PROCESS FOR THE SYNTHESIS OF A POLYCARBONATE, POLYMERIZATION SYSTEM, AND METHOD TO PRODUCE THE COPOL

专利摘要:
PROCESS FOR THE SYNTHESIS OF A POLYCARBONATE; POLYMERIZATION SYSTEM FOR THE COPOLIMERIZATION OF CARBON DIOXIDE AND AT LEAST ONE EPOXIDE; POLYCARBONATE; COPOLYMER OF FORMULA B (A) n; METHOD OF PRODUCTION OF COPOLYMER AND CATALYST. The invention provides a process for the synthesis of a polycarbonate, the process comprising the step of reacting carbon dioxide with at least one epoxide in the presence of a catalyst of formula (I) and a chain transfer agent. The invention also provides a polymerization system for the copolymerization of carbon dioxide and at least one epoxide comprising a catalyst of formula (I) and a chain transfer agent, polycarbonates produced by the inventive process, a block copolymer comprising a polycarbonate produced by the inventive process and a method of producing it. The invention also relates to innovative catalysts of the formula (III).
公开号:BR112014005182B1
申请号:R112014005182-8
申请日:2012-09-07
公开日:2021-02-02
发明作者:Charlotte Williams；Michael Kember；Antoine Buchard；Fabian Jutz
申请人:Imperial Innovations Limited；
IPC主号:

专利说明:

TECHNICAL FIELD
[0001] The present invention relates to a process for the synthesis of a carbon dioxide polycarbonate and an epoxide, in the presence of a bimetallic catalyst and a chain transfer agent. BACKGROUND OF THE INVENTION
[0002] Environmental and economic concerns associated with a depletion of oil resources have triggered a growing interest in the chemical conversion of carbon dioxide (CO2), in order to allow its use as a renewable carbon source. CO2 is, despite its low reactivity, a very attractive carbon raw material, since it is inexpensive, virtually non-toxic, abundantly available in high purity and non-hazardous. Therefore, CO2 can be a promising substitute for substances such as carbon monoxide or phosgene in many processes. One of the applications in CO2 development is copolymerization with epoxides to yield aliphatic polycarbonates, a field initiated by Inoue et al. more than 40 years ago (Inoue, S. et al, J. Polym. Sci., Part B: Polym. Lett. 1969, 7, p. 287).
[0003] In patent document WO2009 / 130470, the contents of which are incorporated into this document as a reference in its entirety, the copolymerization of an epoxide with CO2 with the use of a catalyst of a class represented by formula (I) was described:

[0004] Among the epoxides used in cyclohexene (CHO) received one that the product cyclohexene polycarbonate (PCHC) shows a high glass transition temperature and a reasonable resistance to tension. Propylene oxide has also received interest as it produces a polymer (polypropylene carbonate, known as PPC) with elastomeric properties that are useful in film applications. Kember et al (Angew. Chem., Int. Ed., 2009, 48, page 931 and Inorg. Chem., 2009, 48, page 9,535) recently reported an air-stable zinc acetate complex, coordinated by a macrocyclic ligand, present in formula (I) above, which shows a high catalytic activity, even at an ambient CO2 pressure. The catalyst exhibits excellent copolymerization selectivity, which results in high proportions of carbonate repeating units and low yields of cyclic cyclohexane carbonate (CHC) by-product. The zinc acetate complex is a rare example of a catalyst that is capable of high activity at ambient pressure (0.1 MPa (1 bar)) of CO2, yielding moderate molecular weight PCHC, with a narrow polydispersity index ( PDI) and achieves remarkably high turnover numbers (TON).
[0005] Polycarbonates such as PCHC or PPC are useful for building blocks in the preparation of various copolymeric materials. The polycarbonates produced by copolymerizing an epoxide with carbon dioxide using a catalyst of the class represented by formula (I) are generally terminated at one end with at least one hydroxyl group and at the other end by a group corresponding to one linker X. In order to use these polycarbonates in order to build blocks in the formation of, for example, block copolymers, it is desirable that the entire termination be hydroxyl groups. In a linear polycarbonate, for example, this can allow a direct coupling of additional polymer blocks to the ends of the polycarbonate, or growth of an additional polymer from the ends, that is, through ring opening polymerization, initiated by the terminal hydroxyl groups. Thus, the steps of purifying / collecting additional information may be necessary to replace terminal X groups with hydroxy groups. A method for producing polycarbonates that are terminated with hydroxy groups, which avoids the need for purification / information gathering steps is desirable and it has been determined that this can be achieved through the use of a chain transfer agent (CTA) during polymerization CO2 with an epoxide. SUMMARY
[0006] A process for the synthesis of a polycarbonate is provided through the first aspect of the invention, the process comprising the step of reacting carbon dioxide with at least one epoxide in the presence of a catalyst of the formula (I):

[0007] wherein R1 and R2 are independently hydrogen, halo, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl ether group, or an acetylide group or an alkyl, alkenyl, alkynyl, aryl , optionally substituted heteroaryl, alicyclic or heteroalicyclic;
[0008] R3 is alkylene, alkenylene, alkynylene, heteroalkenylene, heteroalkenylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkynylene optionally substituted can be optionally interrupted by aryl, heteroaryl, or alicylic;
[0009] R4 is H, or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0010] R5 is H, or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0011] E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
[0012] X is OC (O) Rx, OSO2Rx, OSO (Rx) 2, OS (O) Rx, ORx, phosphinate, halo, nitrate, hydroxyl, carbonate, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl optionally replaced;
[0013] Rx is independently hydrogen, aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, arylalkyl or optionally substituted heteroaryl;
[0014] each G is independently absent or a neutral or anionic donor ligand which is a Lewis base;
[0015] M is Zn (II), Cr (II), Co (II), Mn (II), Mg (II), Fe (II), Ti (II), Cr (III) -X, Co (III ) -X, Mn (III) -X, Fe (III) -X, Ca (II), Ge (II), Al (III) -X, Ti (III) -X, V (III) -X, Ge (IV) - (X) 2 or Ti (IV) - (X) 2;
[0016] and a chain transfer agent selected from water or a compound of formula (II):
[0017] Z (W) n (II)
[0018] where
[0019] Z is an optionally substituted chemical moiety selected from the group consisting of aryl, heteroaryl, polyolefin, polyester, polyether, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic polycarbonate or combinations thereof,
[0020] each W is independently selected from a hydroxyl, amine, thiol or carboxylate group, and
[0021] n is an integer that is at least 1.
[0022] The second aspect of the invention provides a polymerization system for the copolymerization of carbon dioxide and at least one epoxide comprising a catalyst as defined in the first aspect, and a chain transfer agent as defined in the first aspect.
[0023] The third aspect of the invention provides a polycarbonate as produced by the process of the first aspect of the invention.
[0024] The fourth aspect of the invention provides a block copolymer of formula B (- A) n, where B is a polycarbonate produced by the process of the first aspect of the invention and A is a polymeric unit that differs in structure from B.
[0025] The fifth aspect of the invention provides a method for producing the block copolymer of the fourth aspect, which comprises the steps of synthesizing a polycarbonate according to the process of the first aspect and either reacts the polycarbonate with at least one additional monomer, or react the polycarbonate with at least one additional polymeric unit.
[0026] In a sixth aspect of the invention, a catalyst of formula (III) is provided:

[0027] wherein R1 and R2 are independently hydrogen, halo, a nitro group, a nitrile group, an imine an amine, an ether group, a silyl ether group or an acetylide or alkyl group, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alicyclic or optionally substituted heteroalicyclic;
[0028] R3 is optionally substituted alkylene, alkenylene, alkylene, heteroalkenylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkenylene can optionally be interrupted by aryl, heteroalkenic ;
[0029] R4 is H, or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0030] R5 is H, or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0031] E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
[0032] each G is independently absent or a neutral or anionic donor ligand which is a Lewis base;
[0033] M is Zn (II), Co (II), Mn (II), Mg (II), Fe (II), Cr (II), Ti (II), Cr (III) -X, Co (III ) -X, Mn (III) -X, Fe (III) -X, Ca (II), Ge (II), Al (III) -X, Ti (III) -X, V (III) -X, Ge (IV) - (X) 2 or Ti (IV) - (X) 2;
[0034] where when both cases of G are absent and all cases of R5 are hydrogen, X is OC (O) RZ, OSO (RZ) 2, OSO2RY, OS (O) RT, ORV, phosphinate, hydroxyl, optionally substituted carbonate, nitrate or aryl, heteroaryl, alicyclic or heteroalicyclic;
[0035] RZ is independently hydrogen or aliphatic C2-20, haloaliphatic C2-20, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or optionally substituted heteroaryl;
[0036] RY is hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl optionally substituted with the proviso that RY is not C7H7; and
[0037] RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroalicyclic;
[0038] RT is hydrogen, or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or optionally substituted heteroaryl; and where when one or both of the G cases are not absent, or one or more R5 is not hydrogen, X is OC (O) Rx, OSO2Rx, OSO (Rx) 2, OS (O) Rx, ORx, phosphinate, optionally substituted halo, nitrate, hydroxyl, carbonate, starch, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; and
[0039] Rx is independently hydrogen or aryl, alkylaryl or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, optionally substituted heteroalicyclic. BRIEF DESCRIPTION OF THE DRAWINGS
[0040] The modalities of the invention are described below by way of example and with reference to the attached drawings in which:
[0041] Figure 1 shows the molecular structure of [L1Mg2Cl2 (dimethylaminopyridine)].
[0042] Figure 2 shows the 1H NMR spectrum of [L1Mg2Cl2 (methylimidazole)]
[0043] Figure 3 shows the 1H NMR spectrum of [L1Mg2Br2 (dimethylaminopyridine)].
[0044] Figure 4 shows the 1H NMR spectrum of [L1Zn2 (O2CCF3) 2] in CDCl3.
[0045] Figure 5 shows the LSIMS spectrum of [L1Zn2 (OOCC (CH3) 3) 2].
[0046] Figure 6 shows the molecular structure of [L1Co2Cl3] [HNEt3].
[0047] Figure 7 shows the molecular structure of [L1Co2Cl2 (methylimidazole)].
[0048] Figure 8 shows the MALDI-TOF MS spectrum of the polycarbonate produced by [L1Co2 (OAc) 3] and 10 ethylene glycol equivalents as CTA.
[0049] Figure 9 shows the overlapping GPC traces of HO-PCHC-OH from ethylene glycol (Mn = 2,000) and PLA-PCHC-PLA (Mn = 30,400).
[0050] Figure 10 shows the 1H NMR spectrum of PCHC produced by [L1Zn2 (O2CCF3) 2]. Peak A is designed for polycarbonate bond methyl protons. The B peaks are designated for methion protons of the terminal hydroxyl end group. Peak C is assigned to the cyclic carbonate by-product CHC. A D peak is assigned to the methane protons of other bonds. An E peak is assigned to an unreacted CHO.
[0051] Figure 11 shows the MHCDI-TOF MS spectrum of PCHC produced by [L1Zn2 (O2CCF3) 2], which shows the polymer series [HO (C7H10O3) nC6H11O2] Li +. [17.01 + (142.15) n + 99.15 + 6.9].
[0052] Figure 12 shows the overlapping 1H NMR spectrum of PCHC (blue) and PLA-PCHC-PLA (red), which shows bonding and terminal methin-cyclohexane protons.
[0053] Figure 13 shows the overlapping GPC traces of PCHC (Mn = 9,100) and PLA-PCHC-PLA (Mn = 51,000) against narrow polystyrene patterns in THF.
[0054] Figure 14 shows the precipitated 1H NMR spectrum of PLA-PCHC-PLA (PCHC Mn = 9,000, 400 PLA equiv., PLA-PCHC-PLA Mn = 51,000).
[0055] Figure 15 shows the molecular weight distributions, determined using SEC, for PCHC produced by catalysts [L1Mg2 (OAc) 2] and [L1Mg2 (OCOCF3) 2] (catalysts 2a and 2c, respectively) in the presence of water. DEFINITIONS
[0056] For the purpose of the present invention, an aliphatic group is a chemical portion of hydrocarbon that can be a straight or branched chair and can be completely saturated, or contains one or more unsaturation units, but which is not aromatic. The term "unsaturated" means a chemical moiety that has one or more double and / or triple bonds. The term "aliphatic" is therefore intended to include alkyl, alkenyl or alkynyl groups and combinations thereof. An aliphatic group is preferably a C1-20 aliphatic group, which is an aliphatic group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an aliphatic group is a C1-15 aliphatic group, more preferably a C1-12 aliphatic, more preferably a C1-10 aliphatic, even more preferably a C1-8 aliphatic, such as a C1-6 aliphatic group.
[0057] An alkyl group is preferably a "C1-20 alkyl group", which is an alkyl group that is a straight or branched chain with 1 to 20 carbons. The alkyl group therefore has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alkyl group is C1-15 alkyl, preferably C1-12 alkyl, more preferably C1-10 alkyl, even more preferably C1-8 alkyl, even more preferably C1-6 alkyl. In certain embodiments, an alkyl group is a "C1-6 alkyl group", which 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. Specifically, examples of "C1-20 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, group n -pentyl, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, group n -pentadecyl, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, group 1- ethylpropyl, n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, group 1,2-dimethylbutyl, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group and the like. The alkenyl and alkynyl groups are preferably "C2-20 alkenyl" and "C2-20 alkynyl" groups, more preferably "C2-15 alkenyl" and "C2-15 alkenyl", even more preferably "C2-12 alkenyl" and "alkynyl" C2-12 ”, even more preferably“ C2-10 alkenyl ”and“ C2-10 alquinyl ”, even more preferably“ C2-8 alkenyl ”and“ C28- alkynyl ”, most preferably“ C2-6 alkenyl ”and“ C2 alkynyl ” -6 ”respectively.
[0058] A heteroaliphatic group is an aliphatic group as described above, which additionally contains one or more heteroatoms. Heteroaliphatic groups, therefore, preferably contain from 2 to 21 atoms, preferably from 2 to 16 atoms, more preferably from 2 to 13 atoms, more preferably from 2 to 11 atoms, more preferably from 2 to 9 atoms, even more preferably from 2 to 7 atoms, where at least one atom is a carbon atom. Particularly preferred heteroatoms are selected from O, S, N, P and Si. When heteroaliphatic groups have two or more heteroatoms, the heteroatoms can be the same or different.
[0059] An alicyclic group is a cyclic saturated or partially saturated monocyclic or polycyclic aliphatic ring system (which includes fused, bridged and spiral fused) that has 3 to 20 carbon atoms, which is an alicyclic group with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alicyclic group has 3 to 15, more preferably 3 to 12, even more preferably 3 to 10, even more preferably 3 to 8 carbon atoms. The term "alicyclic" encompasses cycloalkyl, cycloalkenyl and cycloalkynyl groups. It will be appreciated that the alicyclic group can comprise an alicyclic ring which carries one or more alkyl bonding or non-bonding substituents, such as -CH2-cyclohexyl.
[0060] The cycloalkyl, cycloalkenyl and cycloalkynyl groups have 3 to 20 carbon atoms. The cycloalkyl, cycloalkenyl and cycloalkynyl groups therefore have 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. The cycloalkyl, cycloalkenyl and cycloalkynyl groups preferably have 3 to 15, more preferably 3 to 12, even more preferably 3 to 10, even more preferably 3 to 8 carbon atoms. When an alicyclic group has 3 to 8 carbon atoms, it means that the alicyclic group has 3, 4, 5, 6, 7 or 8 carbon atoms. Specifically, examples of the C3-20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and cyclooctyl.
[0061] A heteroalicyclic group is an alicyclic group as defined above that has, in addition to carbon atoms, one or more ring heteroatoms, which are preferably selected from O, S, N, P and Si. The heteroalicyclic groups preferably contain from one to four heteroatoms, which can be the same or different. The heterocyclic groups preferably contain from 5 to 20 atoms, more preferably from 5 to 14 atoms, even more preferably from 5 to 12 atoms.
[0062] An aryl group is a monocyclic or polycyclic ring system that has 5 to 20 carbon atoms. An aryl group is preferably a "C6-12 aryl group" and is an aryl group consisting of 6, 7, 8, 9, 10, 11 or 12 carbon atoms and includes condensed ring groups such as a monocyclic ring group or a group of bicyclic ring and the like. Specifically, examples of "C6-10 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 indane and tetrahydro naphthalene are also included in the aryl group.
[0063] A heteroaryl group is an aryl group that has, in addition to carbon atoms, from one to four ring heteroatoms that are preferably selected from O, S, N, P and Si. A heteroaryl group preferably has from 5 to 20 , more preferably 5 to 14 ring atoms. Specifically, examples of a heteroaryl group include pyridine, imidazole, N-methylimidazole and 4-dimethylaminopyridine.
[0064] Examples of alicyclic, heteroalicyclic, aryl, and heteroaryl groups include, but are not limited to, cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazol, cinoline, dioxin, dioxane, dioxolane, ditano, ditane , dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, naphthyridine, oxazole, oxadiazole, oxathiazine, oxazazine, phenylazoxin , phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, , thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazine, triazole and tritian.
[0065] The terms "halo" or "halogen" are used interchangeably and as used herein means a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably an atom fluorine, a bromine atom or a chlorine atom, and more preferably a fluorine atom or a bromine atom.
[0066] A haloalkyl group is preferably a "C1-20 haloalkyl group", more preferably a "C1-15 haloalkyl group", more preferably a "C1-12 haloalkyl group", more preferably a "C1-10 haloalkyl group", even more preferably a "C1-8 haloalkyl group", even more preferably a "C1-6 haloalkyl group" and it is a C1-20 alkyl, a C1-15 alkyl, a C1-12 alkyl, a C1-10 alkyl, a C1-8 alkyl or a C1-6 alkyl group, respectively, as described above substituted with at least one halogen atom, preferably 1, 2 or 3 halogen atom (s). Specifically, examples of "C1-20 haloalkyl group" include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, chloromethyl group, bromomethyl group, iodomethyl group and the like.
[0067] An alkoxy group is preferably a "C1-20 alkoxy group", more preferably a "C1-15 alkoxy group", more preferably a "C1-12 alkoxy group", more preferably a "C1-10 alkoxy group", even more preferably a "C1-8 alkoxy group", even more preferably a "C1-6 alkoxy group" and it is an oxy group which is attached to the C1-20 alkyl, C1-15 alkyl, C1-12 alkyl, C1 alkyl group -10, C1-8 alkyl or C1-6 alkyl previously defined, respectively. Specifically, examples of a "C1-20 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, isohexyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-e group 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 2,2-dimethylpropoxy group, 2-methylbutoxy group, 1-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, 1,3-dimethylbutoxy group, 2-ethylbutoxy group, 2-methylpentyloxy group, 3-methylpentyloxy group and the like.
[0068] An alkylthio group is preferably a "C1-20 alkylthio group", more preferably a "C1-15 alkylthio group", more preferably a "C1-12 alkylthio group", more preferably a "C1-10 alkylthio group", even more preferably a "C1-8 alkylthio group", even more preferably a "C1-6 alkylthio group" and it is a thiol group (-S-) which is attached to the C1-20 alkyl, C1-15 alkyl, C1 alkyl group -12, C1-10 alkyl, C1-8 alkyl or C1-6 alkyl previously defined, respectively.
[0069] An alkylaryl group is preferably a "C6-12 C1-20 alkyl aryl group", more preferably a "C6-12 C1-16 alkyl aryl group", even more preferably a "C6-12 aryl C1-6 alkyl group" ”And is an aryl group as defined above attached in any position to an alkyl group as defined above. The point of attachment of the alkylaryl group to a molecule can be through the alkyl moiety and therefore, preferably, the alkylaryl group is -CH2-Ph or -CH2CH2-Ph. An alkylaryl group can also be called "aralkyl".
An ether group is preferably an OR5 group in which R5 can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R5 can be an aliphatic, alicyclic or unsubstituted aryl. Preferably, R5 is an alkyl group selected from methyl, ethyl or propyl. A thioether group is preferably an SR5 group where R5 is as defined above.
[0071] A silyl group is preferably a -Si (Rδ) 3 group, where each R6 can independently be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R6 is independently an aliphatic, alicyclic or unsubstituted aryl. Preferably, each R6 is an alkyl group selected from methyl, ethyl or propyl.
[0072] A silyl ether group is preferably an OSi (R6) 3 group in which each R6 can independently be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R6 may independently be an aliphatic, alicyclic or unsubstituted aryl. Preferably, each R6 is an alkyl group selected from methyl, ethyl or propyl.
[0073] A nitrile group is a CN group.
[0074] An imine group is a -CRNR group, preferably a -CHNR7 group in which R7 is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R7 is aliphatic, alicyclic or unsubstituted aryl. Preferably R7 is an alkyl group selected from methyl, ethyl or propyl.
An acetylide group contains a triple bond -C = C-R9, preferably where R9 can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. For the purposes of the invention when R9 is alkyl, the triple bond can be present at any position along the alkyl chain. In certain embodiments, R9 is aliphatic, alicyclic or unsubstituted aryl. Preferably R9 is methyl, ethyl, propyl or phenyl.
An amino group is preferably -NH2, -NHR10 or -N (R10) 2 where R10 can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, silyl, aryl or heteroaryl group as defined above. It will be appreciated that when the amino group is N (R10) 2, each R10 group can be independently selected from an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic group, a silylalkyl, heteroaryl or aryl group as defined above. In certain embodiments, each R10 is independently an unsubstituted aliphatic, alicyclic or aryl. Preferably R10 is methyl, ethyl, propyl, SiMe3 or phenyl. Wherein W of the chain transfer agent is amine, the amine being preferably NH2 or NHR10.
[0077] An alkylamino group can be a group - NHR10 or -N (R10) 2 as defined above.
[0078] A starch group is preferably - NR11C (O) - or -C (O) -NR11- where R11 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R11 is aliphatic, alicyclic or unsubstituted aryl. Preferably R11 is hydrogen, methyl, ethyl, propyl or phenyl.
[0079] An ester group is preferably - OC (O) R12- or -C (O) OR12- where R12 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R12 is aliphatic, alicyclic or unsubstituted aryl. Preferably R12 is hydrogen, methyl, ethyl, propyl or phenyl.
[0080] A sulfoxide or sulfonate group is preferably -SOR13 or -OS (O) 2R13- where R13 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R13 is aliphatic, alicyclic or unsubstituted aryl. Preferably R13 is hydrogen, methyl, ethyl, propyl or phenyl.
[0081] A carboxylate group is preferably OC (O) R14, where R14 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R14 is aliphatic, alicyclic or unsubstituted aryl. Preferably R14 is hydrogen, methyl, ethyl, propyl, butyl (for example, n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decila, undecyl, dodecyl, tridecyl, tetradecyl , pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl or adamantyl.
[0082] An acetamide is preferably MeC (O) N (R15) 2 where R15 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R15 is aliphatic, alicyclic or unsubstituted aryl. Preferably R15 is hydrogen, methyl, ethyl, propyl or phenyl.
[0083] A phosphinate group is preferably an -OP (O) (R16) 2 group in which each R16 is independently selected from hydrogen, or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R16 is aliphatic, alicyclic or aryl, which is optionally substituted by aliphatic, alicyclic, aryl or C1-6 alkoxy. Preferably, R16 is optionally substituted aryl or C1-20 alkyl, more preferably phenyl optionally substituted by C1-6 alkoxy (preferably methoxy) or unsubstituted C1-20 alkyl (such as hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl ).
[0084] A sulfinate group is preferably - OSOR17 where R17 can be hydrogen, an aliphatic, heteroaliphatic, haloaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R17 is aliphatic, alicyclic or unsubstituted aryl. Preferably R17 is hydrogen, methyl, ethyl, propyl or phenyl.
[0085] It will be appreciated that when any of the above groups is present on a Lewis G basis, one or more additional R groups may be present, as appropriate, in order to complete the valency. For example, in the context of an ether an additional group R may be present to give rise to ROR5, where R is hydrogen, an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. Preferably, R is hydrogen or aliphatic, alicyclic or aryl.
[0086] Any of the groups aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, haloalkyl, alkoxy, alkylthio, alkylaryl, ether, ester, sulfoxide, sulfonate, carboxylate, silyl ether, imine, acetylide, amino, alkylamino or amino acid whenever mentioned in the definitions above, they can be optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl groups optional substituted (for example, optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, amino, alkylamino, imine, nitrile or acetylide).
Exemplary diols or polyols include diols (e.g., 1,2-ethanediol, 1-2-propanediol, 1,3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1 , 5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, catechol and cyclohexenediol), triols (e.g. glycerol, benzenotriol, cyclohexanotriol, tris (methyl alcohol) propane , tris (methyl alcohol) ethane, tris (methyl alcohol) nitropropane), tetraols (for example, calix [4] arene, 2,2-bis (methyl alcohol) -1,3-1,3-propanediol) and polyols (for example, poly (ethylene glycol), D - (+) - glucose and D-sorbitol).
[0088] It will be appreciated that although in formulas (I) and (III), groups X and G are illustrated as being associated with a single metal center M, one or more groups X and G can form a bridge between the two centers of metal M.
[0089] For the purposes of the present invention, the epoxy substrate is not limited. The term epoxide, therefore, refers to any compound that comprises a chemical portion of epoxide. Preferred examples of epoxides for the purposes of the present invention include cyclohexene oxide, styrene oxide, propylene oxide, substituted cyclohexene oxides (such as limonene oxide, C10H16O or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, C11H22O) , alkylene oxides (such as ethylene oxide and substituted ethylene oxides) or substituted oxirans (such as epichlorohydrin, 1,2-epoxybutane, glycidyl ethers). The epoxide preferably has a purity of at least 98%, more preferably> 99%. DETAILED DESCRIPTION
[0090] In the first aspect of the invention, it is

[0091] wherein R1 and R2 are independently optionally substituted heteroaryl, alkyletheroaryl or alkylaryl;
[0092] R3 is optionally substituted alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, in which alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene or heteroalkenylene can optionally be interrupted by aryl, heteroalkenic ;
[0093] R4 is hydrogen, or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0094] R5 is H, or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0095] E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
[0096] X is OC (O) Rx, OSO2Rx, OSO (Rx) 2, OS (O) Rx, ORx, phosphinate, halo, nitrate, hydroxyl, carbonate, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl optionally replaced;
[0097] Rx is independently hydrogen, or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or optionally substituted heteroaryl;
[0098] each G is independently absent or a neutral or anionic donor ligand which is a Lewis base;
[0099] M is Zn (II), Cr (II), Co (II), Mn (II), Mg (II), Fe (II), Ti (II), Cr (III) -X, Co (III ) -X, Mn (III) -X, Fe (III) -X, Ca (II), Ge (II), Al (III) -X, Ti (III) -X, V (III) -X, Ge (IV) - (X) 2 or Ti (IV) - (X) 2;
[0100] and a chain transfer agent selected from water or a compound of the formula (II):
[0101] Z (W) n (II)
[0102] where
[0103] Z is an optionally substituted chemical moiety selected from the group consisting of aryl, heteroaryl, polyolefin, polyester, polyether, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic polycarbonate or combinations thereof,
[0104] each W is independently selected from a hydroxyl, amine, thiol or carboxylate group, and
[0105] n is an integer that is at least 1.
[0106] It will be appreciated that, for catalysts useful in the first aspect of the invention, the groups R1 and R2 can be the same or different. R1 and R2 are preferably selected independently from hydrogen, tBu, Me, CF3, phenyl, F, Cl, Br, I, NMe2, NEt2, NO2, OMe, OSiEt3, CNMe, CN or CCPh, more preferably hydrogen, OMe, Me, NO2, halogen or tBu (for example, hydrogen or tBu). In certain embodiments, R2 is hydrogen and R1 is any one of the groups defined above, preferably NO2, halogen, tBu, OMe or Me, more preferably tBu, OMe or Me.
[0107] It will be appreciated that the group R3 is an alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl or bisubstituted heteroaryl group which may optionally be interrupted by an aryl, heteroaryl, alicyclic or heteroalicyclic group, or it may be an aryl or cycloalkylalkyl group which is a bicycloalkyl alkyl group. acts as a bridging group between two nitrogen centers in the catalyst of formula (I). Thus, where R3 is an alkylene group, such as dimethylpropylene, the group R3 has the structure -CH2-C (CH3) 2-CH2-. The definitions of the alkyl, aryl, cycloalkyl groups, etc. defined above, therefore, also refer respectively to alkylene, arylene, cycloalkylene groups, etc. defined for R3. Preferably, R3 is ethylene, 2,2-dimethylpropylene, propylene, butylene, phenylene, cyclohexylene or biphenylene, more preferably 2,2-dimethylpropylene. When R3 is cyclohexylene, the same can be the racemic form, RR- or SS-.
[0108] Preferably, R4 is independently selected from hydrogen, or alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, heteroaryl or alkyletheroaryl optionally substituted. More preferably, R4 is independently selected from hydrogen, or alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or optionally substituted heteroaryl. Exemplary options for R4 include H, Me, Et, Bn, iPr, tBu or Ph. An additional exemplary option is -CH2- (2-pyridine). R4 is preferably hydrogen.
[0109] Preferably, R5 is independently selected from hydrogen, or aliphatic or optionally substituted aryl. More preferably, R5 is selected from hydrogen, alkyl or aryl. Exemplary R5 groups include hydrogen, methyl, ethyl, phenyl and trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl. In particularly preferred embodiments, R5 is hydrogen.
[0110] It will be appreciated that X acts as the kind of initiation for the process of the first aspect. Each X is independently selected from OC (O) Rx, OSO2Rx, OS (O) Rx, OSO (Rx) 2, ORx, phosphinate, halo, nitrate, hydroxyl, carbonate, starch or aliphatic, heteroaliphatic (for example, silyl), optionally substituted alicyclic, heteroalicyclic, aryl or heteroaryl. In certain embodiments, each X is independently OC (O) Rx, OSO2Rx, OSO (Rx) 2, ORx, halo, nitrate, hydroxyl, carbonate, starch or aliphatic, heteroaliphatic (eg silyl), alicyclic, heteroalicyclic, aryl or optionally substituted heteroaryl. Rx is independently hydrogen, or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or optionally substituted heteroaryl. Preferably, X is OC (O) Rx or ORx. Preferably, Rx is independently hydrogen, aliphatic, haloaliphatic, aryl, heteroaryl, silyl or optionally substituted alkylaryl. Exemplary options for X include OCOCH3, OCOCF3, OSO2C7H7, OSO (CH3) 2, Et, Me, PhOEt, OMe, OiPr, OtBu, Cl, Br, I, F, N (iPr) 2, N (SiMe3) 2, hexanoate, octanoate, decanoate, dodecanoate, stearate, pivalate, adamantyl carboxylate, benzoate, pentafluorobenzoate, dioctyl phosphinate, diphenyl phosphinate and bis (4-methoxy) phenylphosphinate. Preferred exemplary options for X include OCOCH3, OCOCF3, OSO2C7H7, OSO (CH3) 2, Et, Me, PhOEt, OMe, OiPr, OtBu, Cl, Br, I, F, N (iPr) 2 or N (SiMe3) 2 ,.
[0111] When G is not absent, he is a group that is able to donate a single pair of electrons (ie, a Lewis base). In certain embodiments, G is a nitrogen that contains a Lewis base. Each G can be neutral or negatively charged. If G is negatively charged, then one or more positive counterions will be required to balance the charge on the complex. Suitable positive counterions include group 1 metal ions (Na +, K +, etc.), group 2 metal ions (Mg2 +, Ca2 +, etc.), imidazolium ions, an optionally substituted positively charged heteroaryl, heteroaliphatic or heteroalicyclic group, ammonium ions (i.e., N (R12) 4+), iminium ions (i.e., (R12) 2C = N (R12) 2+, such as bis (triphenylphosphine) imine) ions or phosphonium ions (P (R12) 4+), where each R12 is independently selected from hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or optionally substituted heteroaryl. Exemplary counterions include [HB] + where B is selected from triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene and 7-methyl-1,5,7-triazabicyclo [4.4.0] dec- 5-ene.
[0112] G is preferably independently selected from an optionally substituted heteroaliphatic group, an optionally substituted heteroalicyclic group, an optionally substituted heteroaryl group, a haloid, hydroxide, hydride, a carboxylate and water. More preferably, G is independently selected from water, an alcohol, a substituted or unsubstituted heteroaryl (imidazole, methyl imidazole (e.g., N-methyl imidazole), pyridine, 4-dimethylaminopyridine, pyrrole, pyrazole, etc.), an ether (dimethyl ether, diethyl ether, cyclic ethers, etc.), a thioether, carbene, a phosphine, a phosphine oxide, a substituted or unsubstituted heteroalicyclic (morpholine, piperidine, tetrahydrofuran, tetrahydrothiophene, etc.), an amine, an alkyl amine, trimethylamine, triethylamine, etc.), an acetonitrile, an ester (ethyl acetate, etc.), an acetamide (dimethylacetamide, etc.), a sulfoxide (dimethyl sulfoxide, etc.), a carboxylate, a hydroxide, hydride, a halide, a nitrate, a sulfonate, etc. In some embodiments, one or both cases of G are independently selected from among optionally substituted heteroaryl, optionally substituted heteroaliphatic, optionally substituted heteroalicyclic, haloid, hydroxide, hydride, an ether, a thioether, carbene, a phosphine, a phosphine oxide, a amine, an alkyl amine, acetonitrile, an ester, an acetamide, a sulfoxide, a carboxylate, a nitrate or a sulfonate. In certain embodiments, G can be a halo; hydroxide; hydride; Water; a heteroaryl, heteroalicyclic or carboxylate group that are optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile. In preferential modalities, G is independently selected from halo; Water; a heteroaryl optionally substituted by alkyl (e.g., methyl, ethyl, etc.), alkenyl, alkynyl, alkoxy (preferably methoxy), halogen, hydroxyl, nitro or nitrile. In some embodiments, one or both cases of G are negatively charged (for example, haloid). In additional embodiments, one or both cases of G are an optionally substituted heteroaryl. Exemplary G groups include chloride, bromide, pyridine, methylimidazole (for example, N-methyl imidazole) and dimethylaminopyridine (for example, 4-methylaminopyridine).
[0113] It will be appreciated that when a group G is present, the group G can be associated with a single metal center M as shown in formula (I), or the group G can be associated with both metal centers and form a bridge between the two metal centers, as shown below in formula (Ia):

[0114] Where R1, R2, R3, R4, R5, M, G, X, E1 and E2 are as defined for formula (I).
[0115] Preferably M is Zn (II), Cr (III), Cr (II), Co (III), Co (II), Mn (III), Mn (II), Mg (II), Ti (II) , Fe (II), Fe (III), Ca (II), Ge (II), Al (III), Ti (III), V (III), Ge (IV) or Ti (IV), 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). It will be appreciated that when M is Cr (III), Co (III), Mn (III) or Fe (III), the catalyst of formula (I) will contain an additional group X coordinated to the metal center, where X is in conformity defined above. It will also be appreciated that when M is Ge (IV) or Ti (IV), the catalyst of formula (I) will contain two additional groups X coordinated to the metal center, where X is as defined above. In certain embodiments, when M is Ge (IV) or Ti (IV), both G can be absent.
[0116] The knowledgeable person will appreciate that each M can be the same (for example, both M can be Mg, Zn, Fe or Co) or each M can be different and can be present in any combination (for example, Fe and Zn, Co and Zn, Mg and Fe, Co and Fe, Mg and Co, Cr and Mg, Cr and Zn, Mn and Mg, Mn and Zn, Mn and Fe, Cr and Fe, Cr and Co, Al and Mg, Al and Zn, etc.). When M is the same metal, it will be appreciated that each M can be in the same oxidation state (for example, both M can be Co (II), Fe (II) or Fe (III)), or in a different oxidation state (for example, one M can be Co (II) and the other M can be Co (III), one M can be Fe (II) and the other M can be Fe (III), or one M can be Cr (II ) and the other M can be Cr (III)).
[0117] In certain embodiments of the first aspect, the catalyst is selected from:


[0118] [L1Mg2Cl2 (methylimidazole)],
[0119] [L1Mg2Cl2 (dimethylaminopyridine)],
[0120] [L1Mg2Br2 (dimethylaminopyridine)],
[0121] [L1Zn2 (F3CCOO) 2],
[0122] [L1Zn2 (OOCC (CH3) 3) 2],
[0123] [L1Zn2 (OC6H5) 2],
[0124] [L1Fe2Cl4],
[0125] [L1Co2 (OAc) 3],
[0126] [L4Mg2 (OAc) 2],
[0127] [L1Zn2 (adamantyl carbonate) 2],
[0128] [L1Zn2 (pentafluorobenzoate) 2],
[0129] [L1Zn2 (diphenylphosphinate) 2],
[0130] [L1Zn2 (bis (4-methoxy) phenyl phosphinate) 2],
[0131] [L1Zn2 (hexanoate) 2],
[0132] [L1Zn2 (octanoate) 2],
[0133] [L1Zn2 (dodecanoate) 2],
[0134] [L1Mg2 (F3CCOO) 2], and
[0135] [L1Mg2Br2].
[0136] In other modalities of the first aspect, the catalyst is selected from:
[0137] [L1Zn2 (OAc) 2]
[0138] [L2Zn2 (OAc) 2]
[0139] [L3Zn2 (OAc) 2]
[0140] [L1Mg2 (OAc) 2]
[0141] [L1Mg2Cl2 (methylimidazole)],
[0142] [L1Mg2Cl2 (dimethylaminopyridine)],
[0143] [L1Mg2Br2 (dimethylaminopyridine)],
[0144] [L1Zn2 (F3CCOO) 2],
[0145] [L1Zn2 (OOCC (CH3) 3) 2],
[0146] [L1Zn2 (OC6H5) 2],

[0147] In certain embodiments, catalyst (I) is a catalyst of formula (III) as defined in relation to the sixth aspect of the invention.
[0148] The chain transfer agent (CTA) can be water or a compound that has one or more, for example, two or more groups independently selected from hydroxyl (-OH), amine (-NHRW), thiol (-SH ) or carboxylate (- C (O) OH), where RW is hydrogen, aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or optionally substituted heteroaryl, or combinations thereof (i.e., aliphatic aryl, aliphatic heteroaryl, heteroaliphatic, etc.). It will be appreciated that water, which does not have two different "-OH" groups, exhibits chain transfer properties similar to molecules that do not have two different "-OH" groups.
[0149] The chain transfer agent useful in the process of the first aspect is either water or a compound that can be represented by the following formula: Z (- W) n (II).
[0150] Each W is independently selected from hydroxyl (-OH), amine (-NHRW), thiol (-SH) or carboxylic acid (-C (O) OH).
[0151] Z is the nucleus of the chain transfer agent and can be any group that can have one or more, preferably two or more "W" groups attached to it. In preferred embodiments, Z is an optionally substituted chemical moiety selected from the group consisting of aryl, heteroaryl, polyolefin, polyester, polyether, aliphatic polycarbonate, heteroaliphatic, alicyclic, heteroalicyclic or combinations thereof. For example, Z can be an araliphatic, heteroaraliphatic, aliphaticalicyclic group, etc. optionally replaced. Preferably, Z is selected from alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and polyether.
[0152] When Z is a polymer (i.e., when Z comprises a polyolefin, polyester, polyether or polycarbonate group), the molecular weight (Mn) of such polymers is preferably less than 10,000 g / mol. Preferred polymers include poly (ethylene glycol) (PEG) and polylactic acid (PLA).
[0153] The chain transfer agent, in particular the Z group, can optionally be substituted. In certain embodiments, Z is optionally substituted by halogen, nitrile, imine, nitro, aliphatic, acetyl, starch, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl.
[0154] n is an integer that is at least 1. In preferred embodiments, n is an integer selected from 1 to 10 inclusive (that is, n can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), preferably from 2 to 10 inclusive. More preferably, n is an integer selected from 1 to 6 inclusive, even more preferably from 2 to 6 inclusive.
[0155] In certain modalities, each occurrence of W can be the same or different. In other embodiments, each occurrence of W is hydroxyl (that is, the chain transfer agent is an alcohol, which is intended to cover a chain transfer agent with an OH group, or a chain transfer agent with two or more OH groups, in other words, a polyol, for example, a diol, a triol, a tetraol, etc.). In other embodiments, each occurrence of W is amine (that is, the chain transfer agent is an amine that is intended to cover chain transfer agents with one amine group, or chain transfer agents with two or more amine groups , in other words polyamine, for example, diamine, triamine, tetraamine, etc.). In other embodiments, each occurrence of W is carboxylic acid (i.e., the chain transfer agent can comprise a carboxylic acid group, or two or more carboxylic acid groups, in other words, the chain transfer agent can be an acid polycarboxylic, for example, a diacid, a triacid, a tetra-acid, etc.). In other embodiments, each occurrence of W is thiol (that is, the chain transfer agent can comprise a thiol group, or two or more thiol groups, in other words, the chain transfer agent can be a polythiol, for example , a dithiol, a trityl, a tetrathiol, etc.). In other embodiments, the chain transfer agent is water.
[0156] In certain embodiments of the first aspect, when the chain transfer agent is water, X is not OCOCH3, OCOCF3, OSO2C7H7, OSO (CH3) 2, or haloid. In certain other embodiments of the first aspect, when the chain transfer agent is water, X is not OCOCH3, OCOCF3, OSO2C7H7, OSO (CH3) 2, halo, alkyl, alkoxy or starch. In certain other embodiments of the first aspect, when the chain transfer agent is water, the catalyst of formula (I) is a catalyst of formula (III) as described below in relation to the sixth aspect of the invention.
[0157] In certain embodiments of the first aspect, a single chain transfer agent is used. In other embodiments, a mixture of chain transfer agents is used.
[0158] Examples of chain transfer agents useful in the present invention include water, monoalcohols (i.e., alcohols with an OH group, for example, diphenylphosphonic acid, 4-ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, cyclohexanol), diols (e.g. 1,2-ethanediol, 1-2-propanediol, 1,3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, catechol and cyclohexenediol), triols (glycerol, benzenotriol, 1,2,4-butanotriol, tris (methyl alcohol) propane, tris (methyl alcohol) ethane, tris (methyl alcohol) nitropropane, preferably glycerol or benzenotriol), tetraols (eg calix [4] arene, 2,2-bis (methyl alcohol) -1,3-propanediol, preferably calix [4] arene), polyols (for example, D - (+) - glucose or D-sorbitol), dihydroxy-terminated polyesters (for example, polylactic acid), dihydroxy-terminated polyethers (for example, poly (ethylene glycol) ), starch, l ignine, mono-amines (i.e., amines with an NHRW group, for example, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine), diamines (e.g., 1, 4-butanediamine), triamines, diamine-terminated polyethers, diamine-terminated polyesters, mono-carboxylic acids (eg 3,5-di-tert-butylbenzoic acid), dicarboxylic acids (eg maleic acid, malonic acid, acid succinic, glutaric acid or terephthalic acid, preferably maleic acid, malonic acid, succinic acid, glutaric acid), tricarboxylic acids (for example, citric acid, 1,3,5-benzene tricarboxylic acid or 1,3,5-cyclohexanotricarboxylic acid, preferably citric acid), mono-thiols, dithiols, tritols and compounds that have a mixture of hydroxyl, amine, carboxylic acid and thiol groups, for example, lactic acid, glycolic acid, 3-hydroxypropionic acid, nat amino acids urals, unnatural amino acids, monosaccharides, disaccharides, oligosaccharides and polysaccharides (which includes pyranose and furanose forms). In certain embodiments, the chain transfer agent is selected from cyclohexene diol, 1,2,4-butanotriol, tris (methyl alcohol) propane, tris (methyl alcohol) nitropropane, tris (methyl alcohol) ethane, 2,2-bis (methyl alcohol) -1,3-propanediol, 1,3,5-benzene tricarboxylic acid, diphenylphosphinic acid, 1,3,5-cyclohexanotricarboxylic acid, 1,4-butanediamine, 1,6-hexanediol, D-sorbitol, 1-butylamine, terephthalic acid , D - (+) - glucose, 3,5-di-tert-butylbenzoic acid, 4-ethylbenzenesulfonic acid and water.
[0159] In a first aspect embodiment, the chain transfer agent is not water. In an alternative embodiment of the first aspect, the chain transfer agent is water. It was found that both the metal centers and the binder set of the catalysts used in the process of the first aspect are hydrolytically stable (that is, they do not break down in the presence of water). Water works extremely well as a chain transfer agent for the first aspect process and is inexpensive and readily available. Furthermore, it is not necessary to ensure that all reagents, such as monomers (which include carbon dioxide) and solvents, are completely free of water before starting the reaction. This avoids lengthy and expensive purification steps for reagents such as carbon dioxide, which are often contaminated with water (particularly carbon dioxide captured from industrial sources). In fact, as mentioned above, water impurities in the monomers, solvents, etc. it can supply all the amount of chain transfer agent necessary to convert all the end groups of the polycarbonates produced through the first aspect into hydroxyl groups. When the chain transfer agent is water, it can be present in a molar ratio of less than 1: 1 to the metal complex (for example, as an impurity in the reagents that will be used during the polymerization process) , in a molar ratio of about 1: 1 to the metal complex, or in a molar ratio of more than 1: 1 (such as at least 2: 1, at least 4: 1 or at least 8: 1 ) in relation to the metal complex (that is, in excess of the metal complex). In certain embodiments, water will be present in a molar ratio of about 1: 1 to about 128: 1, about 2: 1 to about 64: 1, about 4: 1 to about 32: 1 , or from about 8: 1 to about 16: 1 with respect to the metal complex.
[0160] In certain embodiments, the catalyst is selected from [L1Zn2 (OAc) 2], [L1Zn2 (OC (O) CF3) 2], [L1Mg2 (OAc) 2] and [L1Mg2 (OC (O) CF3) 2 ] (preferably [L1Zn2 (OAc) 2], [L1Zn2 (OC (O) CF3) 2] and [L1Mg2 (OC (O) CF3) 2]), the chain transfer agent is water and is present in a ratio molar ratio of at least 1: 1 with respect to the metal complex. For example, water can be present in a molar ratio of about 1: 1 to 128: 1, such as about 2: 1 to 64: 1, for example, about 4: 1 to 32: 1, for example, from about 8: 1 to 16: 1 with respect to the metal complex.
[0161] In certain embodiments with any of the chain transfer agents as mentioned above, the chain transfer agent is present in a molar ratio of at least 1: 1 to the metal complex (catalyst (I)) . For example, the chain transfer agent is present in a molar ratio of at least 2: 1, at least 4: 1, at least 8: 1, at least 16: 1 or at least 32: 1 with respect to the complex of metal. In certain embodiments, the chain transfer agent will be present in a molar ratio of about 1: 1 to about 128: 1, about 1: 1 to about 100: 1 (for example, about 10: 1 to about 30: 1), about 2: 1 to about 64: 1, about 4: 1 to about 32: 1, or about 8: 1 to about 16: 1 in relation to the metal complex. In certain embodiments, the chain transfer agent is present in a molar ratio of 1: 1 to 9: 1. Preferably, the chain transfer agent is present in a molar ratio of at least 2: 1 to the metal complex.
[0162] A halogenated group X reduces the amount of chain transfer agent required to produce polycarbonate chains that are terminated at both ends with hydroxy groups. In fact, the water impurities that are present either in carbon dioxide or in excess of the catalyst production (for example, if hydrated metal acetates are used in order to produce the catalysts useful in the first aspect), can act as a quantity enough chain transfer agent (where the chain transfer agent is water) to ensure that all polycarbonate chains are terminated in hydroxyl groups. An excess of chain transfer agent is therefore not required. Therefore, in certain embodiments, X is a halogenated group and the molar ratio of chain transfer agent: metal complex is at least 0.1: 1, preferably at least 1: 1, more preferably 0.1: 1 to 9: 1, even more preferably 0.1: 1 to 1: 1. Preferably X is OC (O) Rx, OSO2Rx, OSO (Rx) 2, ORx, OSORx, halophosfinate, haloaryl, haloheteroaryl, haloheteroaliphatic, haloalicyclic, haloheteroalicyclic or haloaliphatic (more preferably OC (O) Rx, OSO2R , ORx or haloaliphatic), wherein one or both of the Rx groups are haloaliphatic, haloaryl or haloalicyclic, more preferably haloaliphatic (such as fluoroaliphatic).
[0163] The process of the first aspect can be carried out in the presence of a solvent. Examples of solvents useful in the first aspect include toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, etc.
[0164] The chain transfer agent can be used to control the molecular weight (Mn) of the polymers produced through the process of the first aspect. Preferably, the molecular weight (Mn) of the polymers produced through the process of the first aspect is from about 1,000 g / mol to about 100,000 g / mol. The molecular weight of the polymers produced through the first aspect can be measured by gel permeation chromatography (GPC) using, for example, a GPC-60 manufactured by Polymer Labs, using THF as the eluent at a flow rate of 1 ml / min in Mixed B columns, manufactured by Polymer Labs. Narrow molecular weight polystyrene standards can be used to calibrate the instrument.
[0165] The process of the first aspect can be carried out using any compound that comprises a chemical portion of epoxide. In certain embodiments of the first aspect, the epoxide can be purified (for example, by distillation, such as over calcium hydride) before a reaction with carbon dioxide. For example, the epoxide can be distilled before being added to the reaction mixture comprising the catalyst and the chain transfer agent.
[0166] In certain embodiments of the process of the first aspect, the process comprises the intermediate steps of (i) providing a catalyst of formula (I) and an epoxide, (ii) adding a chain transfer agent of formula (II) to the same, and (iii) exposing the catalyst, epoxide and chain transfer agent to carbon dioxide.
[0167] The process of the first aspect of the invention can be carried out at a pressure of 101.32 kPa (1 atm) to 10.132 kPa (100 atm), preferably at 101.32 kPa (1 atm) to 1.013.2 kPa (10 atm), more preferably at 101.32 kPa (1 atm) or 202.65 kPa (2 atm). The catalysts used in the process of the first aspect allow the reaction of carbon dioxide with an epoxide to be carried out at low pressures.
[0168] The process of the first aspect of the invention can be carried out at a temperature of about 0 ° C to about 120 ° C, preferably from about 50 ° C to about 100 ° C. The duration of the process can be set to 168 hours, preferably 1 to 24 hours.
[0169] The process of the first aspect of the invention can be carried out in a low catalytic loading, for example, the catalytic loading for the process is preferably in the range of 1: 1,000 to 100,000 of catalyst: epoxide, more preferably in the region between 1: 1,000 to 50,000 catalyst: epoxide, even more preferably in the region between 1: 11,000 to 10,000, and most preferably in the region between 1: 10,000 catalyst: epoxide.
[0170] It should be noted that the catalysts that are used in the process of the first aspect can operate at a remarkably low pressure, for example, 101.32 kPa (1 atm) of CO2, but they are also active at much higher pressures, for example, 4,053 kPa (40 atm) of CO2.
[0171] It will be appreciated that the various resources described above for the process of the first aspect may be present in combination mutatis mutandis.
[0172] In a second aspect of the invention, a polymerization system is provided for the copolymerization of carbon dioxide and at least one epoxide comprising a catalyst as defined in the first aspect, and a chain transfer agent as defined in the first aspect. All preferred features of the chain transfer agent and catalyst as defined in the first aspect of the invention apply in an equivalent manner to the second aspect of the invention.
[0173] The third aspect of the invention provides a product of the process of the first aspect of the invention. All the preferred features of the first aspect of the invention apply to the third aspect of the invention mutatis mutandis.
[0174] The fourth aspect of the invention provides a copolymer of formula B (- A) n, in which B is a polycarbonate, for example, as produced by the process of the first aspect of the invention, A is an additional polymeric unit that can be differentiate in structure from B, and n is an integer that is at least 1, preferably at least 2. The architecture of the polycarbonate will depend on the chain transfer agent (CTA) used in this production. For example, if the CTA is a group Z (W) n where n is 1, the polycarbonate will be linear, terminated with a hydroxyl group at one end only. If the CTA for water or a group Z (W) n where n is 2, the polycarbonate will be linear, terminated with a hydroxyl group at each end. If the CTA is a group Z (W) n where n is 3 or more, the polycarbonate architecture can comprise a major chemical moiety that corresponds to the CTA group Z, with n polycarbonate chains, each terminated with a hydroxyl group that extends from it (such as a star-like architecture). This means that these polycarbonates can be used as macro initiators for a second polymerization in order to produce the copolymers of formula B (—A) n. Hydroxyl groups can be used to initiate several different types of polymerizations in order to form A. For example, a ring-opening polymerization (ROP) of monomers such as lactides, lactones and other cyclic carbonates can be carried out in the presence of a metal alkoxide (for example, zinc alkoxide, magnesium, yttrium, lanthanide, titanium, zirconium, aluminum, tin (IV), tin (II), iron (II), iron (III), cobalt (II), lithium , potassium, sodium, calcium, gallium, indium and scandium) or a nucleophile (for example, carbenes, amines, phosphines, optionally substituted lipase enzymes, or combinations of alcohol (s) and thiourea, alcohol (s) and urea, and acid (s) and Br0nsted alcohol (s) and hydroxyl-terminated polycarbonates produced by the process of the first aspect in order to form copolymers of formula B (- A) n. An epoxide ring opening can also be initiated by the hydroxyl groups of hydroxyl-terminated polycarbonates produced through the process of the first aspect in order to produce polymeric polyether blocks. If the ring opening of an epoxide through a hydroxyl group is carried out in the presence of an anhydride (for example, maleic anhydride) or a di- or polycarboxylic acid, the polymeric block produced is a polyester.
[0175] Polyesters can also be synthesized by adding polyols (i.e., monomers that have two or more hydroxyl groups, such as diols, triols, tetraols and the like) to monomers that have two or more ester, carboxylic acid or chloride groups acid (for example, diesters, diacids and diacid chlorides). It will be appreciated that polycarbonates produced from chain transfer agents that have 2 or more W groups (i.e., when n is 2 or more) can be used as monomers in the production of polymers such as polyesters or polyurethanes.
[0176] In certain embodiments, B is a polycarbonate as produced through the process of the first aspect of the invention and A is a polyester that is produced by adding or a) a polycarbonate as produced through the process of the first aspect of the invention in which n is at least 2 (where A can be the same or different from B) or b) a monomer comprising two or more -OH groups, to a monomer comprising two or more ester, carboxylic acid or acid chloride groups. In other embodiments, B is a polycarbonate as produced through the process of the first aspect of the invention and A is a polyurethane that is produced by adding or a) a polycarbonate as produced through the process of the first aspect of the invention in which n is at least 2 (where A can be the same or different from B) or b) a monomer comprising two or more -OH groups, to a monomer comprising two or more isocyanate groups.
[0177] It will also be appreciated that the hydroxyl groups in the polycarbonates as produced through the process of the first aspect of the invention can be reacted (or "functionalized") to form different functional groups, such as esters, carboxylic acids or amines before the block polymeric To be added. The reagents that are used to functionalize the hydroxyl groups are well known in the art.
[0178] In certain embodiments, the hydroxyl groups in B are reacted with the appropriate reagents to convert the hydroxyl groups into ester, carboxylic acid or amine groups. A is then formed by reacting the functionalized B with one or more monomers. It will be appreciated that when the hydroxyl group (s) in B are converted to carboxylic acid groups, A can be a polyester that is formed by adding a monomer that has two or more hydroxyl groups (the same can be a polycarbonate as produced by the process of the first aspect of the invention where n is at least 2) to a monomer that has two or more carboxylic acid groups (the same can be a polycarbonate as produced by the process of the first aspect of the invention in which n is at least minus 2 and in which the hydroxyl groups were reacted to form carboxylate groups, and can be the same or different from B).
[0179] The skilled person will appreciate that A can be a polyamide if the hydroxyl groups in B are converted to carboxylic acid groups, and A is formed by adding a monomer that has two or more amine groups (the same can be a polycarbonate as produced by the process of the first aspect of the invention where n is at least 2 and where the hydroxyl groups have been reacted to form amine groups) to a monomer that has two or more carboxylic acid groups (the same can be a polycarbonate as produced by the process of the first aspect of the invention where n is at least 2 and where the hydroxyl groups have been reacted to form carboxylate groups, and can be the same or different from B).
[0180] When the hydroxyl group (s) in B are converted to amine groups, A can be an epoxy resin that is formed by adding a monomer that has at least two epoxide groups to a monomer that has at least two amine groups (the same can be a polycarbonate as produced by the process of the first aspect of the invention where n is at least 2 and where the hydroxyl groups have been reacted to form amine groups, and can be the same as B).
[0181] In certain embodiments, A is produced from a monomer selected from the group consisting of a lactide, a lactone, a cyclic carbonate such as propylene carbonate or trimethylene carbonate, an epoxide or combinations thereof, or is produced from starting from a combination of a diisocyanate and a compound comprising two or more hydroxyl groups; a compound comprising two or more amine groups, a compound comprising two or more acid chloride groups, a compound comprising two or more ester groups or a compound comprising two or more hydroxyl groups and a compound comprising two or more groups hydroxyl; an epoxide and anhydride, a compound comprising two or more carboxylic acid groups, or a compound comprising two or more amine groups, or an epoxide which is preferably different from the epoxide used to produce B and carbon dioxide. Preferably, the compound that has two or more hydroxyl groups is a diol, triol, tetraol or polyol or a polycarbonate produced by the process of the first aspect, where n is at least 2. Preferably, the compound that has two or more groups amine is a diamine, a triamine, a tetraamine or a polycarbonate produced by the process of the first aspect, where n is at least 2 and the hydroxyl groups have been functionalized to amine groups. Preferably, the compound comprising two or more carboxylic acid groups is a di or poly carboxylic acid, or a polycarbonate as produced by the process of the first aspect wherein n is at least 2 and the hydroxyl groups have been functionalized to carboxylic acid groups. Preferably, the compound having two or more ester groups is a diester, a triester, a tetraester or a polycarbonate produced by the process of the first aspect, where n is at least 2 and the hydroxyl groups have been functionalized for ester groups. Preferably, the compound having two or more acid chloride groups is a diacid chloride, a tracid chloride, a tetra-acid chloride or a polycarbonate produced by the process of the first aspect, where n is at least 2 and the hydroxyl groups have been functionalized for acid chloride groups.
[0182] A can be, for example, a polyester, a polyether, a polycarbonate, a polyamide, a polyurethane or any combination of copolymer thereof. In certain embodiments, B (—A) n is a tri-block copolymer of the formula A-BA, where A can be, for example, a poly (lactide) formed by opening the lactic acid ring from the terminal hydroxyl groups of the block polycarbonate “B”.
[0183] Alternatively, the hydroxyl-terminated polycarbonate produced through the process of the first aspect can be coupled to a preformed polymeric unit A to yield a copolymer of formula B (- A) n. For example, preform A is terminated at one end with a group capable of reacting with a hydroxyl group, such as an acid chloride, an acid, an ester, an amide, an anhydride, a carboxylic acid, an isocyanurate or a urea, and then reacted with the polycarbonate formed through the process of the first aspect to produce a copolymer of formula B (- A) n. A's identity can be as described above. For example, A may be a polycarbonate produced by the process of the first aspect in which the hydroxyl group (s) have been functionalized to form an ester, carboxylic acid or amine group.
[0184] It will be appreciated that if a mixture of polycarbonate chains with different end groups (for example, a mixture of chains terminated by a hydroxyl end group and an acetate end group and chains terminated at both ends with hydroxy groups) , then a mixture of block copolymers with different architectures can be produced. In the case described above, this is avoided.
[0185] The process of the first aspect produces polycarbonates that are terminated at all ends with hydroxy groups. It will be appreciated by the person skilled in the art that the production of the copolymer of formula B (- A) n can be carried out immediately after the polycarbonate is synthesized (that is, without further purification steps to ensure that both ends are terminated in hydroxyl groups).
[0186] All the preferred features of the first aspect of the invention apply to the fourth aspect of the invention mutatis mutandis.
[0187] The fifth aspect of the invention provides a method for producing the block copolymer of the fourth aspect. The method comprises the steps of synthesis of a polycarbonate according to the process of the first aspect and or reaction of the polycarbonate with at least one additional monomer or reaction of the polycarbonate with at least one additional polymeric unit that differs in structure from the polycarbonate. In preferred embodiments, the polycarbonate reaction step with at least one additional monomer, or the polycarbonate reaction step with at least one polymeric unit that differs in structure from the polycarbonate occurs directly after a polycarbonate synthesis step according to process of the first aspect. The fifth aspect method can further comprise a step of reacting the hydroxyl group (s) in B with suitable reagents to convert the hydroxyl group (s) into an ester, carboxylic acid or amine group (s) before reaction step of the polycarbonate with at least one additional monomer, or reaction of the polycarbonate with at least one additional polymeric unit that differs in structure from the polycarbonate. All the preferred features of the first aspect and the fourth aspect of the invention apply to the fifth aspect of the invention mutatis mutandis. In particular, the identity of the additional monomer or polymeric unit may correspond to the identity described for A in the fourth aspect.
[0188] A class of catalysts that falls within the scope of catalysts that are useful for copolymerization of at least one epoxide and CO2 is known from International patent application No. WO2009 / 130470, the total content of which is incorporated into the present as a reference. An additional class of catalysts has been developed.
[0189] Therefore, in a sixth aspect of the invention, a catalyst of formula (III) is provided:

[0190] wherein R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl ether group or an acetylide group or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl , alicyclic or heteroalicyclic;
[0191] R3 is optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene; wherein alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkynylene can be optionally interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
[0192] R4 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0193] R5 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0194] E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
[0195] each G is independently absent or an anionic or neutral donor ligand which is a Lewis base;
[0196] M is Zn (II), Co (II), Mn (II), Mg (II), Fe (II), Cr (II), Ti (II), Cr (III) -X, Co (III ) -X, Mn (III) -X, Fe (III) -X, Ca (II), Ge (II), Al (III) -X, Ti (III) -X, V (III) -X, Ge (IV) - (X) 2 or Ti (IV) - (X) 2 (preferably Mg (II), Ca (II) or Ge (II));
[0197] where when both instances of G are absent and all instances of R5 are hydrogen, X is OC (O) RZ, OSO (RZ) 2, OSO2RY, OSORT, ORV, phosphinate, hydroxyl, carbonate, or nitrate optionally substituted aryl, heteroaryl, alicyclic or heteroalicyclic;
[0198] RZ is independently hydrogen or aliphatic C2-20, haloaliphatic C2-20, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0199] RY is hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl optionally substituted provided that RY is not C7H7; and
[0200] RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroalicyclic;
[0201] RT is hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0202] and where when either or both instances of G are not absent, or when one or more instances of R5 are not hydrogen, X is OC (O) Rx, OSO2Rx, OSO (Rx) 2, OSORx, ORx , phosphinate, halide, nitrate, hydroxyl, carbonate, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl optionally substituted; and
[0203] Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or optionally substituted heteroaryl.
[0204] In the preferred embodiments, the formula (III) catalyst has the following formula:

[0205] wherein R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, an acetylide or alkyl group, haloalkyl, aryl, heteroaryl, alicyclic or heteroalicyclic optionally substituted;
[0206] R3 is optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene, which can be optionally interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic; arylene; heteroarylene or cycloalkylene;
[0207] R4 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0208] E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
[0209] each G is independently absent or an anionic or neutral donor ligand that is a Lewis base;
[0210] M is Zn (II), Co (II), Mn (II), Mg (II), Fe (II), Cr (II), Cr (III) -X, Co (III) -X, Mn (III) -X, Fe (III) -X, Ca (II), Ge (II), Al (III) -X, Ti (III) -X or V (III) -X;
[0211] where when both instances of G are absent, X is OC (O) RZ, OSO (RZ) 2, OSO2RY, ORV, hydroxyl, carbonate, nitrate or aryl, heteroaryl, alicyclic or optionally substituted heteroalicyclic;
[0212] RZ is independently hydrogen or aliphatic C2-20, haloaliphatic C2-20, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0213] RY is hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl optionally substituted provided that RY is not C7H7; and
[0214] RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroalicyclic;
[0215] and where when either or both instances of G are not absent, X is OC (O) Rx, OSO2Rx, OSO (Rx) 2, ORx, halide, nitrate, hydroxyl, carbonate, starch or optionally substituted aliphatic , heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; and
[0216] Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted.
[0217] In the preferred modalities of the sixth aspect, R1 and R2 can be the same or different. In some embodiments, R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl ether group or an acetylide or alkyl group, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alicyclic or optionally substituted heteroalicyclic. In other embodiments, R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide or alkyl group, alkenyl, alkynyl, haloalkyl, aryl or alicyclic optionally substituted. R1 and R2 are preferably independently selected from hydrogen, tBu, Me, CF3, phenyl, F, Cl, Br, I, NMe2, NEt2, NO2, OMe, OSiEt3, CNMe, CN or CCPh, most preferably hydrogen, OMe, Me, NO2, halogen or tBu (for example, hydrogen or tBu). In certain embodiments, R2 is hydrogen and R1 is any of the groups defined above, preferably NO2, halogen, tBu, OMe or Me, most preferably tBu, OMe or Me.
[0218] In the sixth aspect, R3 is a disubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl or heteroalquinyl group that can be optionally interrupted by an aryl, heteroaryl, alicyclic or heterocyclic group or it may be a disubstituted aryl or cycloalkyl group that acts aryl or cycloalicylic. as a bridge group between two nitrogen centers in the catalyst of formula (III). Thus, where R3 is an alkylene group, such as dimethylpropylene, the group R3 has the structure -CH2- C (CH3) 2-CH2-. The definitions of the alkyl, aryl, cycloalkyl groups, etc. presented above, therefore, also refer respectively to alkylene, arylene, cycloalkylene groups, etc. presented for R3. In certain embodiments, R3 is optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene; wherein alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkynylene can be optionally interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic. In other embodiments, R3 is optionally substituted alkylene, alkenylene, alkylene, or cycloalkylene, wherein alkylene, alkenylene, alkylene may be optionally interrupted by aryl or alicyclic. In preferred embodiments, R3 is a propylene group that is optionally substituted by aliphatic groups (preferably C16 alkyl) or aryl. Preferably R3 is ethylene, 2,2-dimethylpropylene, propylene, butylene, phenylene, cyclohexylene or biphenylene, more preferably 2,2-dimethylpropylene. When R3 is cyclohexylene, it can be in the racemic forms RR- or SS-.
[0219] R4 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl. Preferably, R4 is independently selected from optionally substituted hydrogen or alkyl, alkenyl, alkynyl, aryl or heteroaryl. In certain embodiments, R4 is independently selected from hydrogen or aliphatic, alicyclic, aryl or alkylaryl optionally substituted. Most preferably, R4 is hydrogen. Exemplary options for R4 include H, Me, Et, Bn, iPr, tBu or Ph. R4 is preferably hydrogen.
[0220] R5 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or alkylaryl optionally substituted. Preferably R5 is independently selected from optionally substituted hydrogen or aliphatic or aryl. Most preferably, R5 is selected from hydrogen, alkyl or aryl. Exemplary R5 groups include hydrogen, methyl, trifluoromethyl, ethyl and phenyl (preferably hydrogen, trifluoromethyl and methyl). In particularly preferred embodiments, all instances of R5 are hydrogen. In other particularly preferred embodiments, one or more instances of R5 are not hydrogen.
[0221] In certain embodiments, R1, R2, R3, R4 and R5 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide , or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Preferably R1, R2, R3, R4 and R5 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic and unsubstituted aryl replaced.
[0222] In certain embodiments, E1 is C, E2 is O, S or NH, and preferably E2 is O. In other embodiments, E1 is N and E2 is O.
[0223] When both instances of G are absent, (preferably when both instances of G are absent and all instances of R5 are hydrogen), each X is independently selected from OC (O) RZ, OSO (RZ ) 2, OSO2RY, OSO2RT, ORV, phosphinate, hydroxyl, carbonate, nitrate or aryl, heteroaryl, alicyclic or optionally substituted heteroalicyclic. In certain embodiments, each X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, ORV, hydroxyl, carbonate, nitrate or aryl, heteroaryl, alicyclic or heteroalicyclic optionally substituted. In other embodiments, each X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, OSO2RT, ORV, phosphinate, hydroxyl, carbonate, nitrate or aryl or optionally substituted alicyclic. RZ is independently hydrogen or aliphatic C2-20, haloaliphatic C2-20, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or optionally substituted heteroaryl. RY is hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl optionally substituted, provided that RY is not C7H7. RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroalicyclic. Preferably, X is OC (O) RZ or ORV. RT is hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or optionally substituted heteroaryl. Exemplary groups X for when both instances of G are absent include benzoate, pentafluorobenzoate, pivalate, adamantyl carboxylate, diphenyl phosphinate, dioctyl phosphinate, bis (4-methoxyphenyl) phosphinate, hexanoate, octanoate, dodecanoate, stearate.
[0224] Preferably, RZ is aryl, heteroaryl, alicyclic, heteroalicyclic, alkylaryl, aliphatic C2-20 (preferably, aliphatic C4-20, more preferably, aliphatic C8-20), haloaliphatic C2-20 (preferably, haloaliphatic C2-20, more preferably, haloaliphatic C2-20) or heteroaliphatic C4-20 (preferably heteroC8-20aliphatic) optionally substituted. In certain embodiments, RZ is selected from C2-20 aliphatic, C2-20 haloaliphatic, alicyclic, optionally substituted aryl and alkylaryl. Most preferably, RZ is a C4-20 aliphatic, C4-20 haloaliphatic, optionally substituted alicyclic or aryl group, preferably even larger, an unsubstituted C4-12 aliphatic group, an unsubstituted alicyclic group or an aryl group which is optionally replaced by one or more halogen groups (preferably fluorine). Exemplary RZ groups include phenyl, pentafluorophenyl, n-pentane, n-heptane, n-undecane, n-heptadecane, tert-butyl and adamantane.
[0225] Preferably, RY is aryl, heteroaryl, alicyclic, heteroalicyclic, alkylaryl, aliphatic (preferably C4-20 aliphatic, more preferably C8-20 aliphatic) or C4-20 heteroaliphatic (preferably C8-20 heteroaliphatic) optionally substituted, provided that RY is not C7H7. In certain embodiments, RY is optionally substituted hydrogen, aliphatic, alicyclic, aryl, or alkylaryl, provided that RY is not C7H7. Most preferably, RY is optionally substituted heteroaryl, alicyclic or heteroalicyclic. In certain embodiments, RV is optionally substituted aryl, haloaryl, alicyclic or alkylaryl.
[0226] Preferably, RV is optionally substituted aryl, heteroaryl, alicyclic, heteroalicyclic or C4-20 (preferably C8-20 heteroaliphatic), more preferably aryl, heteroaryl, alicyclic or optionally substituted heteroalicyclic. In the preferred modalities, RV is optionally substituted aryl or alicyclic.
[0227] Preferably, RT is hydrogen or aliphatic, haloaliphatic, alicyclic, aryl or alkylaryl optionally substituted. In the preferred modalities, RT is hydrogen or aliphatic, aryl or alicyclic optionally substituted.
[0228] RZ, RY, RV and RT are optionally substituted by halogen, hydroxyl, nitrile, nitro, starch, amino, imine or C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C6-10 aryl, heteroaryl, C3-6 cycloalkyl, C36 cycloalkenyl, C3-6 cycloalkynyl, unsubstituted alkoxy or alkylthio. In certain embodiments, RZ, RY, RT and RV are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic , heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. In the preferred modalities, RZ, RY, RV and RT are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic and unsubstituted aryl replaced. Preferably, RZ, RY, RV and RT are replaced by halogen, more preferably fluorine.
[0229] As described in the first aspect, when X is a halogenated group, the amount of chain transfer agent required to ensure that both ends of the polycarbonate chains are terminated in hydroxyl groups is considerably reduced. Thus, in a preferred embodiment of the sixth aspect, when both instances of G are absent (preferably, when both instances of G are absent and all instances of R5 are hydrogen), X is OC (O) RZ, OSO (RZ) 2, OSO2RY, OSORT, ORV, halophosphinate, haloaryl, haloheteroaryl, haloalicyclic, haloheteroalicyclic, haloheteroaliphatic or haloaliphatic in which RZ, RY, RV and RT are independently haloaliphatic, haloethyl, halohalo or haloalicyclic, preferably C2-20 haloaliphatic, or haloalicyclic, more preferably C2-20 fluoroaliphatic. When X is OSO (RZ) 2, either or both RZ are C2-20 haloaliphatic, haloaryl or haloalicyclic most preferably C2-20 fluoroaliphatic. In certain other embodiments, when either or both instances of G are not absent, X is preferably OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, halophosphinate, halo-heteroaliphatic, haloaryl, halo-heteroaryl, halo-allylic, haloheteroalicyclic or haloaliphatic (more preferably, OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, halophosphinate or haloaliphatic), in which at least one Rx is haloaliphatic, halo-halo, halo-halo, halo-halo, halo-halo, halo-halo most preferably haloaliphatic, haloaryl or haloalicyclic (such as fluoroaliphatic). For example, Rx can be pentafluorophenyl or trifluoromethyl.
[0230] In certain other modalities, when one or more instances of R5 are not hydrogen, X is preferably OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, halophosphinate, halo-heteroaliphatic, haloaryl, halo-heteroaryl, halo , haloheteroalicyclic or haloaliphatic (more preferably, OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, halophosphinate or haloaliphatic), in which at least one Rx is haloaliphatic, halo-halo, halo-halo, halo-halo or halo-halo , most preferably, haloaliphatic, haloaryl or haloalicyclic (such as fluoroaliphatic). For example, Rx can be pentafluorophenyl or trifluoromethyl.
[0231] When G is not absent, it is a group that can donate a single pair of electrons (ie, a Lewis base). In certain embodiments, G is a nitrogen containing Lewis base. Each G can be independently neutral or negatively charged. If G is negatively charged, then one or more positive counterions are needed to balance the charge on the complex. Suitable positive counterions include group 1 metal ions (Na +, K +, etc.), group 2 metal ions (Mg2 +, Ca2 +, etc.), imidazolium ions, positively charged heteroaryl, heteroalicyclic or optionally heteroaliphatic groups substituted, ammonium ions (ie N (R12) 4+), iminium ions (i.e., (R12) 2C = N (R12) 2+, such as bis (triphenylphosphine) imine) or phosphonium ions (P (R12) 4+), where each R12 is independently selected from hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl optionally substituted. Exemplary counterions include [HB] + where B is selected from triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene and 7-methyl-1,5,7-triazabicyclo [4.4. 0] dec-5-ene.
[0232] G is preferably independently selected from an optionally substituted heteroaliphatic group, an optionally substituted heteroalicyclic group, an optionally substituted heteroaryl group, a halide, hydroxide, hydride, a carboxylate, an ether, a thioether, carbene, a phosphine , a phosphine oxide, an amine, an acetamide, acetonitrile, an ester, a sulfoxide, a sulfonate and water. Most preferably, G is independently selected from water, an alcohol, a substituted or unsubstituted heteroaryl (imidazole, methyl imidazole, pyridine, 4-dimethylaminopyridine, pyrrole, pyrazole, etc.), an ether (dimethyl ether, diethyl ether, cyclic ethers, etc.), a thioether, carbene, a phosphine, a phosphine oxide, a substituted or unsubstituted heteroalicyclic (morpholine, piperidine, tetrahydrofuran, tetrahydrothiophene, etc.), an amine, an alkyl amine (trimethylamine, triethylamine, etc.), acetonitrile, an ester (ethyl acetate, etc.), an acetamide (dimethylacetamide, etc.), a sulfoxide (dimethylsulfoxide, etc.), a carboxylate, a hydroxide, hydride, a halide, a nitrate, a sulfonate, etc. In some embodiments, one or both instances of G is independently selected from optionally substituted heteroaryl, optionally substituted heteroaliphatic, optionally substituted heteroalicyclic, halide, hydroxide, hydride, an ether, a thioether, carbene, a phosphine, a phosphine oxide , an amine, an alkyl amine, acetonitrile, an ester, an acetamide, a sulfoxide, a carboxylate, a nitrate or a sulfonate. In certain embodiments, G can be a halide; hydroxide; hydride; Water; a heteroaryl, heteroalicyclic or carboxylate group that are optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile. In the preferred modalities, G is independently selected from halide; Water; a heteroaryl optionally substituted by alkyl (e.g., methyl, ethyl, etc.), alkenyl, alkynyl, alkoxy (preferably methoxy), halogen, hydroxyl, nitro or nitrile. In some embodiments, one or both instances of G are negatively charged (for example, halide). In the additional embodiments, one or both instances of G are an optionally substituted heteroaryl. Exemplary G groups include chloride, bromide, pyridine, methylimidazole (for example, N-methyl imidazole) and dimethylaminopyridine (for example, 4-methylaminopyridine).
[0233] When one or both instances of G are not absent, each X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate , optionally substituted, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Each Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted. Preferably, X is OC (O) Rx or ORx. Preferably, Rx is optionally substituted hydrogen, aliphatic, alicyclic, haloaliphatic, alkylaryl, aryl or heteroaryl, more preferably, Rx is optionally substituted hydrogen, aliphatic, alicyclic, haloaliphatic, alkyl or aryl. R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl ether group, or an acetylide or alkyl group, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alicyclic or optionally substituted heteroalicyclic. R3 is alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene, heteroalkenylene, arylene, heteroarylene or cycloalkylene optionally substituted, in which alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkynylene can be optionally interrupted by aryl, heteroalicylic or allyl. R4 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl. Preferably, R1, R2, R3, R4, R5 and Rx are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Exemplary groups X for when at least one G is not absent include benzoate, pentafluorobenzoate, pivalate, adamantyl carbonate, diphenyl phosphinate, bis (4-methoxyphenyl) phosphinate, hexanoate, octanoate, dodecanoate, stearate, chloride, bromide, acetate and trifluroracetate (preferably chloride, bromide, acetate or trifluoroacetate).
[0234] When one or more instances of R5 are not hydrogen, each X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, optionally substituted starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Each Rx is independently hydrogen or aliphatic, haloaliphatic, alicyclic, aryl or alkylaryl optionally substituted. Preferably, X is OC (O) Rx or ORx. R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl or alicyclic group. R3 is independently selected from optionally substituted alkylene, alkenylene, alkylene, arylene or cycloalkylene, in which alkylene, alkenylene or alkynylene can be optionally interrupted by aryl or alicyclic. R4 is independently selected from H or aliphatic, alicyclic, aryl or optionally substituted alkylaryl. R5 is preferably aliphatic, alicyclic, aryl or alkylaryl optionally substituted. R1, R2, R3, R4 and R5 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic and unsubstituted aryl. Exemplary groups X for when one or more instances of R5 are not hydrogen include benzoate, pentafluorobenzoate, pivalate, adamantyl carbonate, diphenyl phosphinate, bis (4-methoxyphenyl) phosphinate, hexanoate, octanoate, dodecanoate, stearate, chloride, bromide , acetate and trifluroracetate (preferably chloride, bromide, acetate or trifluoroacetate).
[0235] It should be noted that when a group G is present, the group G can be associated with a single metal center M as shown in formula (III), or the group G can be associated with both metal centers and form a bridge between the two metal centers, as shown below in formula (IIIb):

[0236] Where R1, R2, R3, R4, R5, M, G, X, E1 and E2 are as defined for formula (III).
[0237] Preferably, M is Zn (II), Cr (III), Cr (II), Co (III), Co (II), Mn (III), Mn (II), Mg (II), Fe ( II), Fe (III), Ca (II), Ge (II), Ti (II), Al (III), Ti (III), V (III), Ge (IV) or Ti (IV), of greater preferably, Zn (II), Cr (III), Co (II), Mn (II), Mg (II), Fe (II) or Fe (III) and, most preferably, Zn (II) or Mg (II ). It should be noted that when M is Cr (III), Co (III), Mn (III) or Fe (III), the catalyst of formula (III) will contain an additional group X coordinated to the metal center, where X is as defined above. It should be noted that when M is Ge (IV) or Ti (IV), the catalyst of formula (III) will contain two additional groups X coordinated to the metal center, where X is as defined above. In certain embodiments, when M is Ge (IV) or Ti (IV), both G may be absent.
[0238] The knowledgeable person will also realize that each M can be the same (for example, both M can be Mg, Zn, Fe or Co) or each M can be different and can be present in any combination (for example, Fe and Zn, Co and Zn, Mg and Fe, Co and Fe, Mg and Co, Cr and Mg, Cr and Zn, Mn and Mg, Mn and Zn, Mn and Fe, Cr and Fe, Cr and Co, Al and Mg, Al and Zn, etc.). When M is the same metal, it should be noted that each M can be in the same oxidation state (for example, both M can be Co (II), Fe (II) or Fe (III)), or in a state of different oxidation (for example, one M can be Co (II) and the other M can be Co (III), one M can be Fe (II) and the other M can be Fe (III), or an M can be Cr (II) and the other M can be Cr (III)).
[0239] In certain modalities, when M is Ge (II), Ge (IV) - (X) 2, Ca (II) or Mg (II):
[0240] R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an amine, an imine, an ether group, a silyl ether group or an acetylide group or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl , heteroaryl, alicyclic or heteroalicyclic group;
[0241] R3 is independently selected from alkylene, alkenylene, alkylene, heteroalkenylene, heteroalkenylene, heteroalkenylene, arylene, heteroarylene or cycloalkylene optionally substituted, in which alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene, heteroalkenyl can be optionally interrupted by aralkaline heteroaryl, alicyclic or heteroalicyclic;
[0242] R4 is independently selected from H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl;
[0243] R5 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or alkylaryl (preferably hydrogen) optionally substituted;
[0244] E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
[0245] G is absent or is independently selected from an anionic or neutral donor ligand which is a Lewis base;
[0246] where when both instances of G are absent and all instances of R5 are hydrogen, X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, OSORT, ORV, phosphinate, hydroxyl , optionally substituted carbonate, nitrate or aryl, heteroaryl, alicyclic or heteroalicyclic; preferably when both instances of G are absent and all instances of R5 are hydrogen, X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, ORV, hydroxyl, carbonate, nitrate or aryl, optionally substituted heteroaryl, alicyclic or heteroalicyclic;
[0247] RZ is independently hydrogen or aliphatic C2-20, haloaliphatic C2-20, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0248] RY is hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl optionally substituted provided that RY is not C7H7;
[0249] RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroalicyclic;
[0250] RT is hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0251] and where when either or both instances of G are not absent, or one or more instances of R5 are not hydrogen, X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx ) 2, optionally substituted ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; preferably, when either or both instances of G are not absent, or one or more instances of R5 are not hydrogen, X is independently selected from OC (O) Rx, OSO2Rx, OSO (Rx) 2, ORx, halide, nitrate, hydroxyl, carbonate, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl optionally substituted;
[0252] Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted.
[0253] Preferably, R1, R2, R3, R4, R5, Rx, RV, RY, RZ and RT are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl.
[0254] In certain embodiments, M is Zn (II), Cr (III) -X, Cr (II), Co (III) -X, Co (II), Mn (III) -X, Mn (II), Mg (II), Ti (II), Fe (II), Fe (III) -X, Al (III) -X, Ti (III) -X, V (III) -X or Ti (IV) - (X ) 2 (preferably Zn (II), Fe (II), Fe (III) -X, Co (II) or Co (III) -X, more preferably Zn (II), Fe (II) or Fe ( III) -X);
[0255] G is absent or is independently selected from an anionic or neutral donor ligand which is a Lewis base;
[0256] R5 is H or aliphatic, alicyclic, aryl, or alkylaryl (preferably hydrogen) optionally substituted;
[0257] E1 is C, E2 is O, S or NH or E1 is N and E2 is O; on what
[0258] (i) when both instances of G are absent and all instances of R5 are hydrogen, X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, OSORT, ORV, phosphinate, optionally substituted hydroxyl, carbonate, nitrate or aryl, heteroaryl, alicyclic or heteroalicyclic; preferably when both instances of G are absent and all instances of R5 are hydrogen, X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, ORV, hydroxyl, carbonate, nitrate or aryl, optionally substituted heteroaryl, alicyclic or heteroalicyclic;
[0259] R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide group or an alkyl, alkenyl, alkynyl, haloalkyl, aryl or alicyclic group optionally substituted;
[0260] R3 is independently selected from optionally substituted alkylene, alkenylene, alkylene, arylene or cycloalkylene, in which alkylene, alkenylene or alkylene may be optionally interrupted by aryl or alicyclic.
[0261] R4 is independently selected from H or optionally substituted aliphatic, alicyclic, aryl or alkylaryl;
[0262] RZ is independently hydrogen or aliphatic C2-20, haloaliphatic C2-20, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0263] RY is hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl optionally substituted provided that RY is not C7H7;
[0264] RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroalicyclic;
[0265] RT is optionally substituted hydrogen or aliphatic, haloaliphatic, alicyclic, aryl or alkylaryl;
[0266] R1, R2, R3 and R4 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic and unsubstituted aryl ; and
[0267] RV, RY, RZ and RT are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
[0268] (ii) when either or both instances of G are not absent, X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, starch or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
[0269] Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0270] R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl ether group, or an acetylide or alkyl group, alkenyl, alkynyl, haloalkyl, aryl, optionally substituted heteroaryl, alicyclic or heteroalicyclic;
[0271] R3 is optionally substituted alkylene, alkenylene, alkylene, heteroalkenylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, in which alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkenylene can be optionally interrupted by aryl, heteroalicylic or aryl, heteroalkenyl ;
[0272] R4 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl; and
[0273] R1, R2, R3, R4, R5 and Rx are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; or
[0274] (iii) when or one or more instances of R5 are not hydrogen, X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, phosphinate, halide, nitrate, hydroxyl , carbonate, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl optionally substituted;
[0275] Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted.
[0276] R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide group or an alkyl, alkenyl, alkynyl, haloalkyl, aryl or alicyclic group optionally substituted;
[0277] R3 is independently selected from optionally substituted alkylene, alkenylene, alkylene, arylene or cycloalkylene, wherein alkylene, alkenylene or alkylene may be optionally interrupted by aryl or alicyclic;
[0278] R4 is independently selected from H or aliphatic, alicyclic, aryl or alkylaryl optionally substituted;
[0279] R1, R2, R3, R4 and R5 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic and aryl not replaced; and
[0280] Rx is independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl.
[0281] In certain modalities, M is Ge (II), Ge (IV) - (X) 2, Ca (II) or Mg (II);
[0282] G is absent or is independently selected from an anionic or neutral donor ligand which is a Lewis base;
[0283] R5 is H or aliphatic, alicyclic, aryl, or alkylaryl (preferably hydrogen) optionally substituted;
[0284] E1 is C, E2 is O, S or NH or E1 is N and E2 is O; on what
[0285] i) when both instances of G are absent and all instances of R5 are hydrogen, X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, OSORT, ORV, phosphinate, hydroxyl , optionally substituted carbonate, nitrate or aryl, heteroaryl, alicyclic or heteroalicyclic; preferably when both instances of G are absent and all instances of R5 are hydrogen, X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, ORV, hydroxyl, carbonate, nitrate or aryl, optionally substituted heteroaryl, alicyclic or heteroalicyclic;
[0286] R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide group or an alkyl, alkenyl, alkynyl, haloalkyl, aryl or alicyclic group optionally substituted;
[0287] R3 is independently selected from optionally substituted alkylene, alkenylene, alkylene, arylene or cycloalkylene, wherein alkylene, alkenylene or alkylene may be optionally interrupted by aryl or alicyclic;
[0288] R4 is independently selected from H or aliphatic, alicyclic, aryl or alkylaryl optionally substituted;
[0289] RZ is independently hydrogen or aliphatic C2-20, haloaliphatic C2-20, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0290] RY is hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl optionally substituted provided that RY is not C7H7;
[0291] RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroalicyclic;
[0292] RT is optionally substituted hydrogen or aliphatic, haloaliphatic, alicyclic, aryl or alkylaryl;
[0293] R1, R2, R3 and R4 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic and unsubstituted aryl ; and
[0294] RV, RY, RZ and RT are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
[0295] ii) when either or both instances of G are not absent, X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, phosphinate, halide, nitrate, hydroxyl , carbonate, starch or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
[0296] Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0297] R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl ether group, or an acetylide or alkyl group, alkenyl, alkynyl, haloalkyl, aryl, optionally substituted heteroaryl, alicyclic or heteroalicyclic;
[0298] R3 is optionally substituted alkylene, alkenylene, alkylene, heteroalkenylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, in which alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkenylene can be optionally interrupted by aryl, heteroalkenyl, or ;
[0299] R4 is H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkyletheroaryl or optionally substituted alkylaryl; and
[0300] R1, R2, R3, R4, R5 and Rx are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl; or
[0301] iii) when or one or more instances of R5 are not hydrogen, X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, ORx, phosphinate, halide, nitrate, hydroxyl, optionally substituted carbonate, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
[0302] Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0303] R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide group or an alkyl, alkenyl, alkynyl, haloalkyl, aryl or alicyclic group optionally substituted;
[0304] R3 is independently selected from optionally substituted alkylene, alkenylene, alkylene, arylene or cycloalkylene, wherein alkylene, alkenylene or alkylene may be optionally interrupted by aryl or alicyclic;
[0305] R4 is independently selected from H or aliphatic, alicyclic, aryl or alkylaryl optionally substituted;
[0306] R1, R2, R3, R4 and R5 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic and aryl not replaced; and
[0307] Rx is independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl.
[0308] In certain embodiments, M is independently selected from Mg (II), Zn (II), Ca (II), Ge (II), Co (II), Mn (II), Ti (II), Fe (II), Cr (II), Cr (III) -X, Co (III) -X, Mn (III) -X, Fe (III) -X, Al (III) -X, Ti (III) -X , V (III) -X, Ge (IV) - (X) 2 or Ti (IV) - (X) 2,
[0309] R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide group or an alkyl, alkenyl, alkynyl, haloalkyl, aryl or alicyclic group optionally substituted;
[0310] R3 is independently selected from optionally substituted alkylene, alkenylene, alkylene, arylene or cycloalkylene, wherein alkylene, alkenylene or alkylene may be optionally interrupted by aryl or alicyclic;
[0311] R4 is independently selected from H or aliphatic, alicyclic, aryl or alkylaryl optionally substituted;
[0312] R5 is H or aliphatic, alicyclic, aryl, or optionally substituted alkylaryl;
[0313] E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
[0314] G is absent or is independently selected from an anionic or neutral donor ligand which is a Lewis base;
[0315] X is independently selected from OC (O) RZ, OSO (RZ) 2, OSO2RY, OSORT, ORV, phosphinate, hydroxyl, carbonate, nitrate or aryl, heteroaryl, alicyclic or optionally substituted heteroalicyclic;
[0316] RZ is independently hydrogen or aliphatic C2-20, haloaliphatic C2-20, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted;
[0317] RY is hydrogen or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl optionally substituted provided that RY is not C7H7;
[0318] RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroalicyclic;
[0319] RT is optionally substituted hydrogen or aliphatic, haloaliphatic, alicyclic, aryl or alkylaryl;
[0320] R1, R2, R3, R4 and R5 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic and aryl not replaced; and
[0321] RV, RY, RZ and RT are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl.
[0322] In the preferred modalities, M is Mg (II), one or both G groups are present, or both G are absent and one or more instances of R5 are not hydrogen, G is optionally substituted heteroaryl, X is halogen, phosphinate , or OC (O) Rx, Rx is optionally substituted aryl, alicyclic or aliphatic (preferably C1-6 alkyl or C1-6 haloalkyl), R1 is hydrogen or C1-6 alkyl, R2 is hydrogen, R3 is optionally substituted alkylene with C1-6 alkyl or aryl, R4 is hydrogen, R5 is independently hydrogen or optionally substituted C1-20 aliphatic (preferably methyl or trifluoromethyl), E1 is C and E2 is O. Preferably, G is heteroaryl optionally substituted by amine ( preferably dimethylamine) or C1-6 alkyl (preferably methyl), more preferably G is pyridine, N-methyl imidazole or 4-dimethylaminopyridine.
[0323] Most preferably M is Mg (II), one or both groups G are present, or both G are absent and one or more instances of R5 is not hydrogen, X is chlorine, bromine, iodine, phosphinate, or OC (O) Rx, Rx is C1-20 aliphatic, C1-20 alicyclic or optionally substituted aryl, R1 is hydrogen or tert-butyl, R2 is hydrogen, R3 is propylene or 2,2-dimethyl propylene, R5 is hydrogen or methyl, E1 is C and E2 is O. In particularly preferred embodiments, X is acetate, trifluoroacetate, pivalate, benzoate, pentafluorobenzoate, chloride, bromine, hexanoate, octanoate, dodecanoate, adamantyl carboxylate, diphenyl phosphinate or bis (4-methoxy phosphinate) ) phenyl (preferably acetate).
[0324] In the preferred modalities, M is Zn (II), both groups G are absent, X is phosphinate or OC (O) RZ, RZ is C4-20 aliphatic, alicyclic C4-20 or optionally substituted aryl, R1 is hydrogen or C1-6 alkyl, R2 is hydrogen, R3 is alkylene optionally substituted by C1-6 alkyl or aryl, R4 is hydrogen, R5 is hydrogen or optionally substituted C1-20 aliphatic (preferably trifluoromethyl or methyl), E1 is C and E2 is O. Most preferably, M is Zn (II), both groups G are absent, X is benzoate, pentafluorobenzoate, hexanoate, octanoate, stearate, dodecanoate, adamantyl carboxylate, diphenyl phosphinate, bis phosphinate (4- methoxy) phenyl, dioctanyl phosphinate or pivalate, R1 is hydrogen or tert-butyl, R2 is hydrogen, R3 is propylene or 2,2-dimethyl propylene, R4 is hydrogen, R5 is hydrogen, E1 is C and E2 is O.
[0325] In the preferred modalities, M is Zn (II), one or both groups G are present and are selected from optionally substituted heteroaryl and halogen, X is chlorine, bromine, iodine, phosphinate, or OC (O) Rx , Rx is optionally substituted C1-20 aliphatic, C1-20 alicyclic or aryl, R1 is hydrogen or tert-butyl, R2 is hydrogen, R3 is propylene or 2,2-dimethyl propylene, R5 is hydrogen or independently optionally substituted by aliphatic C1-20 (preferably methyl or trifluoromethyl), E1 is C and E2 is O. In particularly preferred embodiments, X is acetate, trifluoroacetate, pivalate, benzoate, pentafluorobenzoate, chlorine, bromine, hexanoate, octanoate, dodecanoate, carboxylate adamantyl, diphenyl phosphinate or bis (4-methoxy) phenyl phosphinate (preferably acetate). It should be noted that when G is a halogen, one must be present. Preferably, the counterion is [HB] +, where B is preferably selected from NEt3, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 7-methyl-1, 5,7-triazabiciclo [4.4.0] dec-5-ene (MTBD).
[0326] In the preferred modalities, when M is Co (II), one or both groups G are present and are selected from optionally substituted heteroaryl and halogen, X is halogen or OC (O) Rx, Rx is C1- aliphatic 20, optionally substituted C1-20 alicyclic or aryl, R1 is hydrogen or C1-6 alkyl, R2 is hydrogen, R3 is alkylene optionally substituted by C1-6 alkyl or aryl, R4 is hydrogen, R5 is hydrogen or C1-20 aliphatic optionally substituted (preferably, trifluoromethyl or methyl), E1 is C and E2 is O. In preferred embodiments, G is heteroaryl optionally substituted by C1-6 alkyl (preferably methyl) or amine (preferably dimethylamine). Most preferably, M is Co (II), either or both instances of G are present and are pyridine, dimethylaminopyridine (preferably 4-dimethylaminopyridine), methylimidazole (preferably N-methylimidazole), chlorine, bromine or iodine , X is chlorine, bromine or iodine (preferably chlorine or bromine), R1 is hydrogen or tert-butyl, R3 is propylene or 2,2-dimethyl propylene, R4 is hydrogen, R5 is hydrogen, trifluoromethyl or methyl, E1 is C and E2 is O. It should be noted that when G is a halogen, a counter-ion must be present. Preferably, the counter-ion is [HB] +, where B is preferably selected from NEt3, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 7-methyl-1, 5,7-triazabiciclo [4.4.0] dec-5-ene (MTBD).
[0327] In the preferred modalities, M is Fe (II) or Fe (III) -X, one or both groups G are present and are selected from optionally substituted heteroaryl and halogen, X is halogen or OC (O) Rx , Rx is optionally substituted C1-20 aliphatic, C1-20 alicyclic or aryl, R1 is hydrogen or C1-6 alkyl, R2 is hydrogen, R3 is alkylene optionally substituted by C1-6 alkyl or aryl, R4 is hydrogen, R5 is hydrogen or optionally substituted C1-20 aliphatic (preferably trifluoromethyl or methyl), E1 is C and E2 is O. In particularly preferred embodiments, G is a heteroaryl optionally substituted by C1-6 alkyl (preferably methyl) or amine (from preferably dimethylamine). Most preferably, when M is Fe (II) or Fe (III) -X, either or both instances of G are present and are pyridine, dimethylaminopyridine (preferably 4-dimethylaminopyridine), methylimidazole (preferably N- methylimidazole), chlorine, bromine or iodine (preferably chlorine or bromine), X is chlorine, bromine or iodine (preferably chlorine or bromine), R1 is hydrogen or tert-butyl, R3 is propylene or 2,2-dimethyl propylene, R4 is hydrogen, R5 is hydrogen, E1 is C and E2 is O. It should be noted that when G is a halogen, a counterion must be present. Suitable counterions are described in the application above.
[0328] Exemplary catalysts according to the sixth aspect include:
[0329] [L1Mg2Cl2 (methylimidazole)],
[0330] [L1Mg2Cl2 (dimethylaminopyridine)],
[0331] [L1Mg2Br2 (dimethylaminopyridine)],
[0332] [L1Zn2 (OOCC (CH3) 3) 2],
[0333] [L1Zn2 (OC6H5) 2],
[0334] [L1Zn2 (pentafluorobenzoate) 2]
[0335] [L1Zn2 (adamantyl carboxylate) 2]
[0336] [L1Zn2 (diphenyl phosphinate) 2]
[0337] [L1Zn2 (bis (4-methoxy) phenyl phosphinate) 2]
[0338] [L4Mg2 (OAc) 2]
[0339] [L1Zn2 (hexanoate) 2],
[0340] [L1Zn2 (octanoate) 2],
[0341] [L1Zn2 (dodecanoate) 2], and

[0342] A catalyst of the sixth aspect is preferably a catalyst of formula (III), as described above, provided that the catalyst is not [Cθ2L1C12 (CH30H) 2] • H2O, [Cθ2L1Br2 (CH30H) 2] • H2O, [ Mn2L1C12 (CH3OH) 2] • H2O, [M ^ L ^^ CCHβOHH] • H2O, [CoIICoIIIL1C12Br (CH3θH)] • 0.5CH2C12, [MnIIMnIIIL1C12Br (CH3θH)], [FeIIIZnIIL1 (μ-0Ac) (0Ac) (0Ac) )] (Cl04) • H2O, [FeIIICoIIL1 (μ- OAc) (OAc) (H2O)] ClO4 • 2H2O, or [FeIIIMnIIL1 (μ- OAc) (OAc) (H2O)] (ClO4) • 2H2O.
[0343] It should be noted that the various resources described above for the catalyst of the sixth aspect may be present in combination mutatis mutandis. All the preferred features of the sixth aspect of the invention apply to the first aspect of the invention mutatis mutandis.
[0344] In a further aspect of the invention, a process is provided for the synthesis of a polycarbonate, the process comprising the step of reacting carbon dioxide with at least one epoxide in the presence of a catalyst of formula (III) as defined with respect to the sixth aspect of the invention and a chain transfer agent as defined with respect to the first aspect of the invention. The process features of the first aspect of the invention apply equally to that additional aspect mutatis mutandis.
[0345] The invention can be put into practice in several ways and several specific modalities will be described in the following non-limiting examples. EXAMPLES EXAMPLE 1: SYNTHESIS OF MATERIAL CATALYSTS AND METHODS
[0346] The H2L1 ligand, used in the following examples, has the following structure:

[0347] The H2L1 binder can be prepared as described in WO2009 / 130470, the total content of which is incorporated into the present as a reference.
[0348] GENERAL PROCEDURE FOR THE SUMMARY OF [L1MG2X2 (G)]
[0349] H2L1 (0.20 g, 0.36 mmol) was dissolved in THF (10 ml) and transferred to a Schlenk tube containing KH (0.44 g, 1.1 mmol) and cooled to -78 ° C , under nitrogen. The suspension was allowed to warm to room temperature and allowed to stir for 1 hour. Any excess KH was removed by filtration, the nucleophilic group G (0.36 mmol) was added to the solution and left stirring for 5 minutes, after which MgX2 (0.72 mmol) was added, slowly. The reaction was stirred for 16 hours, before the solution was filtered by centrifugation and the solvent removed in vacuo.
[0350] [L1Mg2Cl2 (methylimidazole)] (0.21 g, 0.28 mmol, 77%) Anal. Calc. for C38H60Cl2Mg2N6O2: C, 60.66; H, 8.04; N, 11.17. Found: C, 60.57; H, 8.12; N, 11.03. 1H NMR (Figure 2) (400 MHz, CDCl3) δ 8.60 (s, 1H, MeIm), 7.07 (s, 1H, MeIm), 6.88 (br s, 5H, Ar-H + MeIm ), 5.03 (s, 2H, NH), 4.08 (s, 2H, NH), 3.65 (s, 3H, MeIm), 3.39 and 1.76 (m, 16H, CH2), 1.22 (s, 24H, Ar-C-CH3 + NC-CH3), 0.99 (s, 6H, C-CH3). 13C NMR (101 MHz, CDCl3) δ: 159.1, 142.7, 137.3, 127.7, 126.3, 125.2, 120.3, 62.9, 55.6, 34.3 , 34.1, 33.4, 31.6, 28.2, 21.0. m / z (LSIMS) = 756 (100%, [M - Cl - methylimidazole] +.
[0351] [L1Mg2Cl2 (dimethylaminopyridine)] (0.2 g, 0.26 mmol, 72%). 1H NMR (400 MHz, CDCl3) δ 8.59 (d, J = 6.7, 2H, DMAP), 6.85 (s, 4H, Ar-H), 6.55 (d, J = 6, 9, 2H, DMAP), 4.53 (br s, 4H, NH), 3.06 (d, J = 12.0, 4H, N-CH2), 2.94 (s, 10H, N-CH3 + N-CH2), 2.74 (s, 4H, C-CH2), 2.19 (s, 4H, C-CH2), 1.27 (d, J = 10.6, 6H, C-CH3), 1.22 (s, 18H, Ar-C-CH3), 1.00 (s, 6H, C-CH3). 13C NMR (101 MHz, CDCl3) δ: 159.0, 154.6, 149.9, 137.2, 127.7, 125.1, 107.1, 62.9, 55.6, 39.0 , 34.5, 33.4, 31.6, 28.2, 21.2. m / z (LSIMS) = 756 (100%, [M - Cl - dimethylaminopyridine] +).
[0352] [L1Mg2Br2 (dimethylaminopyridine)] (0.27 g, 0.3 mmol, 84%) Anal. Calc. for C41H64Br2Mg2N6O2: C, 55.87; H, 7.32; N, 9.53. Found: C, 55.78; H, 7.34; N, 9.48. 1H NMR (Figure 3) (400 MHz, CD3CN) δ 8.29 (s, 2H, DMAP), 7.05 (s, 4H, Ar-H), 6.61 (d, J = 6.5, 2H, DMAP), 4.38 (s, 4H, NH), 3.20 (d, J = 12.2, 4H, CH2), 3.00 (s, 6H, N-CH3), 2.94 - 2.55 (m, 8H, CH2), 2.24 (s, 4H, C-CH2), 1.28 (s, 18H, Ar-C-CH3), 1.20 (s, 6H, C-CH3 ), 0.98 (s, 6H, C-CH3). 13C NMR (101 MHz, CDCl3) δ: 158.9, 149.5, 137.6, 128.1, 124.9, 124.4, 106.7, 62.3, 55.0, 38.3 , 33.9, 33.2, 30.9, 27.3, 20.9. m / z (LSIMS) = 678 (100%, [M - Br - dimethylaminopyridine] +).
[0353] Synthesis of [L1Zn2 (F3CCOO) 2]
[0354] H2L1 (0.25 g, 0.45 mmol) was dissolved in methanol (20 ml) and Zn (CF3COO) 2 (0.26 g, 0.90 mmol) was added. The mixture was stirred for 18 hours and the methanol removed in vacuo. The product was taken up in dichloromethane, filtered and the solvent removed in vacuo. The product, a white powder, was dried in a vacuum oven, in the presence of diphosphorus pentoxide, overnight.
[0355] [L1Zn2 (CF3COO) 2] (white powder; 0.30 g, 72%): Found: C, 50.2; H, 6.1; N, 6.1. Calc. for C38H54F6N4O6Zn2: C, 50.3; H, 6.0; N, 6.2. Vmax / cm-1 3,204 (N-H), 1,673 (C = O). (Figure 4) δH (400 MHz; CDCl3) Main isomer: 6.98 (s, 4H, Ar-H), 4.15 and 4.37 (br s, 4H, NH), 3.25 (d, J = 11.2 Hz, 4H, N-CH2-Ar), 3.00 (br s, 4H, N-CH2-Ar), 2.71 (d, J = 11.5 Hz, 4H, N-CH2- C), 2.37 (br s, 4H, N-CH2-C), 1.26 (s, 18H, Ar-CH3) 1.19 (s, 6H NC-CH3), 1.05 (s, 6H NC-CH3) δC (400 MHz; CDCl3) 161.69, 136.91, 127.79, 122.81, 114.69, 62.93, 55.84, 33.86, 33.52, 31.54 , 28.36, 20.72, δF (400 MHz; d4-methanol) -78.13 (s). m / z (FAB) 793 ([M -OAc] +, 100%).
[0356] Synthesis of [L1Zn2 (OOCC (CH3) 3) 2]
[0357] In a conceptacle in the closed chamber, KH (58 mg, 1.45 mmol) was added in small portions to a solution of H2L1 binder (200 mg, 0.36 mmol) in cold THF (10 ml). After 4 hours of stirring, the reaction mixture was centrifuged, then [Zn (OOCC (CH3) 3) 2] (194 mg, 0.72 mmol) was added to the colorless solution, instantly producing a cloudy white mixture, which was left stirring at room temperature for 20 hours. THF was removed in vacuo, then 10 ml of DCM added. Potassium carboxylate salts were eliminated by centrifugation and the white solid residue was finally washed with hexane (3 x 5 ml), then dried under vacuum for 20 hours.
[0358] [L1Zn2 (OOCC (CH3) 3) 2] (white powder, 300 mg, 0.46 mmol, 94%). m / z (LSIMS) (Figure 5): 781 ([M - OOCC (CH3) 3] +, 100%). ). δH (400 MHz; CDCl3) 6.88 and 6.97 (m, 4H, Ar-H), 2.46 and 4.59 (m, 20H, N-CH2-Ar and NH), 0.53 and 1 , 37 (m, 48H, Ar-CH3) ppm. Analysis calculated for C44H72Zn2N4O6: C, 59.79; H, 8.21; N, 6.34. Found: C, 59.68; H, 8.15; N, 6.35.
[0359] Synthesis of [L1Zn2 (OC6H5) 2]
[0360] In a conceptacle in the closed chamber, [Zn (OC6H5) (C2H5)] (136 mg, 0.72 mmol) was added in small portions to a solution of H2L1 binder (200 mg, 0.36 mmol) in THF cold (10 ml), instantly producing a white precipitate and the reaction mixture was allowed to stir at room temperature for 20 hours. The precipitate was separated by centrifugation and diluted with 10 ml of DCM. The cloudy solution was centrifuged and the DCM dried in vacuo. The white solid residue was finally washed with hexane (3 x 5 ml), then dried under vacuum for 20 hours.
[0361] [L1Zn2 (OC6H5) 2] (white powder, 273 mg, 0.31 mmol, 87%). δH (400 MHz; CDCl3) 6.88 and 6.97 (m, 4H, Ar-H), 2.46 and 4.59 (m, 20H, N-CH2-Ar and NH), 0.53 and 1 , 37 (m, 48H, Ar-CH3) ppm. Analysis calculated for C46H64Zn2N4O4: C, 63.66; H, 7.43; N, 6.46. Found: C, 63.59; H, 7.38; N, 6.45.
[0362] General procedure for the synthesis of [L1Co2Cl3] - [B-H] +
[0363] H2L1 (0.25 g, 0.45 mmol) was dissolved in THF (10 ml) in a Schlenk tube. The base (0.9 mmol) was added to the solution and left stirring for 1 hour. CoCl2 (0.12 g, 0.9 mmol) was added to the solution, slowly, to prevent the formation of [L1Co3Cl4] and the solution was left stirring overnight, after which a purple solution was found, with a white precipitate. The precipitate was filtered and the solvent removed, in vacuo, to yield a pink powder that was dried, under vacuum, for several hours,
[0364] [L1Co2Cl3] [HNEt3] (Figure 6) (0.33 g, 0.38 mmol, 84%): m / z (LSI +): 102 (100%, [HNEt3] +), (ESI-) : 803 (100%, [L1Co2 (HCO2) 3] -), 793 (20%, [L1Co2Cl (HCO2) 2] -). Anal. Calc. for C40H70Cl3Co2N5O2: C, 54.77; H, 8.04; N, 7.98. Found: C, 54.84; H, 7.98; N, 8.02. UV-Vis Àmax / nm (ε / dm3mol-1cm-1): 473 (67.9), 541 (61.8), 565 (52.3).
[0365] [L1Co2Cl3] [HDBU] (0.33 g, 0.0.36 mmol, 79%): m / z: (LSI +): 153 (100%, [H-DBU] +), (ESI- ): 803 (100%, [L1Co2 (HCO2) 3] -), 793 (25%, [L1Co2Cl (HCO2) 2] -). Anal. Calc. for C43H71Cl3Co2N6O2: C, 55.64; H, 7.71; N, 9.05. Found: C, 55.69; H, 7.79; N, 9.08.
[0366] [L1Co2Cl3] [HMTBD] (0.31 g, 0.33 mmol, 74%): m / z: (LSI +): 154 (100% [H-MTBD] +), m / z (ESI- ) 803 (100%, [L1Co2 (HCO2) 3] -), 793 (20%, [L1Co2Cl (HCO2) 2] -). Anal. Calc. for C42H70Cl3Co2N7O2: C, 54.28; H, 7.59; N, 10.55%. Found: C, 54.16; H, 7.65; N, 10.41%.
[0367] General procedure for the synthesis of [L1Co2Cl2 (G)]
[0368] H2L1 (0.40 g, 0.72 mmol) was dissolved in THF (10 ml) and transferred to a Schlenk tube containing KH (0.87 g, 2.20 mmol) and cooled to -78 ° C , under nitrogen. The suspension was allowed to warm to room temperature and allowed to stir for 1 hour. Any excess KH was filtered, the nucleophilic group G (0.72 mmol) was added to the solution and left stirring for 5 minutes, after which CoCl2 was added, slowly. The solution initially turned dark blue in addition, but after being left stirring overnight, a dark red solution was developed. The solution was filtered and the solvent removed in vacuo.
[0369] [L1Co2Cl2 (pyridine)] (Figure 7) (0.32 g, 0.39 mmol, 54%): m / z (LSI +): 703 (100%, [L1Co2Cl] +). Anal. Calc. for C38H60Cl2Co2N6O2: C, 55.54; H, 7.36; N, 10.23. Found: C, 55.68; H, 7.50; N, 10.05.
[0370] [L1Co2Cl2 (methylimidazole)] (0.47 g, 0.54 mmol, 75%): m / z (LSI +): 703 (100%, [L1Co2Cl] +). Anal. Calc. for C41H64Cl2Co2N6O2: C, 57.15; H, 7.49; N, 9.75. Found: C, 57.19; H, 7.59; N, 9.63. UV-Vis Àmax / nm (ε / dm3mol-1cm-1): 473 (95.7), 538 (82.4).
[0371] [L1Co2Cl2 (dimethylaminopyridine)] (0.42 g, 0.53 mmol, 70%): m / z (LSI +): 703 (100%, [L1Co2Cl] +). Anal. Calc. for C39H59Cl2Co2N5O2: C, 57.22; H, 7.26; N, 8.55. Found: C, 57.12; H, 7.26; N, 8.46. UV-Vis Àmax / nm (ε / dm3mol-1cm-1): 474 (95.9), 509 (78.9), 535 (76.3). EXAMPLE 2: COOPOLIMERIZATION OF CO2 AND AN EPOXIDE
[0372] General CO2 / cyclohexene oxide copolymerization procedure
[0373] All low pressure catalytic reactions were performed in magnetically agitated Schlenk tubes, using Schlenk techniques. The Schlenk tubes were dried, in an oven at 140 ° C, for 20 hours before any use. In a typical reaction, cyclohexene oxide (2.5 ml, 24.7 mmoles) and the catalyst were added to a Schlenk tube. The cyclohexene oxide was rapidly degassed, before being stirred under 101.32 kPa (1 atm) of CO2 (continuously fed using a reserve cylinder), at 80 ° C, for 24 hours. At the end of the reaction, the crude reaction mixture was taken up in CH2Cl2 and 0.2 ml of a 5% HCl / MeOH solution was added. The solution was evaporated in air, after which the product was dried, in vacuo, overnight. No further purification of the product was performed as the vacuum was sufficient to remove unreacted cyclohexene oxide. Selectivity was determined by normalizing the integrals of the methylene proton resonances in the 1H NMR spectra, including copolymer carbonate bonds (broad signal δ = 4.65 ppm), copolymer ether bonds (broad signal δ = 3 , 45 ppm) and cyclic carbonate (multiplets: δ = 3.9 ppm (trans-CHC) or 4.63 ppm (cis-CHC)). The conversion was calculated as [(mass of the isolated product - weight of the catalyst) / 142.1] / moles of starting CHO. The renewal number (TON) was calculated as conversion / moles of catalyst. The renewal frequency (TOF) was calculated as TON / reaction time (in hours).
[0374] Table 1: Catalytic activities of complexes synthesized in Example 1


[0375] Copolymerization conditions: Cat (0.1 mol% - 1: 1,000), 80 ° C, 101.32 kPa (1 atm) of CO2. a) Catalyst loading 0.05 mol% (1: 2,000). b) Catalyst loading 0.025 mol% (1: 4,000).
[0376] Example 3: Polymerization of CO2 and an epoxide in the presence of a chain transfer agent (CTA) and subsequent reactions with additional monomers
[0377] Experimental details for CTA experiments with [L1Zn2 (OAc) 2] (Complex 1)
[0378] An oven-dried Schlenk tube was loaded with catalyst (x mmol), CHO (2.5 ml, 25 mmol) and CTA (x mmol) under nitrogen. The Schlenk tube was evacuated and refilled with CO2 (101.32 kPa (1 atm)) three, before being left under a constant flow of CO2. The reaction was heated to temperature and stirred under a constant flow of CO2 for the desired time.
[0379] Table 2: Copolymerization of CHO and CO2 using Complex 1, with several species added as chain transfer agents (CTA). Copolymerization conditions: pure CHO, 80 ° C, 24 hours, 100 kPa (1 bar) of CO2.

[0380] at TON = (converted molCHO) x (molcomplex 1) -1. TOF = TON per hour. c Scarbonate = Percentage selectivity for carbonate bonds (PCHC + CHC), as determined from the normalized integrals in the 1H NMR spectra using methylene resonances, including PCHC (δ: 4.65 ppm), ether bonds (δ: 3.45 ppm) and CHC (δ: 3.9 ppm). d Selectivity for PCHC within carbonate products / e Determined by GPC, in THF, with the use of restricted Mn polystyrene standards, for calibration. f CHD = cyclohexane-1,2-diol.
[0381] Experimental details for CTA experiments with [L1Co2 (OAc) 3] / ethylene glycol and subsequent block copolymerization with (rac / L) -lactide

[0382] Scheme 1: Copolymerization of CHO and CO2 with the use of ethylene glycol as a chain transfer agent. i) [L1Co2 (OAc) 3] (0.1 mol%), 101.32 kPa (1 atm) CO2, 80 ° C.
[0383] Low pressure copolymerization of CHO and CO2 with [L1Co2 (OAc) 3] and ethylene glycol
[0384] Cyclohexene oxide (5 ml, 25 mmol), [L1Co2 (OAc) 3] (0.042 g, 0.049 mmol) and ethylene glycol (1 to 20 equivalents) were added to a Schlenk tube. The cyclohexene oxide was degassed, before being stirred under 101.32 kPa (1 atm) of CO2, at a defined temperature, for 4 hours. The crude product was taken up in CH2Cl2 and the solution was allowed to evaporate in air, after which the product was dried in vacuo overnight. No further purification of the polymer was performed as the vacuum was sufficient to remove unreacted cyclohexene oxide. Figure 8 shows a MALDI-TOF spectrum of the polycarbonate produced by the method above. It can be seen that all polymers produced by this method are terminated with hydroxyl groups at both ends of the polymer chains.
[0385] HO-PCHC-OH block copolymerization with (rac / L) -lactide
[0386] Under a nitrogen atmosphere in a closed chamber, (rac / L) -lactide (0.5, 1 or 2 mmoles) was placed in a conceptacle with a stir bar and dissolved in THF (1.5 ml). Separately, PCHC (0.005 mmol) was placed in a conceptacle with Y (5.4 mg, 0.1 mmol) and dissolved in THF (0.5 ml). This solution was then added to the lactide solution and stirred for approximately 5 minutes, until the viscosity had increased, so that the stirring no longer needed to continue. The reaction was terminated and the polymer precipitated by the addition of hexane (approximately 2 ml). The polymer was removed by filtration and dried in vacuo. (Figure 9)

[0387] Scheme 2: PCHC block copolymerization with lactide. i) 1 (2 equiv.), lactide (200 or 400 equiv.), THF, 25 ° C, 5 minutes.
[0388] CHO copolymerization with [L1Zn2 (O2CCF3) 2] producing HO-PCHC-OH and subsequent block copolymerization with (rac / L) -lactide

[0389] Scheme 3: CHO copolymerization and subsequent block copolymerization with lactide. i) [L1Zn2 (O2CCF3) 2] (0.1 mol%), 80 ° C, 101.32 kPa (1 atm) of CO2, 24 hours. ii) Y (2 equiv.), THF, 25 ° C, 5 minutes.
[0390] Copolymerization conditions
[0391] Cyclohexene oxide (2.5 ml, 25 mmoles) and [L1Zn2 (F3CCOO) 2] (0.022 g, 0.025 mmol) were added to a Schlenk tube. The vessel was evacuated and charged with 101.32 kPa (1 atm) of CO2 after which it was left stirring at 80 ° C for 24 hours. The crude reaction mixture was then taken up in CH2Cl2 (10 ml) and evaporated in air. The product was then dried in vacuo overnight. This proved to be sufficient to remove the unreacted monomer, no further purification was required. (Figures 10 and 11)
[0392] Block copolymerization conditions
[0393] Under a nitrogen atmosphere in a closed chamber, (rac / L) -lactide () was placed in a conceptacle with a stir bar and dissolved in THF (1.5 ml). Separately, Poly (cyclohexene carbonate) (0.05 mmol) was placed in a conceptacle with Y (5.4 mg, 0.1 mmol) and dissolved in THF (0.5 ml). This solution was then added to the lactide solution and stirred for approximately 5 minutes, until the viscosity had increased, so that the stirring no longer needed to continue. The reaction was terminated and the polymer precipitated by the addition of hexane (approximately 2 ml). The polymer was removed by filtration and dried in vacuo. (Figure 11)
[0394] Table 3: PCHC and PLA block copolymerization

[0395] aDetermined by gel permeation chromatography with the use of THF as an eluent, against restricted polystyrene standards. bDetermined by relative integrals of Hb and Hc in 1H NMR spectrum cDetermined by relative integrals of proton PCHC Hd vs PCHC carbonate protons Hc vs lactide plus the known weight of PCHC. dDetermined by relative integrals of PLA and unreacted lactide in 1H NMR spectrum. EXAMPLE 3: COPOLIMERIZATION OF CARBON DIOXIDE AND CYCLEHEXEN OXIDE (CHO) IN THE PRESENCE OF SEVERAL CHAIN TRANSFER AGENTS (CTAS)
[0396] The zinc catalysts 1 ([L1Zn2 (OAc) 2]) and 2 ([L1Zn2 (CF3COO) 2]) were sweated, in a 0.1 mol% stoichiometry, to copolymerize cyclohexene oxide (CHO) and carbon dioxide, with the addition of 0.4 mol% of chain transfer agents from A to Q or water, to produce polyols and polycyclohexene oxide carbonate diols.


[0397] Each of the reactions was performed using the following reaction conditions:
[0398] 0.1 mol% catalyst loading, 80 ° C, 700 rpm stirring speed, 0.4 mol% chain transfer agent (CTA), 5 ml CHO.
[0399] Tables 4 and 5 show the catalyst activities and percentage conversions for each reaction.
[0400] Table 4: Zinc catalyst 1 ([L1Zn2 (OAc) 2])

[0401] Table 5: Zinc catalyst 2 ([L1Zn2 (CF3COO) 2])

[0402] The above results show that the catalysts of the invention are compatible with a wide range of chain transfer agents.
[0403] In an additional set of experiments, zinc catalysts 1 ([L1Zn2 (OAc) 2]) and 2 ([L1Zn2 (CF3COO) 2]) were used, in a 0.1% mol% stoichiometry, to copolymerize cyclohexene oxide (CHO) and carbon dioxide, with the addition of 0.1 mol% to 10 mol% of water as a chain transfer agent, to produce polycyclohexene oxide carbonate diols.
[0404] Tables 6 and 7 show the catalyst activities and percentage conversions for each reaction.
[0405] Table 6: Zinc catalyst 1 ([L1Zn2 (OAc) 2])

[0406] Table 7: Zinc catalyst 2 ([L1Zn2 (CF3COO) 2])

EXAMPLE 4: COPOLIMERIZATION OF CARBON DIOXIDE AND CYCLEHEXEN OXIDE (CHO) IN THE PRESENCE OF WATER AS A CHAIN TRANSFER AGENT
[0407] These magnesium catalysts 2a, 2b and 2c were used to copolymerize CHO and carbon dioxide with and without exogenous water as a chain transfer agent.

[0408] Catalysts 2a and 2b were prepared by deprotonation of the macrocyclic ligand H2L1, using KH, followed by a salt metathesis reaction with two equivalents of the appropriate Mg precursor (Mg (OAc) 2, MgBr2. 2c was prepared by reacting 2b with 2 K equivalents (O2CCF3) in THF at room temperature.
[0409] Each reaction was run in pure CHO at a pressure of 101.32 kPa (1 atm) of CO2 and catalyst loading of 1: 1,000 for 3 to 18 hours. Table 8 shows the results of the polymerization reactions.
[0410] Table 8: copolymerization data for catalysts 2a to 2c

[0411] copolymerization performed in 1,215 kPa (12 atm) of CO2 and loading of 1: 10,000; b mol of CHO consumed / mole of cat .; c TON / time (h); d by size exclusion chromatography (SEC) in gmol-1.
[0412] Copolymers formed with 2c were analyzed by MALDI-ToF mass spectrometry (not shown) and SEC (Figure 15), which showed terminal groups from both transfer and chain initiation reactions (Y = OH and O2CCF3; respectively ). In the case of 2c, a significant reduction in HO-PCHC-O2CCF3, that is, a monohydroxyl peak was observed by SEC analysis compared to the copolymer produced by 2a (see Figure 15). This indicated that 2c should show marked selectivity for polyol formation. In order to promote the formation of selective polyol, copolymerization was performed using water, 10 and 30 equivalents versus 2c, as a chain transfer agent. These experiments show that water is an effective chain transfer agent, reducing molecular weight and producing more restricted weight distributions.
[0413] Almost complete suppression of trifluoroacetate end groups was seen when 30 equivalents of water were added (Figure 15). By analyzing the 1H NMR spectrum of the copolymer, it was estimated that 2c produces approximately 50% polyol in the absence of additional water. By adding 30 equivalents of water, selectivity for polyol increases up to approximately 85%. Even using excess water, 2c still shows a catalytic activity (c.f. 2a under the same conditions without water, table 8, entry 4).
[0414] Furthermore, even in the presence of excess water, 2c maintains a high selectivity for copolymer formation (> 99% carbonate bonds,> 99% selectivity for copolymer by 1H NMR). This is particularly noteworthy since other catalysts that are used to co-polymerize CO2 and epoxides are deactivated by water, leading to complete suppression of catalytic activity (Seong, JE et al; Macromolecules 2010, 43, 903 to 908; Lu, X.-B .; Darensbourg, DJ Chem. Soc. Rev. 2012, 41, 1,462 to 1,484; Na, S. J et al; Inorg. Chem. 2009, 48, 10,455 to 10,465). Such a high tolerance for excess water is especially relevant for the integration of this process with carbon capture due to the fact that water is a common contaminant of captured carbon dioxide, including typical concentrations of approximately 2% in carbon dioxide captured from gases combustion of coal combustion. EXAMPLE 5: COPYLIMERIZATION OF CYCLEHEXEN OXIDE AND CO2 IN THE PRESENCE OF SEVERAL CATALYSTS
[0415] The activity of innovative catalysts [L1Zn2 (hexanoate) 2], [L1Zn2 (octanoate) 2] and [L1Zn2 (dodecanoate) 2] has been tested and compared to the catalyst [L1Zn2 (OAc) 2]).
[0416] Each of the reactions was carried out at 80 ° C, 101.32 kPa (1 atm) of CO2 and 0.1% catalyst loading. The results of these tests are shown in table 9.
[0417] Table 9: activity of innovative catalysts and catalyst [L1Zn2 (OAc) 2].

[0418] Example 6: Copolymerization of cyclohexene oxide and CO2 in the presence of various catalysts
[0419] The activity of innovative catalysts that have the formula [L1Zn2X2] has been tested and the results of these tests are shown in table 10 below.
[0420] Table 10: activity of innovative catalysts

[0421] Example 7: Synthesis of L4Mg2 (OAc) 2

[0422] The synthesis of 2,6-diacetyl-4-tert-butylphenol was performed using a literature procedure (Aromi et al, Synth. Comm. 2003, 33, 11 to 18.). The synthesis of L4 was performed using the procedure described in WO2009 / 130470 for the synthesis of L1, in 66% of the general yield, by substituting 2,6-diformil-4-tert-butylphenol with 2,6-diacetyl- 4-tert-butylphenol.
[0423] L4: Anal. Calc. for C38H64N4O2: C, 74.95; H, 10.59; N, 9.20. Found: C, 74.84; H, 10.54; N, 9.27. 1H NMR (400 MHz, CDCl3) δ: 7.10 and 6.80 (m, 4H, Ar-H), 4.10 and 3.70 (m, 4H, NH), 2.60 and 2.10 (m, 8H, C-CH2-N), 1.50 and 1.40 (m, 12H), 1.30 (m, 18H), 1.10 and 0.90 (m, 12H). m / z (ESI) = 609 (100%, [M + H] +).
[0424] H2L4 (0.12 g, 0.20 mmol) was dissolved in THF (10 ml) and transferred to a Schlenk tube containing KH (0.020 g, 0.49 mmol) and cooled to -78 ° C, under nitrogen. The suspension was allowed to warm to room temperature and allowed to stir for 1 hour. Any excess KH was removed by filtration, after which MgOAc2 (0.056 g, 0.39 mmol) was added, slowly. The reaction was stirred for 16 hours, before the solution was filtered by centrifugation and the solvent removed in vacuo.
[0425] L4Mg2 (OAc) 2: Anal. Calc. for C42H68Mg2N4O6: C, 65.21; H, 8.86; N, 7.24. Found: C, 65.11; H, 8.70; N, 7.18. 1H NMR (400 MHz, d2-TCE, 373K) δ: 7.05 and 6.70 (br m, 4H), 4.40 and 1.80 (br m, 14H), 1.60 - 0.80 (br m, 42H), m / z (LSIMS) = 713.5 (100%, [M -OAc] +).

权利要求:
Claims (15)
[0001]
1. PROCESS FOR THE SYNTHESIS OF A POLYCARBONATE, the process being characterized by the stage of reacting carbon dioxide with at least one epoxide in the presence of a catalyst of the formula (I):
[0002]
PROCESS according to claim 1, characterized in that G is independently an optionally substituted heteroaliphatic group, an optionally substituted heteroalicyclic group, an optionally substituted heteroaryl group, a halide, hydroxide, hydride, a carboxylate, an ether, a thioether , carbene, a phosphine, a phosphine oxide, an amine, an acetamide, acetonitrile, an ester, a sulfoxide, a sulfonate or water.
[0003]
PROCESS according to claim 1, characterized in that the chain transfer agent is water, a monoalcohol, a diol, a triol, a tetraol, a polyol, a monoamine, a polyamine, a monothiol, a polyol, an acid monocarboxylic or a polycarboxylic acid.
[0004]
4. PROCESS, according to claim 1, characterized in that the chain transfer agent is selected from the group consisting of water, diphenylphosphonic acid, 4-ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol , cyclohexanol, 1,2-ethanediol, 1-2-propanediol, 1,3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, catechol, cyclohexenediole, glycerol, benzenotriol, 1,2,4-butanotriol, tris (methyl alcohol) propane, tris (methyl alcohol) ethane, tris (methyl alcohol) ) nitropropane, D - (+) - glucose, D-sorbitol, calix [4] arene, 2,2-bis (methyl alcohol) -1,3-propanediol, polylactic acid, poly (ethylene glycol), starch, lignin, methylamine , dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, 1,4-butanediamine, 3,5-di-tert-butylbenzoic acid, maleic acid, malonic acid, succinic acid co, glutaric acid, terephthalic acid, citric acid, 1,3,5-benzenestricarboxylic acid, 1,3,5-cyclohexanotricarboxylic acid, lactic acid, glycolic acid and 3-hydroxypropionic acid.
[0005]
PROCESS, according to claim 1, characterized in that the chain transfer agent is present in a molar ratio between 1: 1 and 100: 1 in relation to the metal complex.
[0006]
6. PROCESS, according to claim 1, characterized in that R5 is hydrogen.
[0007]
7. PROCESS according to claim 1, characterized in that X is independently OC (O) Rx, OSO2Rx, OSO (Rx) 2, ORx, halide, nitrate, hydroxyl, carbonate, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or optionally substituted heteroaryl.
[0008]
8. POLYMERIZATION SYSTEM, for the copolymerization of carbon dioxide and at least one epoxide, characterized by comprising: a) a catalyst of formula (I), as defined in claim 1, and b) a chain transfer agent of formula ( II), as defined in claim 1.
[0009]
9. METHOD TO PRODUCE THE COPOLYMER OF FORMULA B - (- A) N, characterized in that B is a polycarbonate as produced by the process as defined in claim 1, and each A is an additional polymeric unit, the method comprising the steps of: a ) sintering a polycarbonate by the process as defined in claim 1, and b) ii) - reacting the polycarbonate with at least one additional monomer, or c) i) - reacting the polycarbonate with at least one additional polymeric unit.
[0010]
10. METHOD, according to claim 9, characterized by step b) ii) or iii) IN SITU, directly after step a).
[0011]
11. METHOD according to claim 9, characterized in that A is a polymer formed by at least one monomer that is initiated by hydroxyl groups.
[0012]
METHOD according to claim 9, characterized in that A is a polymer formed by lactide, lactone, epoxide, cyclic carbonate, epoxide monomers or combinations thereof, or a combination of an epoxide and an anhydride and / or carbon dioxide and / or a di- or polycarboxylic acid, or a combination of a diisocyanate and a compound comprising two or more hydroxyl groups, or wherein A is a polyester, polyether, polycarbonate, polyamide, polyurethane or any combination of copolymers thereof .
[0013]
PROCESS according to claim 1, characterized in that the chain transfer agent is present in a molar ratio of at least 2: 1 relative to the catalyst of formula (I).
[0014]
PROCESS according to claim 1, characterized in that the chain transfer agent is present in a molar ratio of at least 4: 1 relative to the catalyst of formula (I).
[0015]
PROCESS according to claim 1, characterized in that the chain transfer agent is present in a molar ratio of at least 8: 1 relative to the catalyst of formula (I).

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-16| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-12-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-02-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GB1115565.2|2011-09-08|

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GBGB1115565.2A|GB201115565D0|2011-09-08|2011-09-08|Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent|

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PCT/EP2012/067588|WO2013034750A2|2011-09-08|2012-09-07|Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent|

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