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WO2011163133A1 - Polycarbonates aliphatiques - Google Patents

Polycarbonates aliphatiques Download PDF

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Publication number
WO2011163133A1
WO2011163133A1 PCT/US2011/041084 US2011041084W WO2011163133A1 WO 2011163133 A1 WO2011163133 A1 WO 2011163133A1 US 2011041084 W US2011041084 W US 2011041084W WO 2011163133 A1 WO2011163133 A1 WO 2011163133A1
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Prior art keywords
optionally substituted
certain embodiments
aliphatic
hydrogen
formula
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PCT/US2011/041084
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English (en)
Inventor
Scott D. Allen
Anna E. Cherian
Christopher A. Simoneau
Jay J. Farmer
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Novomer, Inc.
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Publication of WO2011163133A1 publication Critical patent/WO2011163133A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences

Definitions

  • Aliphatic polycarbonates are biocompatible and biodegradable materials with numerous uses ranging from high-performance applications in material science to use as biodegradable consumer packaging.
  • APCs having two carbon atoms separating the carbonate moieties are preferably made by the copolymerization of an aliphatic oxide and C0 2 . While numerous catalyst systems have been developed for epoxide/C0 2 copolymerization, aliphatic polycarbonate polymers made from simple epoxides such as ethylene oxide and propylene oxide possess relatively low glass transition temperatures (T g ) that can limit their industrial applicability.
  • T g glass transition temperatures
  • the present invention encompasses the recognition that aliphatic polycarbonate polymers with higher glass transition temperatures (T g ) possess greater industrial applicability for use in semiconductors, micro electromechanical systems (MEMS), and similar technologies.
  • the invention provides, in one aspect, novel aliphatic polycarbonate polymers (APCs) from the reaction of aliphatic oxides and carbon dioxide (C0 2 ) in the presence of a metal complex.
  • APCs novel aliphatic polycarbonate polymers
  • C0 2 carbon dioxide
  • the present disclosure provides aliphatic polycarbonate polymers that are terpolymers of two aliphatic oxides and carbon dioxide.
  • a provided APC is of formula I:
  • each R a , R b , R c , and R d are independently selected from hydrogen or optionally substituted Ci_3o aliphatic; or an R a and an R b attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings; or an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings;
  • E and G are, independently, suitable terminating groups
  • j is an integer from about 10 to about 15,000;
  • k is an integer from about 0 to about 2,500;
  • n is the sum of j and k, wherein m is an integer from about 10 to about 17,500.
  • the value of j is substantially greater than the value of k.
  • the invention provides methods of synthesizing APCs from the reaction of an aliphatic oxide and carbon dioxide (C0 2 ) in the presence of a metal complex.
  • the present invention provides methods of synthesizing aliphatic polycarbonate polymers, wherein methods comprise a step of reacting an aliphatic oxide with carbon dioxide in the presence of a metal complex,
  • the metal complex is of formula III:
  • M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium and manganese;
  • X is absent or is a nucleophilic ligand
  • each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl, or R 1 and R 2 , or R 2 and R 3 , are joined to form an optionally substituted aryl or optionally substituted heteroaryl ring; and
  • Ring A forms an optionally substituted 5- to 6-membered ring.
  • the metal complex is of formula IV:
  • X' is a nucleophilic ligand
  • each instance of R 1 is independently an optionally substituted group selected from the group consisting of aliphatic, heteroaliphatic, aryl, and heteroaryl; wherein the atom of R 1 attached to the diimidate nitrogen is carbon; each instance of R 2 and R 3 is independently hydrogen, halogen, or an optionally substituted group selected from aliphatic, heteroaliphatic, aryl, and heteroaryl; or R 2 and R 3 are joined with their intervening atoms to form an optionally substituted ring selected from the group consisting of 3-12-membered carbocyclic; 3-12-membered heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 6-10 membered aryl; and 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or R 1 and R 2 are joined with their intervening atoms to form an optionally substituted ring selected from the group consisting of 3-12-membered carbocyclic; 3-12- membered heterocycly
  • Certain compounds of the present invention can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers.
  • inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers.
  • the compounds of the invention are enantiopure compounds.
  • mixtures of enantiomers or diastereomers are provided.
  • certain compounds, as described herein may have one or more double bonds that can exist as either a Z or E isomer, unless otherwise indicated.
  • the invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of enantiomers.
  • this invention also encompasses compositions comprising one or more compounds.
  • isomers includes any and all geometric isomers and stereoisomers.
  • “isomers” include cis- and trans-isomers, E- and Z- isomers, R- and ⁇ -enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
  • a compound may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched.”
  • a particular enantiomer may, in some embodiments be provided substantially free of the opposite enantiomer, and may also be referred to as "optically enriched.”
  • “Optically enriched,” as used herein, means that the compound 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
  • halo and halogen as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -CI), bromine (bromo, -Br), and iodine (iodo, -I).
  • aliphatic or "aliphatic group”, as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-30 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.
  • aliphatic groups contain 1-5 carbon atoms, in some embodiments, aliphatic groups contain 1-4 carbon atoms, in yet other embodiments aliphatic groups contain 1-3 carbon atoms, and in yet other embodiments aliphatic groups contain 1-2 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.
  • aliphatic oxide refers to an epoxide of an aliphatic group as defined above.
  • Aliphatic oxides include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. Such aliphatic oxides may be further optionally substituted as defined herein. In certain embodiments, aliphatic oxides comprise a single epoxide moiety.
  • polymer refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass.
  • a polymer is comprised of only one monomer species ⁇ e.g., polyethylene oxide).
  • a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer of one or more aliphatic oxides and carbon dioxide.
  • a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer of one or more aliphatic oxides and one or more epoxide monomers including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclopentene oxide and cyclohexene oxide.
  • cycloaliphatic used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic, bicyclic, 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, and cyclooctadienyl.
  • the cycloalkyl has 3-6 carbons.
  • cycloaliphatic also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring.
  • a carbocyclic groups is bicyclic.
  • a carbocyclic group is tricyclic.
  • a carbocyclic group is polycyclic.
  • alkyl refers to saturated, straight- or branched-chain hydrocarbon radicals derived from an aliphatic moiety containing between one and six carbon atoms by removal of a single hydrogen atom. Unless otherwise specified, alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbon atoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, in yet other embodiments alkyl groups contain 1-3 carbon atoms, and in yet other embodiments alkyl groups contain 1-2 carbon atoms.
  • alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert- butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.
  • alkenyl denotes a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2-4 carbon atoms, in yet other embodiments alkenyl groups contain 2-3 carbon atoms, and in yet other embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, l-methyl-2-buten-l-yl, and the like.
  • alkynyl refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms.
  • alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2-4 carbon atoms, in yet other embodiments alkynyl groups contain 2-3 carbon atoms, and in yet other 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.
  • aryloxy refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members.
  • aryl may be used interchangeably with the term “aryl ring”.
  • 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.
  • aryl 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.
  • 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
  • heteroatom refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.
  • Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl.
  • heteroaryl and “heteroar-”, as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring.
  • Nonlimiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-l,4-oxazin-3(4H)-one.
  • heteroaryl group may be mono- or bicyclic.
  • heteroaryl may be used interchangeably with the terms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any of which terms include rings that are optionally substituted.
  • heteroarylkyl refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.
  • heterocycle As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclic radical”, and “heterocyclic ring” are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7-14-membered bicyclic heterocyclic moiety that is either saturated or partially unsaturated, and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above.
  • nitrogen includes a substituted nitrogen.
  • the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), ⁇ (as in pyrrolidinyl), or (as in N-substituted pyrrolidinyl).
  • a heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted.
  • saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl.
  • heterocycle refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions independently are optionally substituted.
  • partially unsaturated refers to a ring moiety that includes at least one double or triple bond.
  • partially unsaturated is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as herein defined.
  • compounds of the invention may contain "optionally substituted” moieties.
  • substituted whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent.
  • an "optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position.
  • Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds.
  • stable refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.
  • Suitable monovalent substituents on R° are independently halogen, -(CH 2 ) 0 2 R*, -(haloR*), -(CH 2 ) 0 2 OH, -(CH 2 ) 0 2 OR*, -(CH 2 ) 0 2 CH(OR*) 2 ; -O(haloR'), -CN, -N 3 , -(CH 2 ) 0 2 C(0)R*, -(CH 2 ) 0 2 C(0)OH, -(CH 2 ) 0 2 C(0)OR*, -(CH 2 )o_ 4 C(0)N(R°) 2 ; -(CH 2 ) 0 2 SR*, -(CH 2 ) 0 2 SH, -(CH 2 ) 0 2 NH 2 , -(CH 2 ) 0 2 NHR*, -(CH 2 )
  • Suitable divalent substituents that are bound to vicinal substitutable carbons of an "optionally substituted” group include: -0(CR 2 ) 2 _ 3 0-, 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*, -(haloR*),
  • each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently Ci_ 4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0 -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)CH 2 C(0)R ⁇ , -S(0) 2 R ⁇ , -S(0) 2 NR ⁇ 2 , -C(S)NR ⁇ 2 , -C(NH)NR ⁇ 2 , or -N(R ⁇ )S(0) 2 R ⁇ ; wherein each R ⁇ is independently hydrogen, Ci_ 6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of R ⁇ , taken together with their intervening atom(s
  • Suitable substituents on the aliphatic group of R ⁇ are independently halogen, -R*,
  • each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently aliphatic, -CH 2 Ph, -O(CH 2 ) 0 iPh, or a
  • tautomer includes two or more interconvertable compounds resulting from at least one formal migration of a hydrogen atom and at least one change in valency (e.g., a single bond to a double bond, a triple bond to a single bond, or vice versa). The exact ratio of the tautomers depends on several factors, including temperature, solvent, and pH. Tautomerizations (i.e., the reaction providing a tautomeric pair) may catalyzed by acid or base.
  • Exemplary tautomerizations include keto-to-enol; amide-to-imide; lactam-to- lactim; enamine-to-imine; and enamine-to-(a different) enamine tautomerizations.
  • polymorph refers to a crystalline inventive compound existing in more than one crystalline form/structure. When polymorphism exists as a result of difference in crystal packing it is called packing polymorphism. Polymorphism can also result from the existence of different conformers of the same molecule in conformational polymorphism. In pseudopolymorphism the different crystal types are the result of hydration or solvation.
  • the present invention provides novel APCs that achieve higher glass-transition temperatures (T g ) to facilitate wafer-based fabrication of semiconductors and micro electromechanical systems (MEMS) and similar technologies. It has been unexpectedly found that the incorporation of aliphatic oxides with cyclic or polycylic structures affords the desired increased T g in the resulting APCs. Terpolymers (and higher order heteropolymers) combining simple epoxides with the larger epoxides and C0 2 are also provided. In certain embodiments, the present invention encompasses aliphatic polycarbonates (APCs) incorporating monomers having cyclic or polycyclic motifs. Without wishing to be bound by any particular theory, it is believed that these cyclic and polycyclic ring systems help to rigidify to the polymer chains which can translate into higher definition and more desirable material properties.
  • APCs aliphatic polycarbonates
  • the present invention provides methods of synthesizing aliphatic polycarbonate compositions from aliphatic oxides and carbon dioxide in the presence of a metal complex.
  • the aliphatic polycarbonate polymer is an alternating polymer.
  • the polymer is an alternating polymer of an aliphatic oxide and carbon dioxide (e.g., with regular alternating units of aliphatic oxide and carbon dioxide).
  • the aliphatic polycarbonate polymer is a random copolymer of poly(aliphatic oxide) and aliphatic polycarbonate.
  • the aliphatic polycarbonate polymer is a terpolymer of two aliphatic oxides and carbon dioxide.
  • the aliphatic polycarbonate polymer is a heteropolymer of three or more aliphatic oxides and carbon dioxide.
  • provided aliphatic polycarbonates are copolymers of terpene oxides and carbon dioxide.
  • provided aliphatic terpene polycarbonates are heteropolymers incorporating other simpler epoxide monomers including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclopentene oxide and cyclohexene oxide.
  • aliphatic polycarbonates of the present invention encompass poly(aliphatic carbonate), as well as polymers which comprise poly(aliphatic carbonate), such as, for example, poly(aliphatic oxide)- co-poly(aliphatic carbonate).
  • the present invention provides various aliphatic polycarbonate polymers.
  • Polycarbonates of the present invention can be provided via polymerization of aliphatic oxides and carbon dioxide (C0 2 ) in the presence of a metal complex, and encompass aliphatic polycarbonates, as well as polymers which comprise aliphatic polycarbonates, such as, for example, poly(aliphatic oxide)-co-poly(aliphatic carbonate).
  • a provided APC is of the formula I:
  • each R a , R b , R c , and R d are independently selected from hydrogen or optionally substituted Ci_3o aliphatic; or an R a and an R b attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings; or an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings;
  • E and G are, independently, suitable terminating groups
  • j is an integer from about 10 to about 15,000;
  • k is an integer from about 0 to about 2,500;
  • n is the sum of j and k, wherein m is an integer from about 10 to about 17,500.
  • the value of j is greater than the value of k. In some embodiments, the ratio of j to k is greater than or equal to about 85: 1. In some embodiments, the ratio of j to k is greater than or equal to about 90: 1. In some embodiments, the ratio of j to k is greater than or equal to about 95: 1. In some embodiments, the ratio of j to k is greater than or equal to about 99: 1. In some embodiments, a provided APC is substantially free of poly(aliphatic) oxide, and k is 0.
  • substantially free means that a polymer is comprises units of "j" to "k” in a ratio greater than 99: 1. In some embodiments, the ratio of "j" to “k” is greater than 99.5 : 1. In some embodiments, the ratio of "j" to “k” is greater than 99.9: 1. In some embodiments, the ratio of "j" to “k” is greater than 99.99: 1. In some embodiments, units of k are not detectable by standard methods.
  • the polymer is substantially free of ether linkages (i.e. containing no poly(aliphatic oxide)
  • the polymer is an alternating polymer of formula II:
  • R a , R b , R c , R d , E, G, and j are as defined above for formula I.
  • E is hydrogen. In certain embodiments E is a hydroxyl- protecting group. In certain embodiments, E is a hydroxyalkyl group. In certain embodiments E is an acyl group. In certain embodiments E is a silyl group. In certain embodiments, G is X, where X is as described herein. In certain embodiments, G is halogen. In certain embodiments, G is a hydroxyl group. In certain embodiments, G is an aryl carbonate moiety. In certain embodiments, G is an acetal or ketal linkage to a second polymer chain.
  • j is an integer of between about 10,000 to about 15,000, inclusive. In certain embodiments, j is an integer of between about 12,000 to about 15,000, inclusive.
  • one of R a , R b , R c , and R d is hydrogen. In certain embodiments, two of R a , R b , R c , and R d are hydrogen. In certain embodiments, three of R a , R b , R c , and R d are hydrogen.
  • R a is hydrogen. In certain embodiments, R b is hydrogen.
  • R c is hydrogen. In certain embodiments, R d is hydrogen.
  • R a , R b , R c , and R d are each independently an optionally substituted Ci_ 3 o aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted Ci_ 2 o aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C 1-12 aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted Ci_g aliphatic group.
  • R a , R b , R c , and R d are each independently an optionally substituted C 3 _g aliphatic group. In certain embodiments, R a , R b , R c , and R d are each independently an optionally substituted C 3 _i 2 aliphatic group. [0053] In certain embodiments, R a is an optionally substituted Ci_ 3 o aliphatic group. In certain embodiments, R b is an optionally substituted Ci_ 3 o aliphatic group. In certain embodiments, R c is an optionally substituted Ci_ 3 o aliphatic group. In certain embodiments, R d is an optionally substituted Ci_ 3 o aliphatic group.
  • an R a and an R b attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.
  • an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R a and an R b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.
  • an R a and an R b attached to the same carbon are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an R a and an R b attached to the same carbon are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an R a and an R b attached to the same carbon are taken together to form an optionally substituted 5-7-membered carbocyclic ring. In some embodiments, for each polymer chain of formula I, at least one R a and R b attached to the same carbon are taken together to form carbocyclic rings.
  • At least one R a and R b attached to the same carbon are taken together to form carbocyclic rings selected from Table la, below.
  • units of j or k that do not comprise such cyclic groups are derived from ethylene oxide. In some embodiments, units of j or k that do not comprise such cyclic groups are derived from propylene oxide.
  • an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.
  • an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R b and an R c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.
  • an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an R b and an R c attached to adjacent carbons are taken together to form an optionally substituted 5-7-membered carbocyclic ring. In some embodiments, for each polymer chain of formula I, at least one R b and R c attached to adjacent carbons are taken together to form carbocyclic rings. In some embodiments, for each polymer chain of formula I, at least one R b and R c attached to adjacent carbons are taken together to form carbocyclic rings selected from Table lb.
  • units of j or k that do not comprise such cyclic groups are derived from ethylene oxide. In some embodiments, units of j or k that do not comprise such cyclic groups are derived from propylene oxide. [0062] As described and defined above for provided APCs of the invention, in certain embodiments R a , R b , R c , and R d are each independently optionally substituted Ci_ 30 aliphatic.
  • each R a , R b , R c , and R d are independently selected from hydrogen or optionally substituted Ci_3o aliphatic; or an R a and an R b attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings; or an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings;
  • E and G are, independently, suitable terminating groups; j is an integer from about 10 to about 15,000; k is an integer from about 0 to about 2,500; and m is the sum of j and k, wherein m is an integer from about 10 to about 17,500.
  • R a , R b , R c , and R d are each independently selected from hydrogen or optionally substituted Ci_ 3 o aliphatic.
  • an R a and an R attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings.
  • Exemplary APCs of formula I wherein R a and an R b attached to the same carbon are taken together are depicted in Table la, below.
  • a compound 189 may also be represented by the formula:
  • compounds depicted in Table la may comprise ether linkages such that at least one instance of — represents a bond to another aliphatic oxide monomer, thereby forming a "k" unit. In certain embodiments, at least one instance of represents a bond to another aliphatic oxide monomer.
  • an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings.
  • Table lb represents a bond to a monomer of C0 2 , thereby forming a "j" unit; and represents a bond to a monomer of C0 2 , thereby forming a bond between two "j" units.
  • Additional aliphatic oxides that may be used to provide APCs of formula I, wherein an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings, are described herein.
  • provided APCs comprise aliphatic oxide monomers derives from terpenes (e.g., compounds 190, 191, and 192). The preparation and use of such aliphatic oxides in accordance with the present invention is discussed in greater detail herein.
  • aliphatic oxides comprise epoxides substituted with one or more aliphatic groups, wherein "aliphatic” 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. All aliphatic oxides are contemplated as starting materials according to the invention, and thus APCs provided by the present invention may incorporate any aliphatic oxide monomer. In certain embodiments, the aliphatic oxides comprise one or more optionally substituted Ci_3o aliphatic groups.
  • the aliphatic oxides comprise one or more optionally substituted C 1-12 aliphatic groups. In certain embodiments, the aliphatic oxides comprise one or more optionally substituted Ci_8 aliphatic groups. In certain embodiments, the aliphatic oxide monomers have cyclic or polycyclic motifs.
  • aliphatic oxides described herein may be prepared from a corresponding olefin (i.e., alkene). Any aliphatic alkene may be used that provides a corresponding aliphatic oxide as described herein.
  • the alkene is optionally substituted Ci_3o acyclic.
  • the alkene is optionally substituted Ci_ 3 o cyclic.
  • the alkene is optionally substituted Ci_ 3 o polycyclic.
  • one or more double bonds are exocyclic.
  • one or more double bonds are endocyclic.
  • the alkene is an allylic alcohol.
  • epoxidation of exocyclic and endocyclic double bonds can be achieved by a number of suitable conditions.
  • Suitable epoxidation reagents and conditions are known to one of ordinary skill in the art, and include those described in March (supra); U.S. Pat. No. US 4,882,442; Kratz et al., Peroxide Chemistry, 2005, 39-59; Journal of Molecular Catalysis, 222, 2004, 103-119); and others cited herein.
  • Non-limiting examples of suitable epoxidation reagents include peroxyacids such as m-chloroperoxybenzoic acid, trifluoroperoxyacetic acid, and 3,15-dinitroperoxybenzoic acid; allyl peroxides such as t-butyl hydroperoxide; hydrogen peroxide; complexes of transition metals such as V, Mn, Mg, Mo, Ti, or Co; DCC; Oxone®; VO(0-isopropyl)3 in liquid C0 2 ; polymer-supported cobalt(II) acetate; dimethyl dioxirane; magnesium monoperoxyphthalate; oxygen; and photooxygenation in the presence of a Ti, V, or Mo complex.
  • peroxyacids such as m-chloroperoxybenzoic acid, trifluoroperoxyacetic acid, and 3,15-dinitroperoxybenzoic acid
  • allyl peroxides such as t-butyl hydroperoxide
  • Suitable epoxidation condition may be stoichiometric or catalytic in nature, may optionally comprise metal complexes with or without asymmetric ligands. Catalytic epoxidations may include an oxidant in stoichiometric or superstoichiometric amounts.
  • Suitable epoxidation conditions typically employ a suitable solvent.
  • nonpolar solvents include, but are not limited to, hydrocarbons and halogenated hydrocarbons such as dichloromethane, pentane, benzene, and toluene.
  • the APCs are copolymers of carbon dioxide, spiroepoxides and optionally one or more other epoxides.
  • Suitable spiro-epoxides are well known in the art and many are available through known means by epoxidation of exocyclic double bonds as shown in Scheme A.
  • the spiro-epoxides contain substructures where the epoxide has a spirocyclic linkage with an aliphatic ring.
  • substructures include, but are not limited to:
  • any carbon hydrogen bond may be replaced with an R'" group, where R'" is selected from halogen; -(CH 2 ) 0 ⁇ R°; -(CH 2 ) 0 ⁇ OR°; -O-(CH 2 ) 0 4 C(0)OR°; -(CH 2 ) 0 4 CH(OR°) 2 ;
  • -(CH 2 )o ⁇ SR°; -(CH 2 )o ⁇ Ph, which may be substituted with R°; -(CH 2 ) 0 ⁇ O(CH 2 ) 0 iPh which may be substituted with R°; -CH CHPh, which may be substituted with R°; -N0 2 ; -CN; -N 3 ; -(CH 2 )o ⁇ N(R°) 2 ; -(CH 2 )o 4 N(R°)C(0)R°; -N(R°)C(S)R°; -(CH 2 ) 0 ⁇ N(R o )C(O)NR° 2 ;
  • R° 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.
  • one or more of the carbon atoms of the aliphatic ring may be replaced by a heteroatom.
  • one or more of the bonds in the ring system may be a double bond.
  • Suitable spiroepoxides include, but are not limited to, those shown in Table 2.
  • the epoxide monomers include ring systems wherein the epoxide is part of a fused ring system.
  • Compounds of this class are well known in art and methods to synthesize them are well established ⁇ vide supra).
  • epoxides are accessed through epoxidation of double bonds that are part of a ring system.
  • Suitable fused-ring epoxides include those where the epoxide ring contains two carbons that are part of another aliphatic ring system. Examples of such substructures include, but are not limited to:
  • any carbon hydrogen bond may be replaced with an R" group as defined above.
  • one or more of the carbon atoms of the aliphatic ring may be replaced by a heteroatom.
  • one or more of the bonds in the ring system may be a double bond.
  • Examples of potentially suitable polycyclic epoxides include, but are not limited to, those shown in Table 3. Table 3. Polycyclic Epoxides
  • epoxides depicted in Table 3 may be used to provide APCs similar to those de jppiicctteedd iinn TTaabbllee lb, wherein an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings.
  • aliphatic polycarbonates are provided from terpene oxides.
  • the epoxidation of terpenes is known in the art (see references cited herein) and many of the resulting epoxides are suitable monomers for incorporation into aliphatic polycarbonate polymers of the present invention.
  • Terpene compositions are best known as primary components of essential oils, and are often classified as natural products. They are oligomers of isoprene and originate as complex mixtures of flavors and fragrances in higher plants. Many terpenes are commercially available on an industrial scale and can be purchased in volumes typically ranging from about 5- 2000 gallons. Structurally, terpenes are unsaturated organic compounds having the empirical chemical formula (C 5 Hg) n , signifying the isoprene units from which they are derived. While some terpenes are hydrocarbons, many exist in the form of alcohols, esters, ethers, ketones, and aldehydes. They are further classified as monocyclic (e.g.
  • dipentene dicyclic (e.g. pinene), or acyclic (e.g. myrcene); or as monoterpenes (e.g. pinene, nerol, citral, camphor, methol, limonene), sesquiterpenes (e.g. nerolidol, farnesol), diterpenes (e.g. phytol, vitamin Ai), triterpenes (e.g. squalene).
  • Terpenoids are a subclass of terpenes that do not strictly adhere to the terpene empircal formula (e.g., one or more methyl groups are added, removed, or displaced; or one or more hetereoatoms added).
  • the terms "terpene” and “terpenoid” are used interchangably.
  • provided aliphatic polycarbonates are copolymers of terpene oxides and carbon dioxide.
  • provided aliphatic terpene polycarbonates are heteropolymers incorporating other simpler epoxide monomers including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclopentene oxide and cyclohexene oxide.
  • Such heteropolymers can include random co-polymers, tapered copolymers and block copolymers.
  • terpene oxides can be derived from (i.e., made from) naturally occurring terpenes or synthetic derivatives thereof.
  • the terpene oxide monomers are derived from monoterpenes or their derivatives. In certain embodiments, the terpene oxide monomers are derived from sesquiterpenes or their derivatives. In certain embodiments, the terpene oxide monomers are derived from diterpenes or their derivatives. In certain embodiments, the terpene oxide monomers are derived from sesterterpenes or their derivatives. In certain embodiments, the terpene oxide monomers are derived from triterpenes or their derivatives.
  • mono-epoxides having the formula CioHi 6 0, derived from epoxidation of monoterpenes having the formula CioHi 6i are employed to provide polymers of the present invention.
  • the monoterpene mono-epoxide is limonene oxide.
  • the terpene oxide monomers are derived from sesquiterpenes or derivatives thereof.
  • mono-epoxides of the formula C15H24O derived from sesquiterpenes having the formula C15H24 are employed to provide polymers of the present invention.
  • terpene oxide monomers are derived from diterpenes or derivatives thereof.
  • mono-epoxides of the formula C20H32O derived from diterpenes having the formula C20H32 are employed to provide polymers of the present invention.
  • terpene monomers may contain a plurality of oxidations and have the formula CioH ( i 6 -2n ) O n , Ci 5 H ( 2 4 -2n ) O n , C2oH (3 2-2n ) O n , or C 3 o(H( 4 8-2n ) O n .
  • the terpene monomers described above and herein may have one or more hydrogen atoms independently replaced by R'" groups.
  • terpene oxide monomers are derived from acyclic monoterpenes.
  • such monoterpenes are optionally substituted and selected from the group consisting of (+)-Citronellal, (-)-beta-Citronellol, (+)-beta-Citronellol, (-)-Citronellal, 2, 6-Dimethyl-2, 4, 6-octatriene, 3, 7-Dimethyl-l-octen-3-ol, beta-Citronellol, Citral Dimethyl Acetal, Citronellic Acid, Citronellyl Acetate, Dihydrolinalool, Geraniol, Geranyl Acetate, Geranyl Formate, Geranyl Nitrite, Geranylacetone, Linalool, Linalyl Acetate, Nerol, and Neryl Acetate.
  • terpene oxide monomers are derived from monocyclic monoterpenes.
  • such monoterpenes are optionally substituted and selected from the group consisting of (+)-Limonene, (+)-Pulegone, (+/-)-Limonene, (+/-)- Terpinen-4-ol, (-)-Limonene, (-)-p-Mentha-l,5-diene, (-)-Perillaldehyde, (-)-Terpinen-4-ol, (R)- (-)-Carvone, (S)-(+)-Carvone, alpha-Ionone, alpha-Terpinene, alpha-Terpineol, beta-Ionone, gamma-Terpinene, Ionone, Isopulegol, Terpin Monohydrate, Terpinolene, and trans-Sobrerol.
  • terpene oxide monomers are derived from bicyclic monoterpenes.
  • such monoterpenes are optionally substituted and selected from the group consisting of (+)-3-Carene, (+/-)-Camphene, (-)-beta-Pinene, (lPv)-(+)-alpha-Pinene, (lS)-(-)-alpha-Pinene, and Verbenone.
  • terpene oxide monomers are derived from monoterpenes, diterpenes, triterpenes, terpenoids, sesquiterpenes, or derivatives thereof.
  • such terpenes are optionally substituted and selected from the group consisting of (+/-)-alpha-Bisabolol, Abietic Acid, Abscisic Acid, alpha-Caryophyllene, beta-Caryophyllene, Bisabolene, Ethyl Abietate, Farnesene, Farnesol, Farnesyl Acetate, Geranyl-linalool, Isophytol, Linalool Oxide, Nerolidol, Oleanolic Acid Hydrate, Phytol, Phytyl Acetate, Retinoic Acid, Sodium Abietate, and Squalene.
  • the terpenes are optionally substituted and selected from the group consisting of nerol oxide, myroxide, rose oxide, limetol, linanol oxide, butyldimethyldihydropyran, acetoxyamyltetrahydropyran, tricyclodecenyl methyl ether, estragole, methyleugenol, and benzylisoeugenol.
  • the terpenes are optionally substituted and selected from the group consisting of delta-2-carene, delta-3-carene, dipentene, limonene, myrcene, beta-phellandrene, alpha-pinene, beta-pinene, alpha-terpinene, gamma-terpinene, and terpinolene.
  • aliphatic oxide monomers include epoxides derived from naturally occurring materials such as epoxidized resins or oils.
  • epoxides include, but are not limited to: Epoxidized Soybean Oil; Epoxidized Linseed Oil; Epoxidized Octyl Soyate; Epoxidized PGDO; Methyl Epoxy Soyate; Butyl Epoxy Soyate; Epoxidized Octyl Soyate; Methyl Epoxy Linseedate; Butyl Epoxy Linseedate; and Octyl Epoxy Linseedate.
  • Vikoflex® materials examples include Vikoflex 7170 Epoxidized Soybean Oil, Vikoflex 7190 Epoxidized Linseed, Vikoflex 4050 Epoxidized Octyl Soyate, Vikoflex 5075 Epoxidized PGDO, Vikoflex 7010 Methyl Epoxy Soyate, Vikoflex 7040 Butyl Epoxy Soyate, Vikoflex 7080 Epoxidized Octyl Soyate, Vikoflex 9010 Methyl Epoxy Linseedate, Vikoflex 9040 Butyl Epoxy Linseedate, and Vikoflex 9080 Octyl Epoxy Linseedate.
  • provided aliphatic polycarbonates derived from epoxidized resins or oils are heteropolymers incorporating other simpler epoxide monomers including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclopentene oxide and cyclohexene oxide.
  • These heteropolymers can include random co-polymers, tapered copolymers and block copolymers.
  • monomers include epoxides derived from alpha olefins.
  • epoxides include, but are not limited to those derived from Cio alpha olefin, C12 alpha olefin, C14 alpha olefin, Ci 6 alpha olefin, C 18 alpha olefin, C20-C24 alpha olefin, C24-C28 alpha olefin and C30+ alpha olefins.
  • These and similar materials are commercially available from Arkema Inc. under the trade name Vikolox®.
  • Commerically available Vikolox® materials include those depicted in Table 4, below.
  • provided aliphatic polycarbonates derived from alpha olefins are heteropolymers incorporating other simpler epoxide monomers including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclopentene oxide and cyclohexene oxide.
  • These heteropolymers can include random co-polymers, tapered copolymers and block copolymers. Table 4.
  • terpene epoxides incorporated into provided APCs are modified triterpenes.
  • said modified triterpenes are steroids (e.g., cholesterol, 3-beta-acetoxyandrost-5-en-17-one, lanosterol, cycloartenol, estrogen, progesterone, testosterone) or sapogenins.
  • steroids e.g., cholesterol, 3-beta-acetoxyandrost-5-en-17-one, lanosterol, cycloartol, estrogen, progesterone, testosterone
  • Method for epoxidizing steroids are known in the art, and include U.S. Pat. Nos. 6,841,665, 3,929,769; Ma, et al, Steroids, 2005, 70, 245-250; Hanson, et al, J. Chem. Research (S), 1998, 50-51.
  • provided aliphatic polycarbonates are heteropolymers incorporating two or more of the above-described epoxide monomers (e.g. terpene oxides, epoxides derived from resins or oils, and epoxides derived from alpha olefins).
  • epoxide monomers e.g. terpene oxides, epoxides derived from resins or oils, and epoxides derived from alpha olefins.
  • Such heteropolymers optionally include other simpler epoxide monomers including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclopentene oxide and cyclohexene oxide.
  • These heteropolymers can include random co-polymers, tapered copolymers and block copolymers.
  • Incorporation as used above can refer to use of the monomer as the only comonomer with carbon dioxide, and/or use of the monomer as one constituent in the composition of a heteropolymer containing carbon dioxide and two or more epoxide monomers.
  • the present invention also provides novel metal complexes of the formula (III) as is described in detail below. Methods of making and using metal complexes of formula (III) is described in detail in U.S. Pat. No. 7,304,172, and U.S. Pat. Application Publication Nos. 2007/0255039 and 2008/0108499, the entire content of each of which is hereby incorporated by reference.
  • the metal complex employed is a zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese complex.
  • the metal complex is an aluminum complex.
  • the metal complex is a chromium complex.
  • the complex metal is zinc complex.
  • the metal complex is a titanium complex.
  • the metal complex is a ruthenium complex.
  • the metal complex is a manganese complex.
  • the metal complex is cobalt complex. In certain embodiments, wherein the metal complex is a cobalt complex, the cobalt metal has a valency of +3 ⁇ i.e., Co(III)).
  • the metal complex comprises a tetradentate ligand. In certain embodiments the metal complex comprises a Schiff base. In certain embodiments the metal complex comprises a porphyrin ligand, a salen ligand, or a beta diimidate ligand.
  • the metal complex is any of the above described metal complexes of the formula (III), or subsets thereof.
  • M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium and manganese;
  • X is absent or is a nucleophilic ligand
  • each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl, or R 1 and R 2 , or R 2 and R 3 , are joined to form an optionally substituted aryl or optionally substituted heteroaryl ring; and
  • Ring A forms an optionally substituted 5- to 6-membered ring.
  • the metal is aluminum. In certain embodiments, the metal is chromium. In certain embodiments, the metal is zinc. In certain embodiments, the metal is titanium. In certain embodiments, the metal is ruthenium. In certain embodiments, the metal is manganese. In certain embodiments, the metal is cobalt. In certain embodiments, wherein the metal is cobalt, the cobalt has a valency of +3 ⁇ i.e., Co(III)).
  • the metal complex is a metal catalyst.
  • X is absent.
  • X is a nucleophilic ligand.
  • X is -OR x , wherein R x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.
  • X is -OR x , wherein R x is optionally substituted aryl. In certain embodiments, X is -OR x , wherein R x is optionally substituted phenyl. In certain embodiments, X is -OC 6 H5 or -OC 6 H 2 (2,4-N0 2 ).
  • X is halo. In certain embodiments, X is -Br. In certain embodiments, X is -CI. In certain embodiments, X is -I.
  • X is -0(S0 2 )R x . In certain embodiments X is -OTs. In certain embodiments X is -OS0 2 Me, In certain embodiments X is -OS0 2 CF 3 .
  • X is -N 3 .
  • X is -NC [0115] In certain embodiments, X is -CN.
  • Ring A forms an optionally substituted 5-membered ring. In certain embodiments, Ring A forms an optionally substituted cyclopentyl ring. In certain embodiments, Ring A forms an optionally substituted 5-membered aryl ring.
  • Ring A forms an optionally substituted 6-membered ring. In certain embodiments, Ring A forms an optionally substituted cyclohexyl ring. In certain embodiments, Ring A forms an optionally substituted 6-membered aryl ring.
  • the metal complex of formula (III) may be considered in two portions: a
  • Northern Hemisphere comprising the imine nitrogen atoms and Ring A
  • Southern Hemisphere comprising the rest of the metal complex.
  • the Northern Hemisphere of the metal complex is of the formula (iii-a) :
  • Ring A forms an optionally substituted 5- to 6-membered ring.
  • Ring A forms an optionally substituted 6-membered ring of the formula (iii-b):
  • R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl. In certain embodiments, R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B are, independently, selected from hydrogen and optionally substituted aliphatic. In certain embodiments, R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B are, independently, selected from hydrogen and optionally substituted heteroaliphatic.
  • R , R , R , R , R , and R are, independently, selected from hydrogen and optionally substituted aryl.
  • R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B are, independently, selected from hydrogen and optionally substituted heteroaryl.
  • two or more of R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B are joined to form one or more aliphatic, heteroaliphatic, aromatic, or heteroaromatic rings having 3 to 8 total ring atoms.
  • each of R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B are hydrogen.
  • R 5A , R 5B , R 6A , and R 6B are hydrogen, Ring A forms a 6-membered ring of the formula:
  • Ring A forms an optionally substituted 6-membered ring of the formula (iii-c):
  • c 0 to 4.
  • R 5A and R 5B are, independently, selected from hydrogen and optionally substituted aliphatic. In certain embodiments, R 5A and R 5B are, independently, selected from hydrogen and optionally substituted heteroaliphatic. In certain embodiments, R 5A and R 5B are, independently, selected from hydrogen and optionally substituted aryl. In certain embodiments, R 5A and R 5B are, independently, selected from hydrogen and optionally substituted heteroaryl.
  • each R 5A and R 5B is hydrogen.
  • c is 0 to 2. In certain embodiments, c is 0 to 1. In certain embodiments, c is 0. In certain embodiments, c is 1.
  • each instance of R 12 is, independently, selected from hydrogen and optionally substituted aliphatic. In certain embodiments, each instance of R 12 is, independently, selected from hydrogen and optionally substituted heteroaliphatic. In certain embodiments, each instance of R 12 is, independently, selected from hydrogen and optionally substituted aryl. In certain embodiments, each instance of R 12 is, independently, selected from hydrogen and optionally substituted heteroaryl.
  • each instance of R 12 is hydrogen.
  • Ring A forms an optionally substituted 5-membered ring of the formula (iii-d) :
  • R 4A , R 4B , R 5A , and R 5B are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, or wherein one of R 4A , R 4B , R 5A , and R 5B and one of R 4A , R 4B , R 5A , and R 5B are optionally joined to form a 3- to 7-membered ring.
  • R 4A , R 4B , R 5A , and R 5B are, independently, selected from hydrogen and optionally substituted aliphatic. In certain embodiments, R 4A , R 4B , R 5A , and R 5B are, independently, selected from hydrogen and optionally substituted heteroaliphatic. In certain embodiments, R 4A , R 4B , R 5A , and R 5B are, independently, selected from hydrogen and optionally substituted aryl. In certain embodiments, R 4A , R 4B , R 5A , and R 5B are, independently, selected from hydrogen and optionally substituted heteroaryl.
  • one of R 4A , R 4B , R 5A , and R 5B and one of R 4A , R 4B , R 5A , and R 5B are optionally joined to form a 3- to 6- membered ring.
  • each instance of R 4A , R 4B , R 5A , and R 5B is hydrogen.
  • Ring A forms a 5-membered ring of the formula:
  • Ring A forms an optionally substituted 5-membered ring of the formula (iii—f):
  • R 4A , R 5A , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl. In certain embodiments, R 4A , R 5A , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are, independently, selected from hydrogen and optionally substituted aliphatic.
  • R 4A , R 5A , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are, independently, selected from hydrogen and optionally substituted heteroaliphatic. In certain embodiments, R 4A , R 5A , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are, independently, selected from hydrogen and optionally substituted aryl.
  • R 4A , R 5A , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are, independently, selected from hydrogen and optionally substituted heteroaryl.
  • R , 16B is hydrogen.
  • Ring A forms an optionally substituted 5-membered ring of the formula (iii-g):
  • Ring A forms an optionally substituted 5-membered ring of any of the formulae (iii-h) to (iii-k) :
  • Ring A forms an optionally substituted 5-membered ring of any of the formulae (Hi— I) to (iii-o) :
  • Ring A forms an optionally substituted 5-membered ring of the formula (iii-p):
  • d 0 to 4.
  • d is 0 to 2. In certain embodiments, d is 0 to 1. In certain embodiments, d is 0. In certain embodiments, d is 1.
  • each instance of R 17 is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl. In certain embodiments, each instance of R 17 is, independently, selected from hydrogen and optionally substituted aliphatic. In certain embodiments, each instance of R 17 is, independently, selected from hydrogen and optionally substituted heteroaliphatic. In certain embodiments, each instance of R 17 is, independently, selected from hydrogen and optionally substituted aryl. In certain embodiments, each instance of R 17 is, independently, selected from hydrogen and optionally substituted heteroaryl.
  • each instance of R 17 is hydrogen.
  • Ring A forms an optionally substituted 5-membered ring of the formula (iii-q) :
  • R 1 is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl. In certain embodiments, each instance of R 1 is hydrogen. In certain embodiments, each instance of R 1 is halogen. In certain embodiments, each instance of R 1 is optionally substituted aliphatic. In certain embodiments, each instance of R 1 is optionally substituted heteroaliphatic. In certain embodiments, each instance of R 1 is optionally substituted aryl. In certain embodiments, each instance of R 1 is optionally substituted heteroaryl.
  • each instance of R 2 is hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl. In certain embodiments, each instance of R 2 is hydrogen. In certain embodiments, each instance of R 2 is halogen. In certain embodiments, each instance of R 2 is optionally substituted aliphatic. In certain embodiments, each instance of R 2 is optionally substituted heteroaliphatic. In certain embodiments, each instance of R 2 is optionally substituted aryl. In certain embodiments, each instance of R 2 is optionally substituted heteroaryl.
  • each instance of R 3 is hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl. In certain embodiments, each instance of R 3 is hydrogen. In certain embodiments, each instance of R 3 is halogen. In certain embodiments, each instance of R 3 is optionally substituted aliphatic. In certain embodiments, each instance of R 3 is optionally substituted heteroaliphatic. In certain embodiments, each instance of R 3 is optionally substituted aryl. In certain embodiments, each instance of R 3 is optionally substituted heteroaryl.
  • R 1 and R 2 are joined to form an optionally substituted aryl or optionally substituted heteroaryl ring. In certain embodiments, R 1 and R 2 are joined to form an optionally substituted aryl ring. In certain embodiments, R 1 and R 2 are joined to form an optionally substituted heteroaryl ring.
  • R 2 and R 3 are joined to form an optionally substituted aryl or optionally substituted heteroaryl ring. In certain embodiments, R 2 and R 3 are joined to form an optionally substituted aryl ring. In certain embodiments, R 2 and R 3 are joined to form an optionally substituted heteroaryl ring.
  • each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen, optionally substituted aliphatic, and/or any of R 1 and R 2 , and/or any of R 2 and R 3 , are joined to form an optionally substituted aryl or optionally substituted heteroaryl ring.
  • each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen and/or any of R 1 and R 2 are joined to form an optionally substituted aryl or optionally substituted heteroaryl ring.
  • each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen and/or any of R 2 and R 3 , are joined to form an optionally substituted aryl or optionally substituted heteroaryl ring.
  • each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen and optionally substituted aliphatic. In certain embodiments, each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen and optionally substituted heteroaliphatic. In certain embodiments, each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen and optionally substituted aryl. In certain embodiments, each instance of R 1 , R 2 , and R 3 is, independently, selected from hydrogen and optionally substituted heteroaryl.
  • each instance of R 1 , R 2 , and R 3 is hydrogen. In certain embodiments, each instance of R 1 and R 3 is hydrogen. In certain embodiments, each instance of R 2 and R 3 is hydrogen. In certain embodiments, each instance of R 1 and R 2 is hydrogen. In certain embodiments, each instance of R 1 is hydrogen. In certain embodiments, each instance of R 2 is hydrogen. In certain embodiments, each instance of R 3 is hydrogen.
  • R 1 is an optionally substituted aryl moiety
  • b is 0 to 5, inclusive.
  • b is 0 to 2. In certain embodiments, b is 0 to 1. In certain embodiments, b is 0. In certain embodiments, b is 1.
  • each instance of R 11 is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl, and/or two R 11 groups adjacent to each other are joined to form an optionally substituted 5- to 6-membered ring.
  • each instance of R 11 is, independently, selected from hydrogen and optionally substituted aliphatic.
  • each instance of R 11 is, independently, selected from hydrogen, optionally substituted heteroaliphatic.
  • each instance of R 11 is, independently, selected from hydrogen, optionally substituted aryl.
  • each instance of R 11 is, independently, selected from hydrogen, optionally substituted heteroaryl.
  • each instance of R 11 is hydrogen.
  • the Southern Hemisphere of the metal complex is of the formula (ii-c):
  • M, X, R 1 , R 2 and R 3 are, as defined above and herein;
  • R 7 R 8 , R 9 and R 10 are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl, and/or two groups selected from R 7 R 8 R 9 and R 10 adjacent to each other are joined to form an optionally substituted 5- to 7-membered ring.
  • R 7 R 8 , R 9 and R 10 are, independently, selected from hydrogen and optionally substituted aliphatic.
  • R 7 R 8 , R 9 and R 10 are, independently, selected from hydrogen and optionally substituted heteroaliphatic.
  • R 7 R 8 R 9 and R 10 are, independently, selected from hydrogen and optionally substituted aryl. In certain embodiments, R 7 R 8 , R 9 and R 10 are, independently, selected from hydrogen and optionally substituted heteroaryl. [0161] In certain embodiments, R 7 R 8 , R 9 and R 10 are, independently, selected from hydrogen and optionally substituted aryl. In certain embodiments, R 7 R 8 , R 9 and R 10 are, independently, selected from hydrogen and optionally substituted phenyl.
  • R 7 R 8 , R 9 and R 10 are, independently, selected from hydrogen and optionally substituted Ci_io aliphatic. In certain embodiments, R 7 R 8 , R 9 and R 10 are, independently, selected from hydrogen and optionally substituted Ci_i 0 alkyl.
  • R 7 R 8 R 9 and R 10 are, independently, selected from hydrogen and methyl, trichloromethyl, trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, iso-butyl, n- pentyl, neopentyl, amyl, trityl, adamantyl, thexyl, benzyl and cumyl.
  • each of R 7 R 8 , R 9 and R 10 are hydrogen. In certain embodiments, each of R 8 and R 10 are hydrogen. In certain embodiments, R 8 is hydrogen. In certain embodiments, R 10 is hydrogen.
  • the Southern Hemisphere of the metal complex is of the formula (ii-d) :
  • M, X, R 1 , R 2 , R 3 , R 7 and R 9 are, as defined above and herein.
  • R 7 and R 9 are, independently, selected from hydrogen and optionally substituted Ci_i 2 aliphatic. In certain embodiments, R 7 and R 9 are, independently, selected from hydrogen and optionally substituted Ci_i 2 alkyl. In certain embodiments, R 7 and R 9 are, independently, selected from hydrogen and methyl, trichloromethyl, trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl, benzyl and cumyl. [0166] In certain embodiments, R 7 and R 9 are, independently, selected from hydrogen and optionally substituted aryl. In certain embodiments, R 7 and R 9 are, independently, selected from hydrogen and optionally substituted phenyl.
  • R 7 and R 9 groups influence the rate and selectivity of the polymerization reactions catalyzed by the metal complexes. It is further believed that the relative sizes of these groups, and the absolute size of R 7 exerts an influence on which epoxides can be successfully polymerized with catalysts of this class.
  • the polymerization of certain bulky epoxides, (such as terpene oxides and polycyclic epoxides) it is advantageous that R 7 be smaller than R 9 . In certain embodiments it is advantageous for there to be a difference in the sizes of R 7 andR 9 .
  • the relative size of a group can be determined from the van der Waals surface and/or molecular volume as calculated for that group.
  • the van der Waals surface is a closed surface, and hence, it contains volume. This volume is called the molecular volume, or van der Waals volume, and is usually given in A 3 .
  • the straightforward way of calculating molecular volume on the computer is by numerical integration, i.e., by surrounding the van der Waals envelope with a grid of small bricks and summing up the bricks whose centers are within the van der Waals envelope of the molecule (i.e., are within a van der Waals radius from atom nucleus) (see, for example, Whitley, "Van der Waals surface graphs and molecular shape,” Journal of Mathematical Chemistry (1998) 23:377- 397).
  • the relative size of a group can also be measured from the "A-value" for a given group.
  • the A-value is a measure of the effective size of a given group.
  • the "A-value” refers to the conformational energies (-G 0 values) as determined for a substituted cyclohexane and the relative axial-equatorial disposition of the substituent (see Table 5, provided below, and pages
  • the molecular volume of group R 9 is larger than the molecular volume of group R 7 . In certain embodiments, the molecular volume of R 9 is at least 1.2 times greater than the molecular volume of R 7 . In certain embodiments, the molecular volume of R 9 is at least 1.5 times greater than the molecular volume of R 7 . In certain embodiments, the molecular volume of R 9 is at least 1.8 times greater than the molecular volume of R 7 . In certain embodiments, the molecular volume of R 9 is at least 2 times greater than the molecular volume of R 7 . In certain embodiments, the molecular volume of R 9 is at least 2.5 times greater than the molecular volume of R 7 . In certain embodiments, the molecular volume of R 9 is at least 3 times greater than the molecular volume of R 7 .
  • the A-value of R 9 is greater than the A-value of R 7 . In certain embodiments, the A-value of R 9 is at least 1.2 times greater than the A value of R 7 . In certain embodiments, the A-value of R 9 is at least 1.5 times greater than the A value of R 7 . In certain embodiments, the A-value of R 9 is at least 1.8 times greater than the A value of R 7 . In certain embodiments, the A-value of R 9 is at least 2 times greater than the A value of R 7 . In certain embodiments, the A-value of R 9 is at least 2.5 times greater than the A value of R 7 . In certain embodiments, the A-value of R 9 is at least 3 times greater than the A value of R 7 .
  • the A-value of R 7 is less than about 2.5 kcal/mol. In certain embodiments, the A-value of R 7 is less than about 3 kcal/mol. In certain embodiments, the A-value of R 7 is less than about 3.5 kcal/mol. In certain embodiments, the A-value of R 7 is less than about 4 kcal/mol.
  • the A-value of R 9 is greater than about 2.5 kcal/mol. In certain embodiments, the A-value of R 9 is greater than about 3 kcal/mol. In certain embodiments, the A-value of R 9 is greater than about 3.5 kcal/mol. In certain embodiments, the A-value of R 9 is greater than about 4 kcal/mol.
  • the A-value of R 9 is between about 0 to about 2.5 kcal/mol. In certain embodiments, the A-value of R 9 is between about 0 to about 3 kcal/mol. In certain embodiments, the A-value of R 9 is between about 0 to about 3.5 kcal/mol. In certain embodiments, the A-value of R 9 is between about 0 to about 4 kcal/mol.
  • the A-value of R 7 is between about 0 to about 2.5 kcal/mol. In certain embodiments, the A-value of R 7 is between about 0 to about 3 kcal/mol. In certain embodiments, the A-value of R 7 is between about 0 to about 3.5 kcal/mol. In certain embodiments, the A-value of R 7 is between about 0 to about 4 kcal/mol.
  • the Southern Hemisphere of the metal complex is of the formula (ii-e):
  • R 8 , R 9 , andR 1 l 0 u are, as defined above and herein.
  • the present invention provides a metal complex of the formula (Ill-a) :
  • M, X, R 1 , R 2 , R 3 , R 4A , R 4B , R 5A , R 5B , R 6A , and R 6B are as defined above and herein.
  • the present invention provides a metal complex of the formula (Ill-b) :
  • the present invention provides a metal complex of the formula (III-c):
  • the present invention provides a metal complex of the formula (Ill-d) :
  • M, X, R 1 , R 2 , R 3 , R 4A , R 4B , R 5A , and R 5B are as defined above and herein.
  • the present invention provides a metal complex of the formula (Ill-e) :
  • M, X, R 1 , R 2 , R 3 , R 4A , R 5A , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are as defined above and herein.
  • the present invention provides a metal complex of any one of the formulae (III-f) to (IH-i) :
  • M, X, R 1 , R 2 , R 3 , R 4A , R 5A , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R are as defined above and herein.
  • a particular enantiomer of a compound may, in some embodiments be provided substantially free of the corresponding enantiomer, and may also be referred to as "optically enriched.”
  • “Optically-enriched,” as used herein, means that the compound 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.
  • the present invention provides an optically enriched metal complex of any one of the formulae (Ill-f) to (IH-i). In certain embodiments, the present invention provides an optically enriched metal complex of formula (Ill-f). In certain embodiments, the present invention provides an optically enriched metal complex of formula (Hl-g). In certain embodiments, the present invention provides an optically enriched metal complex of formula (Ill-h). In certain embodiments, the present invention provides an optically enriched metal complex of formula (Ill-i).
  • the present invention provides a metal complex of the formula (Ill-j) :
  • the present invention provides a metal complex of any one of the formulae (Ill-k) to (III-n) :
  • the present invention provides an optically enriched metal complex of any one of the formulae (Ill-k) to (III-n). In certain embodiments, the present invention provides an optically enriched metal complex of formula (Ill-k). In certain embodiments, the present invention provides an optically enriched metal complex of formula (III-l). In certain embodiments, the present invention provides an optically enriched metal complex of formula (III-m). In certain embodiments, the present invention provides an optically enriched metal complex of formula (III-n).
  • the present invention provides a metal complex of the formula (III-o):
  • the present invention provides a metal complex of the formula (III-p):
  • the present invention provides a metal complex of the formula (Ill-q):
  • R , R are as defined above and herein.
  • the present invention provides a metal complex of the formula (Ill-r) :
  • the present invention provides a metal complex of the formula (Ills) :
  • the present invention provides a metal complex of the formula (Ill-t) :
  • the present invention provides a metal complex of the formula (III-u):
  • M, X, R 1 , R 2 , R 3 , R 4A , R 5A , R 7 , R 8 , R 9 , R 10 , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are as defined above and herein.
  • the present invention provides a metal complex of the formula (III-v) :
  • M, X, R 1 , R7', R8°, R9 y and R 1 1 0 U are as defined above and herein.
  • the present invention provides a metal complex of the formula (III-w):
  • M, X, R 1 , R 2 , R 3 , R 4A , R 5A , R 7 , R 9 , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are as defined above and herein.
  • the present invention provides a metal complex of formula (III-x):
  • M, X, R 1 , R 2 , R 3 , R 7 and R 9 are as defined above and herein.
  • the present invention provides a metal complex of the formula (Ill-y) :
  • R are as defined above and herein.
  • the present invention provides a metal complex of the formula (III-z) :
  • M, X, R 4A , R 5A , R 7 , R 9 , R 13A , R 13B , R 14A , R 14B , R 15A , R 15B , R 16A , R 16B are as defined above and herein.
  • the present invention provides a metal complex of the formula (III-aa):
  • the present invention provides a metal complex of the formulae (III-bb) to (III-ee):
  • the present invention provides an optically enriched metal complex of any one of the formulae (III-bb) to (III-ee). In certain embodiments, the present invention provides an optically enriched metal complex of formula (III-bb). In certain embodiments, the present invention provides an optically enriched metal complex of formula (III-cc). In certain embodiments, the present invention provides an optically enriched metal complex of formula (III-dd). In certain embodiments, the present invention provides an optically enriched metal complex of formula (III-ee).
  • the present invention provides a metal complex of the formula (III-ffi :
  • the present invention provides a metal complex formula (III-gg) :
  • M, X, R 1 , R7', R8°, R9 y and R 1 1 0 U are as defined above and herein.
  • the present invention provides a metal complex of the formula (III-hh) :
  • the present invention provides a metal complex of the formula (Ill-ii) :
  • M, X, R 1 , R 2 , R 3 , R 7 and R 9 are as defined above and herein.
  • the present invention provides a metal complex of the formula (III-jj) :
  • the present invention provides a metal complex of the formula (III-kk):
  • the present invention provides a metal complex of the formula (III-ll) :
  • the metal complex is selected from any one of the following, wherein X is absent or is a nucleophilic ligand:
  • X is absent.
  • the metal complex is a cobalt (Co) complex selected from any of the following structures:
  • APCs of the present invention are provided using metal complexes of formula IV:
  • X' is a nucleophilic ligand
  • each instance of R 1 is independently an optionally substituted group selected from the group consisting of aliphatic, heteroaliphatic, aryl, and heteroaryl; wherein the atom of R 1 attached to the diimidate nitrogen is carbon;
  • each instance of R 2 and R 3 is independently hydrogen, halogen, or an optionally substituted group selected from aliphatic, heteroaliphatic, aryl, and heteroaryl; or R 2 and R 3 are joined with their intervening atoms to form an optionally substituted ring selected from the group consisting of 3-12-membered carbocyclic; 3-12 membered heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 6-10 membered aryl; and 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or R 1 and R 2 are joined with their intervening atoms to form an optionally substituted ring selected from the group consisting of 3-12-membered carbocyclic; 3-12 membered heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 6-10 membered aryl; and 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • X' is a nucleophilic ligand.
  • X' is -OR x , wherein R x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.
  • R x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.
  • X' is -OR x , wherein R x is optionally substituted aryl.
  • X' is -OR x , wherein R x is optionally substituted phenyl.
  • X is -OC 6 H5 or
  • X' is halo. In certain embodiments, X' is -Br. In certain embodiments, X' is -CI. In certain embodiments, X' is -I.
  • X' is -0(S0 2 )R x . In certain embodiments X' is -OTs. In certain embodiments X' is -OS0 2 Me. In certain embodiments X' is -OSO 2 CF 3 .
  • X' is -N 3 .
  • X' is -NC
  • X' is -CN.
  • R 1 is optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl. In certain embodiments, each instance of R 1 is optionally substituted aliphatic. In certain embodiments, each instance of R 1 is optionally substituted heteroaliphatic. In certain embodiments, each instance of R 1 is optionally substituted aryl. In certain embodiments, each instance of R 1 is optionally substituted heteroaryl.
  • each instance of R 2 is hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl. In certain embodiments, each instance of R 2 is hydrogen. In certain embodiments, each instance of R 2 is halogen. In certain embodiments, each instance of R 2 is optionally substituted aliphatic. In certain embodiments, each instance of R 2 is optionally substituted heteroaliphatic. In certain embodiments, each instance of R 2 is optionally substituted aryl. In certain embodiments, each instance of R 2 is optionally substituted heteroaryl.
  • R 3 is hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, or optionally substituted heteroaryl. In certain embodiments, R 3 is hydrogen. In certain embodiments, R 3 is halogen. In certain embodiments, R 3 is optionally substituted aliphatic. In certain embodiments, R 3 is optionally substituted heteroaliphatic. In certain embodiments, R 3 ' is optionally substituted aryl. In certain embodiments, R 3 is optionally substituted heteroaryl.
  • R 2 and R 3 are joined with their intervening atoms to form an optionally substituted ring selected from the group consisting of 3-12-membered carbocyclic; 3-12 membered heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 6-10 membered aryl; and 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 2 and R 3 are joined with their intervening atoms to form an optionally substituted 3-12-membered carbocyclic ring.
  • R 2 and R 3 are joined with their intervening atoms to form an optionally substituted 3-12 membered heterocyclyl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In some embodiments, R 2 and R 3 are joined with their intervening atoms to form an optionally substituted 6-10 membered aryl ring. In some embodiments, R 2 and R 3 are joined with their intervening atoms to form an optionally substituted 5-10 membered heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • one R 2 group is joined with R 3 to form an optionally substituted ring selected from the group consisting of 3-12-membered carbocyclic; 3-12 membered heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 6-10 membered aryl; and 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 1 and R 2 are joined with their intervening atoms to form an optionally substituted ring selected from the group consisting of 3-12-membered carbocyclic; 3-12 membered heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 6-10 membered aryl; and 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • R 1 and R 2 are joined with their intervening atoms to form an optionally substituted 3-12-membered carbocyclic ring.
  • R 1 and R 2 are joined with their intervening atoms to form an optionally substituted 3-12 membered heterocyclyl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In some embodiments, R 1 and R 2 are joined with their intervening atoms to form an optionally substituted 6-10 membered aryl ring. In some embodiments, R 1 and R 2 are joined with their intervening atoms to form an optionally substituted 5-10 membered heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • one R 1 group is joined with R 2 to form an optionally substituted ring selected from the group consisting of 3-12-membered carbocyclic; 3-12 membered heterocyclyl having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 6-10 membered aryl; and 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • each instance of R 2 and R 3 is hydrogen. In certain embodiments, each instance of R 2 is hydrogen.
  • each instance of R 2 is independently hydrogen or optionally substituted aliphatic. In some embodiments, each instance of R 2 is independently hydrogen or optionally substituted Ci_ 6 aliphatic. In some embodiments, each instance of R 2 is independently hydrogen or optionally substituted Ci_ 3 aliphatic. In some embodiments, each instance of R 2 is independently hydrogen or methyl. In some embodiments, each instance of R 2 is independently hydrogen or trifluoromethyl.
  • R 3 is independently hydrogen or optionally substituted aliphatic.
  • the metal complex is of the formula IV-a:
  • R h is, independently, hydrogen, optionally substituted aliphatic, optionally substituted
  • heteroaliphatic optionally substituted aryl, optionally substituted heteroaryl; and/or two R 11 groups adjacent to each other are joined to form an optionally substituted 5- to 6-membered ring;
  • b is 0 to 5, inclusive.
  • b is 0 to 2. In certain embodiments, b is 0 to 1. In certain embodiments, b is 0. In certain embodiments, b is 1.
  • each instance of R 11 is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl, and/or two R 11 groups adjacent to each other are joined to form an optionally substituted 5- to 6-membered ring.
  • each instance of R 11 is, independently, selected from hydrogen or optionally substituted aliphatic.
  • each instance of R 11 is, independently, selected from hydrogen or optionally substituted heteroaliphatic.
  • each instance of R 11 is, independently, selected from hydrogen or optionally substituted aryl.
  • each instance of R 11 is, independently, selected from hydrogen or optionally substituted heteroaryl.
  • each instance of R 11 is hydrogen.
  • each instance of R 11 is independently selected from hydrogen, optionally substituted aliphatic, or optionally substituted heteroaliphatic. In some embodiments, each instance of R 11 is independently selected from hydrogen or optionally substituted aliphatic. In some embodiments, each instance of R 11 is independently selected from hydrogen or optionally substituted Ci_ 6 aliphatic. In some embodiments, each instance of R 11 is independently selected from hydrogen or optionally substituted Ci_ 3 aliphatic. In some embodiments, each instance of R 11 is independently selected from hydrogen or ethyl. In some embodiments, each instance of R 11 is independently selected from hydrogen or propyl.
  • the present invention also provides methods of making various aliphatic polycarbonate polymers.
  • aliphatic polycarbonate polymers are provided via polymerization of an aliphatic oxide and carbon dioxide (C0 2 ) in the presence of a metal complex, and encompass poly(aliphatic carbonate), as well as polymers which comprise poly(aliphatic carbonate), such as, for example, poly(aliphatic oxide)-co-poly(aliphatic carbonate).
  • the present invention provides a method of synthesizing an aliphatic polycarbonate polymer, the method comprising the step of reacting an aliphatic oxide with carbon dioxide in the presence of a cobalt complex of any of the above described metal complexes of the formula III, or a subset thereof, wherein M is cobalt.
  • the present invention provides a method of synthesizing an aliphatic polycarbonate polymers, the method comprising the step of reacting an aliphatic oxide with carbon dioxide in the presence of a zinc complex of any of the above described metal complexes of the formula IV, or a subset thereof.
  • aliphatic polycarbonate polymers comprising cyclic or polycylic aliphatic oxide monomers are provided using a metal complex of formula IV.
  • aliphatic polycarbonate terpolymers comprising two aliphatic oxide monomers and carbon dioxide are provided using a metal complex of formula IV.
  • aliphatic polycarbonate polymers comprising three or more aliphatic oxide monomers and carbon dioxide are provided using a metal complex of formula IV. While not wishing to be bound by any particular theory, it is believed that the size of the R groups can be modified to afford APCs comprising cyclic and polycyclic monomers with desirable properties ⁇ vide infra).
  • aliphatic polycarbonate polymers comprising cyclic or polycylic aliphatic oxide monomers are provided using a metal complex of formula III.
  • aliphatic polycarbonate terpolymers comprising two aliphatic oxide monomers and carbon dioxide are provided using a metal complex of formula III.
  • aliphatic polycarbonate polymers comprising three or more aliphatic oxide monomers and carbon dioxide are provided using a metal complex of formula III. While not wishing to be bound by any particular theory, it is believed that the size of the R 1 , R 7 , and R 9 groups can be modified to afford APCs comprising cyclic and polycyclic monomers with desirable properties ⁇ vide infra).
  • methods of making an APC of formula I using either a metal complex of formula III or formula IV, or two, three, or more aliphatic oxide monomers produce an APC that is a tapered, block, or random co-polymer.
  • the present invention provide a method of synthesizing an APC of formula I:
  • each R a , R b , R c , and R d are independently selected from hydrogen or optionally substituted Ci_3o aliphatic; or an R a and an R b attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings; or an R b and an R c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings;
  • E and G are, independently, suitable terminating groups
  • j is an integer from about 10 to about 15,000;
  • k is an integer from about 0 to about 2,500;
  • m is the sum of j and k, wherein m is an integer from about 10 to about 17,500.
  • the value of j is greater than the value of k.
  • the ratio of j to k is greater than or equal to about 85 : 1.
  • the ratio of j to k is greater than or equal to about 90: 1.
  • the ratio of j to k is greater than or equal to about 95 : 1.
  • the ratio of j to k is greater than or equal to about 99: 1.
  • a provided APC is substantially free of poly(aliphatic) oxide, and k is 0.
  • the polymer is an alternating polymer of aliphatic oxide and carbon dioxide (e.g.., with regular alternating units an aliphatic oxide and carbon dioxide).
  • the polymer is substantially free of poly(aliphatic) oxide
  • the polymer is an alternating polymer of formula II:
  • R a , R b , R c , R d , E, G, and j are as defined above for formula I.
  • E is hydrogen. In certain embodiments E is a hydroxyl- protecting group. In certain embodiments E is an acyl group. In certain embodiments E is a silyl group. In certain embodiments, G is X, where X is as described above. In certain embodiments, G is a hydroxy 1 group.
  • j is an integer of between about 10,000 to about 15,000, inclusive. In certain embodiments, j is an integer of between about 12,000 to about 15,000, inclusive.
  • the metal complex is a zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese complex.
  • the metal complex is an aluminum complex.
  • the metal complex is a chromium complex.
  • the complex metal is zinc complex.
  • the metal complex is a titanium complex.
  • the metal complex is a ruthenium complex.
  • the metal complex is a manganese complex.
  • the metal complex is cobalt complex.
  • the cobalt metal has a valency of +3 ⁇ i.e., Co(III)).
  • the method further comprises one or more co-catalysts.
  • the present invention encompasses aliphatic polycarbonates (APCs) incorporating monomers having cyclic or polycyclic motifs.
  • APCs aliphatic polycarbonates
  • polymers of the present invention have T g values above
  • the T g value of the polymer is in the range of about 50 to about 120 °C. In some embodiments, the T g value of the polymer is in the range of about 50-70 °C. In other embodiments, the T g value of the polymer is above about 70 °C. In certain embodiments, the T g value of the polymer is between about 70 °C and about 120 °C. In certain embodiments, the T g value of the polymer is between about 80 °C and about 120 °C. In certain embodiments, the T g value of the polymer is between about 90 °C and about 120 °C. In certain embodiments, the T g value of the polymer is between about 100 °C and about 120 °C.
  • polymers of the present invention have average molecular weight numbers (M n ) between about 50,000 and about 300,000 g/mol.
  • M n of the polymer is in the range of about 75,000 to about 250,000 g/mol.
  • the M n of the polymer is in the range of about 75,000 to about 200,000 g/mol.
  • the M n of the polymer is in the range of about 100,000 to about 200,000 g/mol.
  • the M n of the polymer is in the range of about 100,000 to about 150,000 g/mol.
  • the M n of the polymer is in the range of about 75,000 to about 150,000 g/mol.
  • the polydispersity index (PDI) of the polymers is between 1 and about 2. In certain embodiments the PDI of the polymers is less than 1.5. In certain embodiments the PDI of the polymers is less than 1.4. In certain embodiments the PDI of the polymers is less than 1.3. In other embodiments of the present invention, the PDI of the polymers is less than 1.2. In certain embodiments the PDI of the polymers is less than 1.1.
  • the polymer contains less than
  • the polymer contains less than 5 % ether linkages. In certain embodiments, the polymer contains less than 1 % ether linkages. In other embodiments, the polymers are substantially free of ether linkages. In some embodiments, the polymers contain no detectable ether linkages (e.g. as detected bv NMR, IR, or Raman spectroscopy).
  • the polycarbonate compositions decompose at temperatures below about 300 °C. In some embodiments, the polymers decompose essentially completely at temperatures below 300 °C. In other embodiments, the polymers decompose at temperatures below about 250 °C. In certain embodiments of the present invention, the polymers decomposed essentially completely leaving minimal residue. In certain embodiments, the polymers decompose to leave essentially no residue.
  • the present invention provides polymer solutions suitable for spin casting polymer films.
  • the polymer solutions have viscosities ranging from about 10,000 cP to about 100,000 cP.
  • any of the above methods further comprise use of one or more co-catalysts.
  • a co-catalyst is a Lewis base.
  • exemplary Lewis bases include, but are not limited to: N-methylimidazole (N-Melm), dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO), triethyl amine, and diisopropyl ethyl amine.
  • a co-catalyst is a salt.
  • a co- catalyst is an ammonium salt, a phosphonium salt or an arsonium salt.
  • a co-catalyst is an ammonium salt.
  • a co-catalyst is a phosphonium salt.
  • the co-catalyst is an arsonium salt.
  • a co-catalyst is the ammonium salt bis(triphenylphosphoranylidene)ammonium chloride ([PPN]C1).
  • the anion of a salt co-catalyst has the same structure as the ligand X of the above described metal complexes of the formula (III), or subsets thereof, wherein X is a nucleophilic ligand.
  • the co-catalyst is ([PPN]X) or (n-Bu) 4 NX.
  • any of the above methods comprise a ratio of about 500: 1 to about 500,000: 1 of aliphatic oxide to metal complex. In certain embodiments, any of the above methods comprise a ratio of about 500: 1 to about 100,000: 1 of aliphatic oxide to metal complex. In certain embodiments, any of the above methods comprise a ratio of about 500: 1 to about 50,000: 1 of aliphatic oxide to metal complex. In certain embodiments, any of the above methods comprise a ratio of about 500: 1 to about 5,000: 1 of aliphatic oxide to metal complex. In certain embodiments, any of the above methods comprise a ratio of about 500: 1 to about 1,000: 1 of aliphatic oxide to metal complex.
  • any of the above methods comprise aliphatic oxide present in amounts between about 0.5 M to about 20 M. In certain embodiments, aliphatic oxide is present in amounts between about 0.5 M to about 2 M. In certain embodiments, aliphatic oxide is present in amounts between about 2 M to about 5 M. In certain embodiments, aliphatic oxide is present in amounts between about 5 M to about 20 M. In certain embodiments, aliphatic oxide is present in an amount of about 20 M. In certain embodiments, liquid aliphatic oxide comprises the reaction solvent.
  • C0 2 is present at a pressure of between about 30 psi to about 800 psi. . In certain embodiments, C0 2 is present at a pressure of between about 30 psi to about 500 psi. In certain embodiments, C0 2 is present at a pressure of between about 30 psi to about 400 psi. In certain embodiments, C0 2 is present at a pressure of between about 30 psi to about 300 psi. In certain embodiments, C0 2 is present at a pressure of between about 30 psi to about 200 psi. In certain embodiments, C0 2 is present at a pressure of between about 30 psi to about 100 psi.
  • C0 2 is present at a pressure of between about 30 psi to about 80 psi. In certain embodiments, C0 2 is present at a pressure of about 30 psi. In certain embodiments, C0 2 is present at a pressure of about 50 psi. In certain embodiments, C0 2 is present at a pressure of about 100 psi. In certain embodiments, the C0 2 is supercritical.
  • any of the above methods comprise the reaction to be conducted at a temperature of between about 0 °C to about 100 °C. In certain embodiments, the reaction is conducted at a temperature of between about 23 °C to about 100 °C. In certain embodiments, the reaction to be conducted at a temperature of between about 23 °C to about 80 °C. In certain embodiments, the reaction to be conducted at a temperature of between about 23 °C to about 50 °C. In certain embodiments, the reaction to be conducted at a temperature of about 23 °C.
  • reaction step of any of the above methods does not further comprise a solvent.
  • the reaction step of any of the above methods does further comprise one or more solvents.
  • the solvent is an organic solvent.
  • the solvent is a hydrocarbon.
  • the solvent is an aromatic hydrocarbon.
  • the solvent is an aliphatic hydrocarbon.
  • the solvent is a halogenated hydrocarbon.
  • the solvent is an organic ether. In certain embodiments the solvent is a ketone.
  • suitable solvents include, but are not limited to: methylene chloride, chloroform, 1 ,2-dichloroethane, propylene carbonate, acetonitrile, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitromethane, caprolactone, 1,4-dioxane, and 1,3-dioxane.
  • suitable solvents include, but are not limited to: methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, propylene oxide, tetrahydrofuran, monoglyme, triglyme, propionitrile, 1-nitropropane, cyclohexanone.
  • the reaction step of any of the above methods produces cyclic carbonate as a by-product in amounts of less than about 20%. In certain embodiments, cyclic carbonate is produced as a by-product in amounts of less than about 15%. In certain embodiments, cyclic carbonate is produced as a by-product in amounts of less than about 10%>.
  • cyclic carbonate is produced as a by-product in amounts of less than about 5%. In certain embodiments, cyclic carbonate is produced as a by-product in amounts of less than about 1%. In certain embodiments, the reaction does not produce any detectable byproducts (e.g., as detectable by 1H-NMR and/or liquid chromatography (LC)).
  • the aliphatic polycarbonate polymer is a copolymer of units "j" and "k":
  • the aliphatic polycarbonate polymer is a tapered copolymer of units j and k (e.g., wherein the incorporation of k increases or decreases along the length of a given polymer chain.):
  • the aliphatic polycarbonate polymer is a block copolymer of homopolymer units of j and k; the union of the homopolymer subunits may require an intermediate non-repeating subunit, known as a junction block.
  • Block copolymers with two or three distinct blocks are called diblock copolymers and triblock copolymers, respectively.
  • the tapered or block co-polymer of aliphatic polycarbonate is of the formula I:
  • a provided block-co-polymer comprises two or more different aliphatic carbonates.
  • co-polymers include poly(propylene carbonate- co-norbornene carbonate), poly(ethylene carbonate-co-norbornene carbonate), poly(cyclohexene carbonate-co-norbornene carbonate), poly(propylene carbonate-co-limonene carbonate), poly(propylene carbonate-co-carvone carbonate), poly(propylene carbonate-co-carene carbonate- co-limonene carbonate), poly(ethylene carbonate-co-carene carbonate-co-limonene carbonate), and poly(propylene carbonate-co-carene carbonate), to name but a few.
  • Co-polymers comprising two or more different aliphatic carbonates may be provided as tapered, block, and random co-polymers, as defined and described above and herein.
  • the present invention contemplates said co-polymers comprising any of the aliphiatic oxides described above and herein.
  • the present invention provides a method of making a aliphatic polycarbonate block co-polymer, comprising the steps of (i) providing a polyaliphatic oxide polymer, and (ii) reacting the polyaliphatic oxide polymer with ethylene oxide and carbon dioxide in the presence of a metal complex.
  • the metal complex is a metal complex of formula III or IV, or any subset thereof.
  • the polyaliphatic oxide polymer of step (i) is provided by reacting an aliphatic oxide in the presence of a metal complex.
  • the metal complex is a metal complex of formula III or IV, or any subset thereof.
  • block copolymer compositions may be produced by varying or removing the C0 2 pressure during part of the polymerization process.
  • the catalyst When the C0 2 pressure is low or non-existent, the catalyst will produce polymer having a higher degree of ether linkages than when the C0 2 pressure is high.
  • the polymerization may be initiated with any of the metal complexes described above at a relatively high C0 2 pressure (for example, higher than 100 psi, higher than about 200 psi, or higher than about 400psi). These conditions will produce polymer having a predominance of carbonate linkages.
  • the C0 2 pressure is lowered (for example to less than 100 psi, less than 50 psi, or to atmospheric pressure) or is removed completely. These conditions result in new block with more ether bonds being incorporated into the growing polymer chains.
  • the above described process can optionally be repeated one or more times to build diblock, triblock or multiblock polymers. Additionally, several different C0 2 pressure levels can be used in the process to produce polymers with several different block types.
  • the C0 2 pressure is initially low and is then increased.
  • the C0 2 pressure is varied periodically.
  • the C0 2 pressure is varied smoothly over time to form tapered polyether co polycarbonate polymer compositions or blocks with a tapered copolymeric structure.
  • APCs are biocompatible and biodegradable materials with numerous uses ranging from high-performance applications in material science to use as biodegradable consumer packaging.
  • the present invention provides APCs having two carbon atoms separating the carbonate moieties made by the copolymerization of an aliphatic oxide and C0 2 .
  • APCs made from simple epoxides such as ethylene oxide and propylene oxide possess relatively low glass transition temperatures (T g ) that can limit their industrial applicability.
  • T g glass transition temperatures
  • the present invention encompasses the recognition that APCs with higher T g possess greater industrial utility.
  • APCs have desirable properties and find a range of uses.
  • APCs have been used in the manufacture of photoelectric cells, flexible electronic assemblies, display devices, microelecromechanical systems (MEMS) and microstructure technology (MST) devices, fuel cells, batteries, and electrochromic, and photochromic devices.
  • MEMS microelecromechanical systems
  • MST microstructure technology
  • fuel cells fuel cells
  • batteries electrochromic, and photochromic devices.
  • APCs may be preferred for functionality including use as a carrier, a dispersant, or a sacrificial binder.
  • APCs may be preferred for functionality including use as a carrier, a dispersant, a general binder, a sacrificial binder, or a proton conductor.
  • APCs may be preferred for uses including, but not limited to, carrier, dispersant, or sacrificial light- absorbing material.
  • APCs may be preferred for uses including carrier, dispersant, or sacrificial binder.
  • uses of APCs may include use as a proton conductor.
  • uses of APCs may include one or more of the following: carrier, dispersant, general binder, or proton conductor.
  • a I L capacity pressure reactor was charged with catalyst VI (2.23 g, 4.6 mmol) and limonene oxide (300 mL, 1.83 mol 1 :1 mixture of cis and trans isomers).
  • the reaction vessel was pressurized with 100 psi C0 2 and stirred at ambient temperature for 16 hours.
  • the reaction vessel was vented and the polymer was precipitated by pouring the reaction mixture into 1500 mL of vigorously stirred methanol.
  • the mixture was filtered and the filtrate dried to provide 120.8 g of poly(limonene carbonate) with Mn of 12.4 kg/mol and PDI of 1.17.
  • Example 2 is performed under the conditions described for Example 1, except exo-norbornene oxide is used in place of limonene oxide.
  • Example 2a is performed under the conditions described for Example 1, except exo-norbornene oxide is used in place of limonene oxide.
  • Example 2a is performed under the conditions described for Example 1, except exo-norbornene oxide is used in place of limonene oxide and catalyst VII is used in place of catalyst VI.
  • Example 3 is performed under the conditions described for Example 1, except 1- methy cyclopentene oxide is used in place of limonene oxide.
  • Example 3a is performed under the conditions described for Example 1, except 1- methy cyclopentene oxide is used in place of limonene oxide and catalyst VII is used in place of catalyst VI.
  • Example 4 is performed under the conditions described for Example 1, except alpha pinene oxide is used in place of limonene oxide.
  • Example 4a is performed under the conditions described for Example 1, except alpha pinene oxide is used in place of limonene oxide and catalyst VII is used in place of catalyst VI.
  • Example 5 is performed under the conditions described for Example 1, except
  • 3,4-epoxytricyclo(5.2.1.0)-decane is used in place of limonene oxide.
  • Example 5a is performed under the conditions described for Example 1, except
  • 3,4-epoxytricyclo(5.2.1.0)-decane is used in place of limonene oxide and catalyst VII is used in place of catalyst VI.
  • Example 6 is performed under the conditions described for Example 1, except caryophyllene oxide is used in place of limonene oxide.
  • Example 6a is performed under the conditions described for Example 1, except caryophyllene oxide is used in place of limonene oxide and catalyst VII is used in place of catalyst VI.
  • Example 7 is performed under the conditions described for Example 1, except cedrene epoxide is used in place of limonene oxide.
  • Example 7a cedrene epoxide is used in place of limonene oxide.
  • Example 7 is performed under the conditions described for Example 1, except cedrene epoxide is used in place of limonene oxide and catalyst VII is used in place of catalyst VI.
  • reaction vessel 300 mL trans-limonene oxide (1.83 mol), and 12.7 mL propylene oxide (0.18 mol).
  • the reaction vessel is pressurized to 100 psi with C0 2 and stirred at ambient temperature for 16 hours.
  • the reaction vessel is vented and the polymer precipitated by pouring the reaction mixture into 1500 mL of vigorously stirred methanol.
  • the mixture is filtered and the filtrate dried to provide poly(limonene-co-propylene carbonate) .
  • Example 9 is performed under conditions similar to Example 8, except 250 mL limonene oxide is added and 50 mL cyclohexene oxide is used in place of the propylene oxide.
  • the polymers depicted in the Examples are shown as pure aliphatic polycarbonates, it will be understood that provided polymers may be polycarbonate/polyether mixtures, as described above.

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Abstract

La présente invention concerne de nouveaux polymères polycarbonates aliphatiques (APC) provenant de la réaction d'oxydes aliphatiques et de dioxyde de carbone (CO2) en présence d'un complexe métallique, et des procédés de fabrication de ceux-ci. L'invention concerne également des terpolymères incorporant deux oxydes aliphatiques et du dioxyde de carbone. Selon un aspect, l'invention concerne des polymères de formule (I), dans laquelle E, G, Ra, Rb, Rc, Rd, j, k et m sont tels que définis dans la description.
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