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  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
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  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
  • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
  • B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
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  • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
  • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
  • C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
  • C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
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  • B01J2531/0213—Complexes without C-metal linkages
  • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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  • B01J2531/26—Zinc
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Definitions

• the present invention provides a novel catalyst and its use in the co-polymerisation of carbon dioxide and an epoxide.
• Carbon dioxide is an attractive reagent for synthetic chemistry as it is abundant, inexpensive, of low toxicity and the waste product of many chemical processes.
• the copolymerization of carbon dioxide and epoxides known for several decades as illustrated in figure 1, is a particularly promising route to activate and use CO 2 as a renewable C-I source.
• the copolymer has a high glass transition temperature and tensile strength, but is also degradable.
• R 1 and R 2 are independently hydrogen, alkyl, haloalkyl, aryl, halide, amine, a nitro group, an ether group, a silyl ether group, a nitrile group or an acetylide group;
• R 3 is alkylene, arylene or cycloalkylene
• R 4 is H, alkyl, aryl or alkylaryl
• Ei is C, E 2 is O, S or NH or Ei is N and E 2 is O;
• X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 , alkyl, alkoxy, halide or amido;
• M is Zn(II), Co(II), Mn(II), Mg (II), Fe(II), Cr(II), Cr (HI)-X, Co(III)-X, Mn(III)-X or Fe(III)-X.
• an alkyl group is preferably a "Ci -6 alkyl group", that is an alkyl group that is a straight or branched chain with 1 to 6 carbons.
• the alkyl group therefore has 1, 2, 3, 4, 5 or 6 carbon atoms.
• Examples of "Ci -6 alkyl group” include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, l-ethyl-2-methylpropyl group, 1,1,2- trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3- dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3
• a cycloalkyl group is preferably a "C 3-8 cycloalkyl group” that is a cycloalkyl group with 3 to 8 carbon atoms.
• the cycloalkyl group therefore has 3, 4, 5, 6, 7 or 8 carbon atoms.
• examples of the C 3-8 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
• the cycloalkyl group may comprise a cycloalkyl ring bearing one or more linking or non-linking alkyl subsitutents, such as -CH 2 -cyclohexyl.
• halide used herein means a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.
• a haloalkyl group is prefereably a "Ci -6 haloalkyl group” and is a Q -6 alkyl group as described above substituted with 1, 2 or 3 halogen atom(s).
• examples of "Ci- 6 haloalkyl group” include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluroethyl group, trifluoroethyl group, chloromethyl group, bromomethyl group, iodomethyl group and the like.
• An alkoxy group is preferably a "C 1-6 alkoxy group” and is an oxy group that is bonded to the previously defined "C 1-6 alkyl group".
• examples of "Ci -6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n- pentyloxy group, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, iso- hexyloxy group, 1,1-dimethylpropoxy group, 1,2- 1 dimethylpropoxy group, 2,2- dimethylpropoxy group, 2-methylbutoxy group, l-ethyl-2-methylpropoxy group, 1,1,2-trimethylpropoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group,
• An aryl group is preferably a "C 6 - I2 aryl group” and is an aryl group constituted by 6, 7, 8, 9, 10, 11 or 12 carbon atoms and includes condensed ring groups such as monocyclic ring group, or bicyclic ring group and the like.
• examples of "C 6-1 Q aryl group” include phenyl group, biphenyl group, indenyl group, naphthyl group or azulenyl group and the like. It should be noted that condensed rings such as indan and tetrahydro naphthalene are also included in the aryl group.
• alkylaryl group is preferably a "C 1-16 alkyl C 6-12 aryl group" and is an aryl group as defined above bonded at any position to an alkyl group as defined above.
• the alkylaryl group is -CH 2 -Ph or -CH 2 CH 2 -Ph.
• An ether group is preferably a group OR 5 wherein R 5 can be an alkyl group or an aryl group as defined above.
• R 5 is an alkyl group selected from methyl, ethyl or propyl.
• a silyl ether group is preferably a group OSi(Ro) 3 wherein each R 6 can be independently an alkyl group or an aryl group as defined above.
• each R 6 is an alkyl group selected from methyl, ethyl or propyl.
• a nitrile group is preferably a group CN or a group CNR 7 wherein R 7 is an alkyl group or an aryl group as defined above.
• R 7 is an alkyl group selected from methyl, ethyl or propyl.
• R 8 can be an alkyl group or an aryl group as defined above.
• the double bond can be present at any position along the alkyl chain.
• R 8 is methyl, ethyl, propyl or phenyl.
• An acetylide group contains a triple bond -C ⁇ C-Rg, wherein R 9 can be an alkyl group or an aryl group as defined above.
• R 9 can be an alkyl group or an aryl group as defined above.
• the triple bond can be present at any position along the alkyl chain.
• R 9 is methyl, ethyl, propyl or phenyl.
• An amino group is preferably NH 2 , NHR 1O or N(Rio) 2 wherein Rio can be an alkyl group, a silylalkyl group or an aryl group as defined above. It will be appreciated that when the amino group is N(R 10 ) 2 , each Ri 0 group can be independently selected from an alkyl group, a silylalkyl group or an aryl group as defined above.
• R 10 is methyl, ethyl, propyl, SiMe 3 Or phenyl.
• An amido group is -NR 11 C(O)- Or -C(O)-NRu- wherein R 11 can be hydrogen, an alkyl group or an aryl group as defined above.
• R 11 is hydrogen, methyl, ethyl, propyl or phenyl.
• R 1 and R 2 may be the same or different.
• R 1 and R 2 are preferably independently selected from hydrogen, tBu, Me, CF 3 , phenyl, F, Cl, Br, I, NMe 2 , NEt 2 , NO 2 , OMe, OSiEt 3 , CNMe, CN or CCPh, more preferably hydrogen, OMe, Me or tBu (e.g. hydrogen or tBu).
• R 2 is hydrogen and Ri is any one of the groups defined above, preferably tBu, OMe or Me.
• R 3 is a disubstituted alkyl, aryl or cycloalkyl group which acts as a bridging group between two nitrogen centres in the catalyst of formula (I).
• R 3 is a alkylene group, such as dimethylpropylene
• the R 3 group has the structure -CH 2 -C(CH 3 ) 2 -CH 2 -.
• the definitions of the alkyl, aryl and cycloalkyl groups set out above therefore also relate respectively to the alkylene, arylene and cycloalkylene groups set out for R 3 .
• R 3 is ethylene, 2,2- dimethylpropylene, propylene, butylene, phenylene, cyclohexylene or biphenylene, more preferably 2,2-dimethylpropylene.
• R 3 is cyclohexylene, it can be the racemic, RR- or SS- forms.
• R 4 is H, Me, Et, Bn, iPr, tBu or Ph, more preferably hydrogen.
• X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 , Et, Me, PhOEt, OMe, OiPr, OtBu, Cl, Br, I, F, N(iPr) 2 or N(SiMe 3 ) 2, , more preferably OCOCH 3 .
• M is Zn(II), Cr(III), Cr(II), Co(III), Co(II), Mn(III), Mn(II), Mg (II), Fe(II) or Fe(III), more preferably Zn(II), Cr(III), Co(II), Mn(II), Mg(II), Fe(II) or Fe(III), and most preferably Zn(II) or Mg(II).
• the catalyst of formula (I) will contain an additional X group co-ordinated to the metal centre, wherein X is as defined above.
• a catalyst selected from:
• a catalyst of formula (I) of the first aspect of the invention may be prepared by complexation of a ligand (for example H 2 L 1 , H 2 L 2 or H 2 L 3 , where L 1 , L 2 or L are as represented within the structures shown above) with a metal complex comprising the groups M and X. Carrying out this complexation in the presence of water where X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide may lead, in addition to the formation of a catalyst of formula (I), to the formation of a dimeric catalyst species comprising two catalyst complexes of formula (I), linked by a bridging ligand X, with a bound water molecule.
• a ligand for example H 2 L 1 , H 2 L 2 or H 2 L 3 , where L 1 , L 2 or L are as represented within the structures shown above
• a metal complex comprising the groups M and X. Carrying out this complexation in the presence of
• the invention provides a dimeric catalyst formed from two of the same monomelic subunits and a bound water molecule, wherein each monomelic subunit is a catalyst of formula (I) of the first aspect of the invention wherein X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide, and wherein the two monomelic subunits are linked by a bridging ligand X.
• the bridging group X may bridge between one M of each monomelic subunit, with a water molecule being bound to an M of one monomelic subunit.
• Each monomelic subunit of formula (I) which forms the dimeric complex has the same structure (i.e. each subunit has the same group at the R 1 , R 2 , R 3 , R 4 , Ei, E 2 and M positions, respectively).
• the dimeric catalyst of the second aspect can be illustrated by the formula (II):
• X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide.
• X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 or OSO(CH 3 ) 2 and more preferably OCOCH 3 .
• M is preferably Zn(II) or Mg(II), more preferably Mg(II).
• a ligand for example H 2 L 1 , H 2 L 2 or H 2 L 3
• a metal complex comprising the groups M and X
• the product formed may be a mixture of the catalyst of formula (I) of the first aspect and the dimeric catalyst of the second aspect of the invention, wherein X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide.
• a third aspect of the invention provides a mixture of the catalytic species of the first aspect and the second aspect of the invention.
• the fourth aspect of the invention provides a process for the reaction of carbon dioxide with an epoxide in the presence of a catalyst of the first aspect, the second aspect or the third aspect of the invention.
• the epoxide substrate is not limited.
• the term epoxide therefore relates to any compound comprising an epoxide moiety.
• Preferred examples of epoxides for the purposes of the present invention include cyclohexene oxide, propylene oxide, substituted cyclohexene oxides (such as limonene oxide, C 10 Hi 6 O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
• alkylene oxides such as ethylene oxide and substituted ethylene oxides
• substituted oxiranes such as epichlorohydrin, 1,2-epoxybutane, glycidyl ethers
• the process of the fourth aspect of the invention is particularly provided for the reaction of carbon dioxide with an epoxide at low pressures.
• the reaction can therefore be carried out at a pressure of 1 to 10 atmospheres, preferably at 1 or 2 atmospheres.
• the process of the fourth aspect of the invention can be carried out at a temperature of 50°C to 100°C.
• the duration of the process can be up to 48 hours preferably 20 to 24 hours.
• the process of the fourth aspect of the invention can advantageously be carried out at low catalytic loading, for example, the catalytic loading for the process is preferably in the range of 1: 1000-10000 catalyst.epoxide, more preferably in the region of 1:1000 catalyst:epoxide, and most preferably in the region of 1:10000 catalyst:epoxide.
• the present invention provides a bimetallic catalytic complex and allows the reaction of epoxides with carbon dioxide with high turn over numbers and turn over frequencies.
• the catalysts of the present invention operate at remarkably low pressure, e.g. 1 atm of CO 2 . Indeed, the catalysts show comparable TON and TOF to literature catalysts but operate at 1/60 of the pressure of CO 2 .
• the fifth aspect of the invention provides a product of the process of the fourth aspect of the invention.
• the sixth aspect of the invention provides a process for the production of a catalyst of the first aspect of the invention, said process comprising reaction of a compound of formula (III)
• the number of the groups X present in the metal complex will depend on the valency of the metal M.
• M is Zn(II) and X is OAc
• the metal complex will be Zn(OAc) 2 .
• the metal complex may have the formula M-XH.
• the reaction of the compound of formula (III) with a metal complex can be carried out in the presence or absence of a base.
• the base can be selected from one or more of an amine base, such as Et 3 N or a hydride base, such as NaH, LiH or KH.
• the reaction of the compound of formula (III) with a metal complex can be carried out in a solvent (for example THF, toluene, dichloromethane or methanol).
• a solvent for example THF, toluene, dichloromethane or methanol.
• the solvent is preferably anhydrous.
• the process is carried out under anhydrous conditions and preferably the metal complex is anhydrous.
• a process as defined in the sixth aspect of the invention may be used to produce a catalyst of the second or third aspect of the invention, wherein X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide, by the inclusion of water within the reaction, for example by providing a metal complex which is not completely anhydrous.
• the seventh aspect of the invention provides a ligand as illustrated below:
• the ligand of the seventh aspect of the invention is provided for use in the production of a catalyst of the first, second or third aspects of the invention.
• the seventh aspect of the invention therefore further provides a process for the production of a catalyst of the first aspect of the invention, said process comprising reaction of the ligand of the seventh aspect of the invention with a metal complex comprising the groups M and X as defined in the first aspect of the invention.
• the seventh aspect of the invention yet further provides a process for the production of a catalyst of the second or third aspects of the invention, said process comprising reaction of the ligand of the seventh aspect of the invention with a metal complex comprising the groups M and X, wherein X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide, wherein the reaction is carried out in the presence of water, for example by providing a metal complex which is not completely anhydrous.
• the process for the production of a catalyst of the first, second or third aspects of the invention is carried out in a solvent (for example THF, toluene, dichloromethane or methanol), preferably wherein the solvent is anhydrous.
• a solvent for example THF, toluene, dichloromethane or methanol
• the process for the production of a catalyst of the first, second or third aspects of the invention may be carried out in the presence of KH.
• the metal complex is preferably Zn(OAc) 2 or Mg(OAc) 2 .
• Figure 2 shows the synthesis of the dizinc complex [L 1 Zn 2 (OAc) 2 ].
• Reagents and conditions i) KH, THF, -78 0 C ⁇ RT, 1 hour, ii) Zn(OAc) 2 , THF, RT, 16 hours.
• Figure 3 shows a plot showing the M n of the polycarbonate, as determined by GPC, versus the percentage conversion, as determined by 1 H NMR.
• the values in parentheses represent the polydispersity index
• Figure 4 shows a 1 H NMR spectrum, at 110 0 C of the dizinc complex [L 1 Zn 2 (OAc) 2 ].
• Figure 5 shows an X-ray crystallography structure for the dimeric catalyst complex [L 1 Z Mg 4 (OAc) 4 (H 2 O)]
• the tert-butyl and acetate methyl groups resonate as singlets with integrals of 18H and 6H, respectively.
• the methyl groups on the ligand backbone are also diastereotopic and are observed as two singlets, each with a relative integral of 6H. 0
• the complex was tested, under very mild conditions, for the copolymerization of carbon dioxide and cyclohexene oxide as illustrated in figure 1. Results of the copolymerization are set out in table 1 below. Thus, at only 1 atm pressure of carbon dioxide and at 70 0 C, poly(cyclohexene carbonate) was produced with a TON of 300 and a TOF of 12 h "1 .
• the catalyst is also selective, yielding a polymer with >99% polycarbonate linkages.
• [L 1 Zn 2 (OAc) 2 ] is remarkably robust, it is still active after 24 h of reaction and at loadings of 0.01 mol%. It is also stable in air; indeed comparable TONs and TOFs are obtained for polymerizations when
• H 2 L 1 (0.40 g, 0.72 mmol) was dissolved in dry THF (10 mL) and transferred into a Schlenk tube containing KH (0.04 g, 1.08 mmol), and cooled to -78 0 C, under nitrogen. This suspension was allowed to warm to room temperature and left to stir for 1 hour. The excess KH was filtered off and the solution transferred to a Schlenk tube containing Zn(OAc) 2 (0.27 g, 1.48 mmol). The reaction was left to stir for 16 hours overnight, after which the THF was removed in vacuo, and the product taken up in dry CH 2 Cl 2 (10 mL). This was then filtered and the CH 2 Cl 2 removed in vacuo to yield the title compound as a white powder (0.40 g, 69.5 %).
• Cyclohexene oxide (5 mL, 49.4 mmol) and [L 1 Zn 2 (OAc) 2 ] (0.049 mmol) were added to a Schlenk tube.
• the cyclohexene oxide was degassed, before being left stirring under 1 atm CO 2 , at a certain temperature, for 24 hours.
• the crude reaction mixture was then taken up in CH 2 Cl 2 and evaporated in air, after which the product was dried in vacuo overnight.
• the dimeric structure is formed due to the presence of an impurity of water during the complexation of the macrocyclic ligand H 2 L 1 with Mg(OAc) 2 .
• Mg(OAc) 2 is not commercially available in anhydrous form.
• Commercially available Mg(OAc) 2 '4H 2 O was dried under vacuum at 100°C, prior to use in the complexation reaction. It has been found that this drying was insufficient to remove all of the water, and therefore provides a source of water to allow the formation of a dimeric complex.
• catalyst complexes of formula (I) of the present invention may form a dimeric structure or mixture of monomer and dimer where catalyst synthesis is carried out in the presence of water. Dimer formation is avoided when the synthesis is anhydrous.
• Table 4 Comparison of [L Zn 2 (OAc) 2 ] and magnesium complex activities for copolymerization of cyclohexene oxide and CO 2 .
• [L 1 Mg 2 (OAc) 2 ] represents a mixture of [L 1 Mg 2 (OAc) 2 ] and FlJ 2 Mg 4 (OAc) 3 (H 2 O)].
• the molar catalyst loading is 1: 1000 (catalyst.epoxide) at 1 atm CO 2 and 1:10000 (catalyst:epoxide) at 10 atm CO 2 .
• the magnesium catalyst mixture shows a TOF of almost 34 h 1 at 80 0 C and 1 atm CO 2 , this value increases to almost 97 h "1 when the temperature is increased to 100 °C (entries 2 and 4). If the pressure is increased to 10 atm, the activity is increased further still (entry 6). In addition, there is no evidence for the formation of any cyclic carbonate in the 1 H NMR spectra. This is observed for all copolymerisations using the magnesium catalyst and is very unusual, as the formation of cyclic carbonate is generally held to be under thermodynamic control, increasing with temperature.
• the polymer properties are very similar to those produced by [L 1 Zn 2 (OAc) 2 ], with similar polydispersities, molecular weights and no observable ether linkages.
• H 2 L 1 (0.40 g, 0.72 mmol) was dissolved in dry THF (10 mL) in a Schlenk tube The solution was transferred to another Schlenk tube containing Mg(OAc) 2 (0.21 g, 1.48 mmol). The reaction was left to stir for 16 hours overnight, after which the THF was removed in vacuo, and the product taken up in dry CH 2 Cl 2 (10 mL). The solution was then filtered, the solvent removed in vacuo and the white powdery product dried under vacuum overnight.

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