher Titration.

Diphenylmethane 4,4'-diisocyanate (MDI) was used as received from the supplier and its isocyanate content was checked by di-n-butylamine titration method (ASTM D-5155). Preparation of NCO-prepolymers:

The NCO-prepolymers were synthesized utilizing a standard laboratory procedure for prepolymer preparation as follows: MDI melted at 60°C was placed in the heated reaction kettle, which was equipped with a stirrer, thermometer, and continuous flow of nitrogen. Preheated polyol was added slowly to isocyanate at 60°-65°C and reaction was continued at 70-80°C for about 105 minutes. The NCO% of the prepolymers was checked periodically during the synthesis. Afterwards, the prepolymer was degassed under vacuum, transferred into glass jars and sealed under dry nitrogen. The NCO% of the resulting prepolymers was checked after 24 hours according to ASTM D5155.

Preparation of polyurethane elastomers:

TPUs were prepared by reacting NCO-prepolymers with a chain extender at an isocyanate index of 1.02.

TPU sheets and round bottom samples were prepared to test their physico-mechanical properties. The TPU sheets were prepared using a laboratory compression molding method (Carver press). NCO-prepolymer was preheated at 80°C, weighed into a Speed Mixer cup and heated at 120°C for 15 minutes in an air circulation oven. A chain extender (conditioned at 80°C) was added to the prepolymer and all components were mixed via Speed Mixer (FlackTek Inc.) for 20 seconds at 2200 rpm and transferred into an aluminum mold covered with a Teflon sheet that was preheated at 120°C. At the gel time, the mold was closed and cured for 2 hours at 120°C. Afterwards, the samples were post-cured for 20 hours at 110°C.

TPUs with 50% hard segment concentration based on Fomrez 44-160 were prepared by adding straight MDI to the prepolymer prior to adding the chain extender. TPU based on UH-50 at 50% hard segment concentration were prepared by adding calculated amount of UH-50 polyol to the chain extender.

Cylindrical "button samples" (6.5cm² x 1.3 cm) for testing of hardness and resilience were prepared by casting of degassed polyurethane system into a Teflon coated mold with multiple cavities which was preheated at 120°C. The mold was then covered with Teflon coated aluminum plate, transferred into an oven at 120°C, cured for 2 hours and then post- cured for 20 hours at 110°C.

The samples of TPUs were kept in the desiccators and aged for seven days at RT prior to testing.

Testing:

POLYOLS:

The following measurements were carried out on polyols (Table E6-2):

• Hydroxyl number, ASTM D 4274-05

• Acid number, ASTM D4662-08

• Viscosity, 50° and 70°C, ASTM D 4878-08

• Water, Karl Fisher method, ASTM D 4672-08

• Glass transition temperature, DSC (DSC Q 10, TA Instruments at heating rate of 10°C per minute)

• Mn and Mw, GPC analysis

NCO-PREPOLYMERS:

NCO% was measured according to ASTM D 5155 and viscosity at 70°C via R eometrics.

ELASTOMERS:

The following properties were measured on TPUs:

• Hardness, ASTM D-2240, Shore D

• Tensile properties (Tensile strength at Yield and Break and Young's modulus), ASTM D 412

• Toughness at yield (tensile strength x elongation% at yield)

• Tear Strength, Die C, ASTM D 6240 • Abrasion Resistance, ASTM D 1044 (H22 wheels, weight load 500g, 2000 cycles)

• Flexural strength and modulus (ASM D 790)

• Resilience, % (Bashore rebound), ASTM D2632

• Dynamic mechanical analysis, DMA, in bending mode (DMA 2980, TA

instruments)

• Thermo-mechanical analysis, TMA (TMA Q 400, TA Instruments)

• Differential scanning calorimetry, DSC (DSC Q 10, TA Instruments at heating rate of 10°C per minute)

• Heat resistance of elastomers: tensile properties at 50° and 70°C were measured by using heat chamber attached to Instron tester.

Solvent resistance to various polar and non-polar solvents, including oil and water, was measured as weight change and retention of properties of TPUs upon their immersion in the solvents at RT for seven days.

Moisture resistance of TPUs was measured after their exposure to 50°C and 100% relative humidity for seven days; the moisture uptake and retention of properties was measured.

Oxidative resistance was measured upon immersion of TPUs in 30% hydrogen peroxide solution for two weeks at 3 °C.

Polyols:

Results of GPC analysis carried out on poly(l,2-propylene carbonate) diol (Novomer polycarbonate NOV-58-076) and two reference diols, poly(l,6-hexametylene carbonate) diol (Eternacoll UH-50) and poly(l,4-butylene adipate) diol (Fomrez 44-160) are shown in Table E6-2. The Polydispersity Index (Mw/Mn) of Novomer polycarbonate polyol was low at 1.37 (Table E6-2), indicating a narrow molecular weight distribution. Polydispersity Index of Eternacoll UH-50 polyol was 7.7, which is relatively high. The Polydispersity Index of Fomrez 44-160 polyol was 2.75, which is typical for commercial aliphatic polyester polyols. All three tested polyols are solid at room temperature. Their viscosities at 50° and 70°C are reported in Table E6-2. The viscosity of the Novomer polyol was lower than that of Eternacoll UH-50. However, Tg of Eternacoll UH-50 polyol was lower than that of Novomer polyol (Table E6-2), which can be ascribed to the longer hexamethylene chain in the polyol backbone of Eternacoll UH-50 polyol.

Polyurethane elastomers:

Thermoplastic polyurethane elastomers based on all three types of polyols were prepared by the prepolymer method at a 1.02 isocyanate index and hard segment concentration of 50%. Their properties are shown in Table E6-3.

At 50% hard segment concentration, the TPU based on Novomer polyol was harder at T (Shore D 78) than TPUs based on Eternacoll UH-50 polyol (Shore D 67) and polyester polyol (Shore D 62). The hardness of TPUs based on Novomer polyol changed slightly when heated to 50° and 70°C, while hardness of TPUs based on Eternacoll UH-50 changed significantly (Table E6-3).

As expected, the resilience measured by Bashore rebound was relatively low in the case of all three TPUs. The resilience of TPU based on Eternacoll UH-50 was somewhat higher (30%) than that of Novomer type TPU (22%), which can be ascribed to the longer sequence of CH₂-chains between carbonate groups in the case Eternacoll UH-50 polyol (Table E6-3).

The stress-strain test results indicate that all three types of elastomers exhibited yield at relatively low strains. TPUs based on Novomer polyol exhibited significantly higher tensile strength at yield (11,712 psi at 6% strain) in comparison to other two types of TPUs (Table E6-3).

The toughness at yield of TPUs based on Novomer polyol was similar to TPUs based on Eternacoll UH-50 polyol and 50% higher than the toughness of TPUs based on polyester polyol (Table E6-3).

Stress-strain measurements indicate that TPUs based on Novomer polyol are very hard, high strength plastic materials.

TPUs based on Novomer polyol exhibited higher flexural strength and modulus in comparison to TPUs based on commercial polycarbonate and polyester polyols (Table E6-3).

The abrasion resistance of all three types of TPUs was about 1% (Table E6-3).

The glass transition temperature of TPUs based on the Novomer polyol, as measured by DSC, was slightly higher as compared to TPUs based on Eternacoll UH-50 polyol and significantly higher than that of TPUs based on polyester polyol. Similar relationship was obtained when the glass transition was measured with DMA (Figures 2 and 3) and TMA method. Coefficient of thermal expansion measured by TMA below respective Tg's was lower and above respective Tg's higher for TPU based on the Novomer polyol than those based on reference polycarbonate and polyester glycols (Table E6-3).

Heat resistance of elastomers was measured as retention of tensile properties at 50° and 70°C relative to those at room temperature (Table E6-3, Figure 4). The retention of tensile strength at yield of TPUs based on the Novomer 076 polyol at 50°C was excellent; it retains the strength measured at room temperature. The tensile strength of at yield of PUs based on Eternacoll UH-50 polycarbonate polyol decreased significantly at 50°C. The tensile strength of TPUs based on Novomer 58-076 at 70°C was significantly lower than that at 50°C; still tensile strength at yield of TPUs based on Novomer 58-076polyol was higher than that of other two types of TPUs.

The oil and water resistance of all three TPUs, as measured by weight gain upon immersion in solvents at RT, was excellent and very similar (Figure 4). However, TPUs based on Novomer polyol exhibited better resistance in non-polar solvent (toluene and xylene).

The retention of tensile strength of TPUs based on the Novomer polycarbonate polyol upon exposure to different media for 7 days at room temperature was good (Figure 5). The retention of properties was good in non-polar solvents such as oil and xylene as well as in hydrochloric acid and sodium hydroxide solution.

The oxidative resistance of TPUs based on Novomer polyol was excellent. The retention of tensile strength at yield after immersion in 30% hydrogen peroxide oxidative solution for two weeks at 37°C was over 80% (Figure 5).

The water (moisture resistance test) was carried out at by exposing TPUs based on the Novomer polycarbonate polyol to 100% relative humidity at 50°C for 1 week. The retention of the tensile strength was 74% which is good (Figure 5).

In conclusion, Novomer PPC polyols exhibit a unique set of performance properties when compared to existing specialty polycarbonate polyols and commodity polyester polyols in representative TPU formulations. The PPC-based TPUs are high performance products delivering exceptional hardness, very good tensile and flexural strength, good hydrolytic stability and good chemical & oxidative resistance.

Example 7

The purpose of this example was to evaluate the properties of TPUs made with poly(propylene carbonate) diols having higher molecular weights.

Raw materials used in this Example are shown in Tables E7-1 and E7-2.

Aliphatic polycarbonate polyols used in this Example conform to formula Q5:

For polyol 74-145, R¹ is methyl, t is 2, and n is on average in the composition approximately 7.4. For polyol 58-076, R¹ is methyl, t is approximately 8, and n is on average in the composition approximately 5.6. The properties of the polyols are shown in Table

Polyols and 1,4-BD were dried for 24 hours at 75°-80°C under vacuum of 1-3 mm Hg and continuous mixing by magnetic stirrer prior being used. The water content after drying was checked by Karl Fisher Titrator.

Diphenylmethane diisocyanates, Mondur M and Mondur MLQ were used as received from the supplier and their isocyanate content was checked by di-n-butylamine titration method (ASTM D-5155).

Preparation of NCO-prepolymers:

The NCO-prepolymers were prepared as follows: MDI (melted at 60°C) was placed in the heated reaction kettle, which was equipped with a stirrer, thermometer and continuous flow of nitrogen. Preheated polyol was added slowly to isocyanate at 60°-65°C and reaction was continued at elevated temperature as indicated in Table E7-3. The NCO% of the prepolymers was checked periodically during synthesis. Afterwards, the prepolymer was degassed under vacuum, transferred into glass jars and sealed under dry nitrogen.

Formulations of NCO-prepolymers and processing conditions are shown in Table E7-3.

The NCO% of prepolymers was checked after 24 hours. The NCO% was measured according to ASTM D5155. Preparation of TPUs:

PREPOLYME METHOD

TPUs sheets and round bottom samples were prepared to test physico-mechanical properties of the elastomers. Formulations and curing conditions utilized in preparation of TPUs are shown in Tables E7-4 and E7-5.

The elastomer sheets were prepared using a laboratory compression molding method (Carver press). NCO-prepolymer was preheated at 80°C, weighed into a Speed Mixer cup and heated at 120°C for 15 minutes in an air circulation oven. A chain extender (conditioned at 80°C) was added to the prepolymer and all components were mixed via Speed Mixer (FlackTek Inc.) for 20 seconds at 2200 rpm and transferred into an aluminum mold covered with Teflon sheet that was preheated at 120°C. At the gel time the mold was closed and placed into Carver press for 2 hours at 120°C. Afterwards, the samples were post-cured for 20 hours at 110°C.

Cylindrical "button samples" (6.5cm² x 1.3 cm) for testing of hardness were prepared by casting of degassed polyurethane system into a Teflon coated mold with multiple cavities which was preheated at 120°C. The mold was then covered with a Teflon coated aluminum plate, transferred into an oven at 120°C. Samples were cured for 2 hours and then post-cured for 16 hours at 110°C. The samples of TPUs were kept in the desiccators and aged for seven days at RT prior to testing.

ONE-SHOT METHOD

TPUs were prepared by reacting MDI and a mixture composed of polyester polyol, chain extender and small amount of tin-gelling catalyst (if used) at an Isocyanate Index of 1.02.

Sheets and round bottom samples were prepared to test physico-mechanical properties of the TPUs. The sheets were prepared using a laboratory compression molding method (Carver press). Degassed preheated polyol and a chain extender containing small amount of tin catalyst, were weighed into Speed Mixer cup, mixed for 30 seconds at 2200 rpm using Speed Mixer (FlackTek Inc.) and subsequently heated for 15 minutes in an air-circulating oven at 120°C. Liquid isocyanate conditioned at 80°C was added via syringe to the mixture of polyol and the chain extender, and all components were mixed via Speed Mixer for 20 seconds at 2200 rpm and transferred into an aluminum mold covered with Teflon sheet that was preheated at 120°C. At the gel time, the mold was closed and TPU was cured for 2 hours at 120°C. Afterwards, the samples were post-cured for 16 hours at 110°C.

Testing of TPUs

The following test methods were used in TPUs testing:

• Hardness, ASTM D-2240, Shore A and Shore D

• Tensile properties (Tensile Strength, Tensile Modulus and Elongation%), ASTM D 412

• Differential scanning analysis (DSC)

• FTIR analysis

The NCO-prepolymer based on Novomer 74-145 and 4,4'-MDI was synthesized and NCO% of the prepolymer was very close to the theoretical value. The prepolymer was solid at room temperature (Table E7-3).

Table Formulation and properties of NCO-prepolymers

The prepolymer based on 4,4'-MDI and Novomer 74-276 was a viscous liquid at room temperature. The measured NCO% of the prepolymer was 3.62% which was close to the theoretical value of 3.89% (Table E7-3).

NCO-prepolymer based on Mondur MLQ and Novomer 74-276 was prepared as well.

It was difficult to measure viscosity of prepolymers at elevated temperature due to their reactivity with of ambient moisture.

TPUs based on Novomer 74-145

Formulations of TPUs based Novomer 74-145, 4,4'- MDI, and 1, 4-BD as a chain extender prepared by NCO-prepolymer method are shown in Table E7-4. The miscibility of PU system was poor and elastomers were not possible to cast. Poor miscibility could be due to high viscosity of prepolymer, high degree of hydrogen bonding or just poor compatibility of components.

In order to overcome high viscosity of the polyurethane systems based on NCO- prepolymers, TPUs were also prepared by one-shot method (Table E7-4). The gel time of one-shot systems was good (short) with good response to Dabco T-12 catalyst. In this case it was possible to cast TPU sheets. However, TPU sheets were too brittle for cutting the tensile test specimens. This indicates that this TPU is inherently brittle even at low hard segment concentration (-23%).

FTIR spectra of one-shot TPUs based on Novomer 74-145, 4,4' -MDI and 1,4-BD indicate that there is no residual isocyanate and that polymerization is completed. The glass transition temperature (Tg) of these TPUs was at 39.3°C.

TPUs based on Novomer 74-276

The formulation of TPUs based Novomer 74-276 are shown in Table E7-5. TPU systems based on NCO-prepolymer were formulated at 25% and 34% hard segment concentration. It was difficult to handle those systems as it was case with those based on 74- 145 polyol. In order to decrease viscosity, a small amount of propylene carbonate, which is aviscosity depressant, was added to the prepolymer based on Novomer 74-276 and MLQ (Formulation Novomer 74-276-C in Table E7-5). Propylene carbonate was miscible with the prepolymer and viscosity decreased somew^rhat. Table E7-5. Formulations and Curing Conditions of TPUs based on Novomer 74-276 polyol prepared by

the prepolymer method

^•

One-shot TPUs based on Novomer 74-276 were formulated at -25% hard segment concentration (Tables E7-6 and E7-7). 4,4'-MDI and Mondur MLQ were used as isocyanates. The reactivity of one shot TPU systems was relatively low without catalyst. The reactivity was adjusted by introduction of Dabco T-12 (Table E7-6).

Stress-strain properties of TPUs prepared by one shot method are shown in Table E7- 7. TPU based on Mondur MLQ at 25% hard segment concentration exhibited stress at yield of about ~1900 psi and relatively low elongation at yield of 5.7% (Table E7-7). FTIR spectra of TPUs indicate that there is no residual isocyanate and that polymerization is completed. Glass transition temperature of this TPU was at 25.3°C.

One shot TPUs based on 4,4' -MDI exhibited tensile strength of 727 psi and relatively high elongation at yield of 411% (Table E7-7).

TPUs based on Novomer 74-276 were also prepared via prepolymer method using Mondur MLQ as an isocyanate and 1, 4-BD as a chain extender (Table E7-6). The tensile strength of this TPU was lower than those of TPUs prepared by one shot method (Table E7- 7).

Example 8

The objective of this example was to evaluate transparent polyurethane elastomers of the present invention.

Transparent polyurethane elastomers have many applications that include various types of synthetic glass (such as windshield, visors, synthetic roof, synthetic glass, various moldings, etc.), transparent adhesives, coatings, various polyurea spray systems for outside applications, clear sheets and foils, etc.

Transparent polyurethanes are commonly prepared using aliphatic isocyanates such as hydrogenated MDI (H12MDI) and isophorone diisocyanate (IPDI). Aliphatic isocyanates provide lasting color and don't yellow with exposure to UV light. Raw materials used in this Example are shown in Tables E8-1 and E8-2. Prior to preparation of prepolymers, polyols were dried for 24 hours at 75° - 80°C under vacuum of 1- 3 mm Hg and continuous mixing by magnetic stirrer. The water content after drying was checked by Karl Fisher Titrator.

Methylene bis (4-cyclohexylisocyanate), Desmodur W H12MDI, was used as received from the supplier and its isocyanate content was checked by di-n-butyl amine titration method (ASTM D-5155).

Aliphatic polycarbonate polyols used in this Example conform to formula Q5,

For 74- 145, R^l is methyl, t is 2, and n is on average in the composition approximately 7.4. For 58-076, R¹ is methyl, t is 2, and n is on average in the composition approximately 3.1. The properties of the polyols are shown in Table E8-2. Table E8-2. Polyol Properties

-

- -

-

Preparation of NCO-prepolymers:

The NCO-prepolymers were prepared utilizing laboratory procedure for the prepolymer preparation, as follows: Desmodur W was placed in the heated reaction kettle, which was equipped with a stirrer, thermometer, and continuous flow of nitrogen. Preheated polyol was added slowly to the preheated isocyanate at 80°C and afterwards the temperature was increased to ~140°C. Total reaction time was calculated from the time when the last portion of polyol was added to the isocyanate (Table E8-3). The NCO% of the prepolymers was checked periodically during synthesis. Afterwards, the prepolymer was degassed under vacuum, transferred into glass jars, and sealed under dry nitrogen. Formulations of NCO- prepolymers and processing conditions are shown in Table E8-3.

The NCO% of prepolymers was checked after 24 hours. NCO% of the NCO- prepolymers was measured according to ASTM D5155 and viscosities at 70°C with a Rlieometer (Table E8-3).

Preparation of poly(urethane-urea) elastomers:

Poly(urethane-urea) elastomers were prepared by reacting H12MDI- prepolymer (preparation described in the previous section) with Ethacure 100 at an isocyanate index of 1.05. Elastomer sheets and round bottom samples were prepared to test physico-mechanical properties of the elastomers. The formulation and curing conditions in elastomers preparation are shown in Table 4.

The elastomer sheets were prepared using a laboratory compression molding method (Carver press). NCO-prepolymer was preheated at 120°C, weighed into a Speed Mixer cup and heated at 120°C for 15 minutes in air circulation oven. Ethacure 100 (conditioned at 80°C) was added to the prepolymer and all components were mixed via Speed Mixer (FlackTek Inc.) for 20 seconds at 2200 rpm and subsequently transferred into an aluminum mold covered with Teflon sheet that was preheated at 120°C. At the gel time the mold was closed and cured for 2 hours at 120°C. Afterwards, the samples were post-cured for 20 hours at l l0°C.

Cylindrical "button samples" (6.5cm² x 1.3 cm) for testing of hardness and resilience were prepared by casting of degassed polyurethane system into a Teflon coated mold with multiple cavities which was preheated at 120°C. The mold was then covered with Teflon coated aluminum plate, transferred into an oven at 120°C for a 2 hour cure and then post- cured for 20 hours at 110°C.

The samples of elastomers were kept in the desiccators and aged for seven days at RT prior to testing.

Testing:

Polvols:

The following properties of polios were tested (Table E8-2):

• Hydroxyl number, ASTM D 4274-05

• Acid number, ASTM D4662-08

• Viscosity, 50 and 70°C, ASTM D 4878-08

• Water, Karl Fisher method, ASTM D 4672-08

NCO-Prepolymers: NCO% was measured according to ASTM D 5155 and viscosity at 70°C via Rlieometrics (Table 3).

Elastomers:

The following properties were measured on elastomers:

• Hardness, ASTM D-2240, Shore D

• Tensile properties (Tensile strength at Yield and Break, Tensile Modulus and

Elongation% at Yield and Break and Young's modulus), ASTM D 412

• Toughness at yield (tensile strength x elongation% at yield)

• Tear Strength, Die C, ASTM D 6240

• Abrasion Resistance, ASTM D 1044 (H22 wheels, weight load 500g, 2000 cycles)

• Flexural strength and modulus (ASM D 790)

• Resilience, % (Bashore rebound), ASTM D2632

• Differential scanning calorimetry, DSC (DSC Q 10, TA Instruments)

• Heat resistance of elastomers: tensile properties at 50 and 70°C were measured by using heat chamber attached to Instron tester.

DSC analyses were carried out under nitrogen at heating rate of 10°C per minute in a temperature range of from -80°C to +200°C on DSC Q10 Model from TA Instruments.

DMA and TMA analyses were carried out on Type #2 cast elastomer (Tables E8-4 and E8-6,). DMA analysis was carried out under nitrogen at heating rate of 3°C per minute in a temperature range of from -80°C to +130°C on DMA 2980 Model from TA Instruments. TMA analysis was carried out under nitrogen at heating rate of 10°C per minute in a temperature range of from -80°C to +130°C on TMA Q400 Model from TA Instruments.

Solvent resistance (including water and oil resistance) of elastomers was measured as follows: 3 elastomer specimens (10 x 40 x 2mm, cut from the sheet) were weighed together and immersed in solvent at room temperature. The samples were taken out after 3 days of immersion. Their weight change was measured.

NCO- prepolymers:

Two types of NCO-prepolymers based on cycloaliphatic isocyanate H12MDI and NOVOMER polycarbonate prepolymer were prepared (Table 3): • Prepolymer Type A, based on low molecular polyol Novomer 58-076 polyol (MW 616), and

• Prepolyme Type B, based on a mixture of low molecular weight Novomer 58-076 polyol (MW 616) and higher molecular weight Novomer 74-145polyol (MW 1650).

In both cases, measured NCO% of the prepolymer was very close to the theoretical NCO%.

Results:

Both prepolymers were solid at room temperature. The viscosity at 70°C of the Prepolymer Type A as measured via Rheometrics, was high (~1, 380,000 cPs) and that of the Prepolymer Type B was significantly lower (-35,800 cPs) (Table E8-3).

Polyurethane cast elastomers:

Poly(urethane-urea) cast elastomers were prepared by reacting NCO-prepolymers with Ethacure 100 hindered aliphatic diamine. Polymerization of aliphatic isocyanate prepolymers with aliphatic diamine is a common method to prepare this type of elastomers. Amines react much faster with isocyanates than glycols and aliphatic isocyanate prepolymers are much less reactive than aromatic isocyanate prepolymers. The formulation and processing condition of cast elastomers are shown in Table E8-4. Three types of elastomers were prepared:

• Type 1, Elastomers based on Prepolymer Type A

• Type 2, Elastomer based on Prepolymer Type B.

• Type 3, Elastomers based on 50/50 pbw mixture of Prepolymer Type A/Prepolymer Type B

All elastomers were prepared at Isocyanate Index 105. The reaction systems exhibited good reactivity. The gel time was 60 seconds for preheated reactive components that were mixed for 20 seconds via Speed Mixer.

The properties of cast elastomers are shown in Table E8-6. All three types of elastomers were hard and transparent, as expected.

Type 1 elastomers, based on low molecular weight polyols, exhibited very high hardness of Shore D 81. The hardness of Type 2 and Type 3 elastomers containing higher molecular weight polyol was lower, Shore D 72 and Shore D 75 (respectively). The resilience of those elastomers is low, from 16 to 24 %. Type 2 elastomers containing higher proportion of higher molecular weight polyol had resilience of 24% (Table E8-6). In general, polycarbonate elastomers have low resilience.

FTIR spectra of Type 1, Type 2, and Type 3 elastomers are similar. There was no or low traces of absorption at -2270 c f'that can be ascribed to ~NCO groups, which indicated completeness of polymerization.

The Type 1 elastomer was too brittle to be tested for stress-strain properties at RT. The samples broke during cutting of test specimens. The tensile strength and strain at break of this elastomer at 50°C was low -900 psi and 2%, respectively (Table E8-6). Surprisingly, the tensile strength increased when tested at 70°C(~3000 psi at 29% strain) (Table E8-6).

Both Type 2 and Type 3 elastomers exhibited yield at relatively low strain in stress- strain testing at RT (Table E8-6). The strain at break was 60% for Type 2 elastomer and 3% for Type 3 elastomer, which indicates that higher molecular weight polyol imparts some flexibility to polyurethane. However, the tensile strength of both Type 2 and Type 3 elastomers at RT was very good, 5745 psi and 5093 psi, respectively (Table E8-6).

Based on these initial results, Type 2 elastomer was selected for more complete testing. This elastomer exhibited good combination of hardness and stress-strain properties.

Heat resistance of Type 2 elastomers was measured as retention of tensile properties at 50°C and 70°C relative to those at room temperature (Table E8-6 ). The elastomer retained 57% of properties at 50°C and 31% at 70°C, which are good values for cycloaliphatic isocyanate based elastomers.

The stress-strain graphs of elastomers tested at 50°C and 70°C indicate less pronounced yield in comparison to the RT results (Table E8-6).

Type 2 elastomer exhibited 21 mg weight loss (1.7%) in the Taber Abrader Abrasion resistance test, which is quite good for elastomer with this hardness.

The glass transition temperature measured via TMA and DMA was at 20°C and 43 °C, respectively (Table E8-6). Table E8-6A. Properties of Cast Elastomers

Elastomer Designation Type #1 Type #2 Type #3

Three transitions were observed in Type 2 elastomer as measured via DSC at -3°C,°C, and 58°C (Table E8-6). Three transitions were also observed in TMA of the same elastomer (Table E8-6). Multi-phase transitions can be related to the presence of a mixture of two polyols in the elastomer.

Example 9

The objective of this Example was to determine performance of CCVbased poly (ethylene carbonate) diol (PEC-1.7-DPG) in thermoplastic polyurethane elastomers (TPUs).

Chemicals:

Raw materials used in this Example are shown in Table E9-1. The polyol and 1,4-BD were dried for 24 hours at 75°- 80°C under vacuum of 1-3 mm Hg and continuous mixing by magnetic stirrer prior being used. The water content after drying was checked by Karl Fisher Titrator.

The aliphatic polycarbonate (PEC- 1.7- DPG aka 69-255) used conforms to structure

Q4:

where R is methyl, t is 2, and n is on average in the composition about 9.

Aromatic diisocyanates, Mondur M and Mondur MLQ were used as received from the supplier and their isocyanate content was checked by di-n-butyl amine titration method (ASTM D-51 5).

Table E9-1. Materials

Preparation of TPUs:

TPUs were prepared by the one-shot method by reacting aromatic diisocyanate (Mondur M or Mondur MLQ) and a mixture composed of polyol, chain extender and small amount of tin-gelling catalyst at an Isocyanate index of 1.02.

Sheets and round bottom samples were prepared to test physico-mechanical properties of the TPUs. The sheets were prepared using a laboratory compression molding method (Carver press). Degassed preheated polyol and a chain extender containing small amount of tin catalyst, were weighed into Speed Mixer cup, mixed for 30 seconds at 2200 rpm using Speed Mixer (FlackTek Inc.) and subsequently heated for 15 minutes in an air-circulating oven at 120°C. Liquid isocyanate conditioned at 80°C was added via syringe to the mixture of polyol and the chain extender, and all components were mixed via Speed Mixer for 20 seconds at 2200 rpm and transferred into an aluminum mold covered with Teflon sheet that was preheated at 120°C. At the gel time, the mold was closed and TPU was cured for 2 hours at 120°C. Afterwards, the samples were post-cured for 20 hours at 100°C. Formulations and curing conditions utilized in preparation of TPUs via one-shot method are shown in Tables E9-3 through E9-5. Table E9-3. Formulations and Curing Conditions of TPUs based on Novomer PEC-1.7-DPG polyol and Mondur MLQ isocyanate prepared by one-shot method at 28% hard segment concentration

Table £9-5. Formulations and Curing Conditions of TPUs based on Novomer

PEC-1.7-DPG polyol and Mondur M isocyanate prepared by one-shot

method at 40% hard se ment concentration

Testing of TPUs:

The following test methods were used in TPUs testing:

• Hardness, ASTM D-2240, Shore A and Shore D

• Differential scanning analysis (DSC), ASTM 3418, (DSC Q10, TA Instruments).

• FTIR analysis (FT-IR Spectrometer, Spectrum 2, Perkin Elmer with PIKE Miracle ATR cell).

Solvent resistance of TPUs, including water and oil resistances were measured: 3 TPU specimens (10 x 40 x 2mm) were weighed together and immersed in a solvent at room temperature. The weight change of the samples was measured after 3 and 7 days of immersion.

TPUs based on Novomer PEC- 1.7- DPG and Mondur MLQ:

TPUs based on Novomer PEC- 1.7- DPG polyol were prepared using two types of isocyanates, Mondur MLQ and Mondur M. The elastomers were prepared using one-shot method. The formulation of TPUs based on Novomer PEC- 1.7- DPG polyol and Mondur MLQ is shown in Table 3. Polyurethane system without catalyst was very slow. The gel time was about 3 minutes in the presence of 0.01 pbw of tin-catalyst in the polyurethane system. FTIR spectra of cured elastomer indicate that polymerization was completed; there was no absorption at 2230 cm^"1 that relates to -NCO absorption.

The properties of TPUs are shown in Table E9-6. The hardness of elastomer was Shore A 82 and resilience relatively low 33. TPUs exhibited relatively high elasticity, 722% elongation at break and tensile strength was 1366 psi. The stress-strain curve exhibited a shape characteristic for elastomeric polyurethanes. In contrast, TPUs based on Novomer 750 polyol and high molecular poly (propylene carbonate) diol exhibited yield in stress-strain measurement (see other Examples 6,7,8).

The glass transition temperature of TPUs, as measured by DSC, was at 15.4°C and small transition was detected at 62°C that could be associated with hydrogen bonding of hard and soft segments of TPUs.

It was noticed that color of Mondur MLQ-based TPUs was amber. This could probably relate to reddish color of Mondur MLQ. The elastomers based on Mondur M exhibited yellowish color which was expected.

TPUs based on Novomer PEC- 1.7-DPG and Mondur M:

TPUs based on Novomer PEC- 1.7-DPG and Mondur M were prepared at two hard segment concentrations, 29.6% and 40%. The formulation and curing condition of TPUs are shown in Tables 4 and 5. The TPUs were prepared with the presence of small amount of tin- catalyst in polyurethane system. The gel time of the TPU system was found to depend on the concentration of catalyst, as expected (Tables E9-4 and E9-5).

FTIR spectra of both types of TPUs based on Novomer PEC-1.7-DPG and Mondur M indicate that polymerization was completed; there was no absorption at 2230 cm^"1 that relates to the -NCO absorption. The properties of TPUs based on Novomer PEC- 1.7 DPG and Mondur M prepared at 29.6% hard segment concentration are shown in Table E9-7. The hardness of TPUs was Shore D 48, tensile strength was 2014 psi and elongation at break 505%. The stress - strain curve exhibited shape characteristic for elastomeric TPUs.

The hardness of TPUs increased to Shore D 65 as hard segment concentration increased to 40% (Table E9-8). The tensile strength of these TPUs was very good, 4262 psi, at elongation at break of 535%. The stress- strain curve exhibited shape characteristic for elastomeric polyurethanes. The heat resistance of these TPUs was measured by measuring stress-strain properties at 50°C and 70°C. At 70°C the elastomers retained about 50% tensile strength and 90% of elongation at break as compared to the room temperature properties (Table E9-8).

Table E9-7. Properties of TPUs based on Novomer PEC-1.T-

DPG polyol and Mondur M isocyanate prepared at 29.6% hard

segment concentration

Table E9-8. Properties of TPUs based on Novomer PE01.7-DPG polyol and Mondur M isocyanate prepared at 40% hard segment

concentration

Overall, the tensile properties of TPUs based on Novomer PEC- 1.7- DPG exceeded significantly the properties of TPUs based on high molecular weight poly(propylene carbonate) diol. This could be due to more ordered and better packaged structure of polyurethane polymer network based on poly(ethylene carbonate) diol.

DSC spectra of TPUs based on Novomer PEC-1.7-DPG and Mondur M were similar, regardless on hard segment concentration. TPUs prepared at 29.6% hard segment concentration exhibited the following transitions: Tg of the soft segment at 1 .5°C, hard- soft segment hydrogen bonding at 66°C and transition at ~175°C which can be ascribed to hard segment melting.

Solvent resistance of TPUs based on Novomer PEC-1.7-DPG and Mondur M prepared at 40% hard segment concentration was tested. The solvent resistance was tested by measuring the weight gain at room temperature in toluene, MEK, oil and water. TPUs exhibited low absorption in water and in non-polar media (toluene and oil). The absorption in polar MEK was high (Table E9-9). Table E9-9. Solvent resistance of TPUs based Novomer

PEC-1.7-DPG polyol and Mondur M isocyanate prepared at 40% hard segment concentration

Weight increase, % Weight increase, %,

Solvent

(3 days of immersion) (7 days of immersion)

In conclusion, TPUs based on Novomer PEC-1.7-DPG exhibited good elastomeric properties. Overall, the TPUs based on poly(ethylene carbonate) diol exhibited better properties than those based on high molecular weight poly(propylene carbonate) diol (Example 8).

EQUIVALENTS

All material cited in this application, including, but not limited to, patents and patent applications, regardless of the format of such literature and similar materials, are expressly incorporated herein by reference in their entirety. In the event that one or more of the incorporated literature and similar materials differs from or contradicts this application, including but not limited to defined terms, term usage, described techniques, or the like, this application controls.

The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described in any way. While the present disclosure has been particularly shown and described with reference to specific illustrative

embodiments, it should be understood that various changes in form and detail may be made without departing from the spirit and scope of the present disclosure. Therefore, all embodiments that come within the scope and spirit of the present disclosure, and equivalents thereto, are intended to be claimed. The claims and descriptions of the present disclosure should not be read as limited to the described order of elements unless otherwise stated.

Claims

CLAIMS What is claimed is:

1. A thermoplastic polyurethane composition comprising segments derived from one or more aliphatic polycarbonate polyols having a primary repeating unit with a structure:

where R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain, independently selected from the group consisting of -H, fluorine, an optionally substituted C_1-4o aliphatic group, an optionally substituted Ci-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R¹, R², R³, and R⁴ may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

2. The thermoplastic polyurethane composition of claim 1, wherein the aliphatic

polycarbonate polyol is derived from the copolymerization of carbon dioxide and one or more epoxides.

3. The thermoplastic polyurethane composition of claim 1, wherein the aliphatic

polycarbonate polyol is derived from the copolymerization of carbon dioxide with an epoxide selected from the group consisting of ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide, and a mixture of any of these with one or more additional epoxides.

4. The thermoplastic polyurethane composition of claim 1, wherein the aliphatic

polycarbonate polyol is characterized in that at least 95%, at least 96%, at least 97% or at least 98%, at least 99%, at least 99.5%, at least 99.8% or at least 99.9% of the end groups are -OH groups.

5. The thermoplastic polyurethane composition of any one of claims 1-4, wherein the

aliphatic polycarbonate polyol comprises a copolymer of carbon dioxide and ethylene oxide.

6. The thermoplastic polyurethane composition of any one of claims 1-4, wherein the aliphatic polycarbonate polyol comprises a copolymer of carbon dioxide and propylene oxide.

7. The thermoplastic polyurethane composition of any one of claims 1-4, wherein the

aliphatic polycarbonate polyol has a number average molecular weight (M„) in the range of about 500 g/'mol to about 10,000 g/mol.

8. The thermoplastic polyurethane composition of claim 7, wherein the aliphatic

polycarbonate polyol has a number average molecular weight (M_B) between about 500 g/^'mol and about 3,000 g/mol; or wherein the aliphatic polycarbonate polyol has a number average molecular weight (M„) between about 500 g/mol and about 1,500 g/mol.

9. The thermoplastic polyurethane composition of any one of claims 1-4, wherein the

aliphatic polycarbonate polyol is characterized in that it has a PDI less than 2 or less than about 1.5, or wherein the aliphatic polycarbonate polyol is characterized in that it has a PDI between about 1.0 and 1.2.

10. The thermoplastic polyurethane composition of any one of claims 1-4, wherein the aliphatic polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 85% or greater.

11. The thermoplastic polyurethane composition of claim 10, wherein the aliphatic

polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 90% or greater; 95% or greater; 98% or greater; or 99% or greater.

12. The thermoplastic polyurethane composition of any one of claims 1-4, wherein the the aliphatic polycarbonate polyol has a structure PI:

wherein, n is at each occurrence, independently an integer from about 3 to about 1,000;

Y is, at each occurrence, independently -H or a site of attachment to a chain- extending moiety or isocyanate; is a multivalent moiety; and x and j are each independently an integer from 0 to 6, where the sum of x and

y is between 2 and 6.

13. The thermoplastic polyurethane composition of claim 12,

derived from a polyfunctional chain transfer agent having a formula:

14. The thermoplastic polyurethane composition of claim 13, wherein

is derived from a dihydric alcohol.

15. The thermoplastic polyurethane composition of claim 14, wherein:

the dihydric alcohol comprises a C2-40 diol; or

wherein 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, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-l,3-diol, 1,3-cyclopentanediol, 1,2- cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2- cyclohexanedimethanol, 1 ,3-cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these; or wherein 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 up to about 2000; or

wherein the dihydric alcohol comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, and a hydroxy acid.

16. The thermoplastic polyurethane composition of claim 14, wherein the dihydric alcohol comprises a polymeric diol selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, polyoxymethylene polymers, and alkoxylated analogs of any of these.

17. The thermoplastic polyurethane composition of claim 14, wherein the aliphatic

polycarbonate polyol is selected from the group consisting of:

where, t is an integer from 1 to 12 inclusive, and R^l is independently at each occurrence H, or -CH₃.

18. The thermoplastic polyurethane composition of claim 17, comprising poly(ethylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(ethylene carbonate) of formula Ql having an average molecular weight number of about 500 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or

comprising polyethylene carbonate) of formula Ql having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene carbonate) of formula Ql having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene carbonate) of formula Ql having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 500 g mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene-co-propylene 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 1 1), a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or comprising 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 95% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 500 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; or comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 500 g mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of between about 500 g mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 500 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; or comprising poly(ethylene-co-propylene carbonate) of formula Q6 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 90% carbonate linkages, and at least 98% -OH end groups; or

comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups.

19. The thermoplastic polyurethane composition of any one of claims 1-4, further

comprising one or more additional polyols selected from the group consisting of polyether polyols, polyester polyols, and mixtures of these.

20. The thermoplastic polyurethane composition of claim 5, comprising 100 parts by weight of a polyol component, wherein the aliphatic polycarbonate polyol comprises from about 5 weight percent to 100 weight percent of the polyol component.

21. The thermoplastic polyurethane composition of claim 20, further comprising one or more components selected from:

0.01 to 20 parts by weight of one or more blowing agents;

0 to 1 parts by weight of one or more catalysts;

0 to 20 parts by weight of one or more reactive small molecules, wherein the reactive small molecules comprise one or more functional groups selected from the group consisting of hydroxyls, amines, thiols, and carboxylic acids; and

0 to 10 parts by weight of one or more additives selected from the group consisting of: compatibilizers, colorants, surfactants, flame retardants, antistatic compounds, antimicrobials, UV stabilizers, plasticizers, and cell openers.

22. An injection molding composition comprising a thermoplastic polyurethane composition of any one of claims 1 through 21.

23. An article of manufacture comprising a thermoplastic polyurethane composition of any one of claims 1 through 21.

24. A method of manufacturing a thermoplastic polyurethane composition, the method

comprising the step of reacting a polyisocyanate with an aliphatic polycarbonate polyol of formula PI:

wherein, Y is -H; n is at each occurrence, independently an integer from about 3 to about 1,000; is a multivalent moiety; and x and j are each independently an integer from 0 to 6, where the sum of x and

y is between 2 and 6.

25. The method of claim 24, wherein

is derived from a dihydric alcohol.

26. The method of claim 25, wherein the dihydric alcohol comprises a C2-40 diol; or

27. The method of claim 25, wherein the dihydric alcohol comprises a polymeric diol

selected from the group consisting of polyethers, polyesters, hydroxy -terminated polyolefms, polyether-copolyesters, polyether polycarbonates, polycarbonate- copolyesters, polyoxymethylene polymers, and alkoxylated analogs of any of these.

28. The method of claim 25, wherein the aliphatic polycarbonate polyol is selected from the group consisting of:

where, t is an integer from 1 to 12 inclusive, and R* is independently at each occurrence - H, or -CH₃.

29. The method of claim 25, wherein the aliphatic polycarbonate polyol is selected from the group consisting of:

poly(ethylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, 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 Ql having an average molecular weight number of about 500 g/mol, a pol disperisty index less than about 1.25, at least 85% 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, 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, 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, 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, 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, a polydisperisty index less than about 1.25, at least

95% carbonate linkages, and at least 98% -OH end groups;

poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 90% 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 95% 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, 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, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; poly(propylene carbonate) of formula Q5 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, 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 Q5 having an average molecular weight

95% carbonate linkages, and at least 98% -OH end groups;

poly(propylene carbonate) of formula Q5 having an average molecular weight

95% carbonate linkages, and at least 98% -OH end groups;

poly(propylene carbonate) of formula Q5 having an average molecular weight

95% carbonate linkages, and at least 98% -OH end groups;

poly(propylene carbonate) of formula Q5 having an average molecular weight

95% carbonate linkages, and at least 98% -OH end groups;

poly(ethylene-co-propylene carbonate) of formula Q6 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 90% carbonate linkages, and at least 98% -OH end groups; poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; and a mixture of any two or more of these.