CATALYST, PROCESS AND PRODUCT

专利摘要:
The present invention relates to the field of polymerization catalysts and to systems comprising these catalysts for polymerizing carbon dioxide and an epoxide, a lactide and / or lactone and / or an epoxide and an anhydride. The catalyst is of formula (I): (Formula (I)) in which at least one of M1 or M2 is selected from Ni (II) and Ni (III) -X. A process for reacting carbon dioxide with an epoxide; an epoxide and an anhydride; and / or a lactide and / or a lactone in the presence of the catalyst is also described.
公开号:BR112017001081B1
申请号:R112017001081-0
申请日:2015-07-22
公开日:2020-12-29
发明作者:Colin KEYWORTH；Andy CHAPMAN；Anthony CHARTOIRE；Emma HOLLIS；Charlotte Williams；Michael Kember
申请人:Econic Technologies Ltd；
IPC主号:

专利说明:

Field of Invention
The present invention relates to the field of polymerization catalysts and systems comprising said catalysts for polymerizing carbon dioxide and an epoxide, a lactide and / or lactone and / or an epoxide and an anhydride. Foundations
[002] Environmental and economic concerns associated with the depletion of oil resources have triggered an increasing interest in the chemical conversion of carbon dioxide (CO2) in order to allow its use as a renewable carbon source. CO2 is, in spite of its low reactivity, a highly attractive carbon feed stock, as it is cheap, virtually non-toxic, abundantly available in high purity and is not harmful. Therefore, CO2 can be a promising substitute for substances such as carbon monoxide, phosgene or other petrochemical feed stocks in many processes. One of the applications in CO2 development is copolymerization with epoxides to produce aliphatic polycarbonates. The development of effective catalysts to carry out such a useful process is the goal of continuous research.
[003] In WO2009 / 130470, the contents of which are incorporated herein by reference in their entirety, the copolymerization of an epoxide with CO2 using a catalyst of a class represented by formula (I) has been described:

[004] WO2013 / 034750, whose contents are incorporated in this reference in its entirety, discloses the copolymerization of an epoxide with CO2 in the presence of a chain transfer agent using a catalyst of a class represented by the formula (II):

[005] Various compounds according to formulas (I) and (II) above have been tested for their ability to catalyze the reaction between different epoxides and carbon dioxide. In both WO2009 / 130470 and WO2013 / 034750, M is specified as being selected from 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.
[006] Among the epoxides used in the copolymerization reactions of the prior art, cyclohexene oxide (CHO) received special interest, as the product, poly (cyclohexene carbonate) (PCHC) shows a high glass transition temperature and reasonable tensile strength. Ethylene oxide, propylene oxide and butylene oxide have also been of interest when they produce polymers (polyalkylene carbonates, such as PPC) with elastomeric properties that are useful in many applications, for example, films.
[007] WO2012 / 037282 discloses a catalyst of the formula:

[008] WO2012 / 037282 indicates that these compounds can be useful for the copolymerization of an epoxide with CO2. WO2012 / 037282 establishes that M1 and M2 can be any metal atom. However, these complexes have not been tested to determine whether anyone has the necessary catalytic activity.
[009] The inventors have now surprisingly observed that bimetallic catalysts having at least one nickel metal center, are active as polymerization catalysts. In particular, the inventors have observed that bimetallic catalysts having at least one nickel metal center and, preferably, having two nickel metal centers, are better in terms of activity and / or selectivity than the catalysts previously disclosed in the art. In particular, the catalysts of the invention have improved activity in the reaction to bisubstituted meso-epoxides (e.g., cyclohexene oxide) and monosubstituted epoxides (for example, propylene oxide) and, in addition, improved selectivity to monosubstituted epoxides. Summary of the Invention
[0010] According to a first aspect of the present invention, a catalyst of formula (I) is provided:
where: M1 and M2 are independently selected from Zn (II), Cr (II), Co (II), Cu (II), Mn (II), Mg (II), Ni (II), Fe (II), Ti (II), V (II), Cr (III) -X, Co (III) - X, Mn (III) -X, Ni (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; wherein at least one of M1 or M2 is selected from Ni (II), and Ni (III) -X; R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an alicyclic or heteroalicyclic alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio optionally substituted group; R3 is independently selected from alkylene, alkenylene, alkylene, heteroalkenylene, heteroalkenylene, heteroalkenylene, arylene, heteroarylene or cycloalkylene optionally substituted, in which alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkenylene, can be optionally interrupted by aryl, heteroalicylic, aryl, heteroalkenyl heteroalicyclic; R5 is independently selected from H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or optionally substituted alkylaryl; E1 is C, E2 is O, S or NH or E1 is N and E2 is O; E3, E4, E5 and E6 are selected from N, NR4, O and S, where when E3, E4, E5 or E6 are N, it is == m and when E3, E4, E5 or E6 are NR4, O or S, is; R4 is independently selected from H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or optionally substituted alkylaryl; X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, S (O) Rx, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, nitro, starch or aliphatic, heteroaliphatic, alicyclic , optionally substituted, heteroalicyclic, aryl or heteroaryl; Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted and G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base.
[0011] In a second aspect of the invention, a process is provided for the reaction of (i) carbon dioxide with an epoxide, (ii) an anhydride and an epoxide and / or (iii) a lactide and / or a lactone in the presence of a catalyst according to the first aspect, optionally in the presence of a chain transfer agent.
[0012] The third aspect of the invention provides a product of the process of the second aspect of the invention.
[0013] In another aspect, the invention extends to methods of preparing ligands, complexes and catalysts according to the first aspect and / or as defined herein. Definitions
[0014] For the purpose of the present invention, an aliphatic group is a hydrocarbon moiety that can be straight or branched and can be completely saturated or contain one or more unsaturation units, but which is not aromatic. The term "unsaturated" means a portion 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, that is, an aliphatic group having 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.
[0015] 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 a C1-6 alkyl group. Specifically, examples of "C1-20 alkyl groups" 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, 1-ethylpropyl group, 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, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group and others.
[0016] The alkenyl and alkynyl groups are preferably "C2-20 alkenyl" and "C2-20 alkenyl", more preferably "C2-15 alkenyl" and "C2-15 alkenyl" groups, even more preferably "C2-12 alkenyl" and "C2-12 alkynyl", even more preferably "C2-10 alkenyl" and "C2-10 alkenyl", even more preferably "C2-8 alkenyl" and "C2-8 alkenyl", more preferably "C2-6 alkenyl" and "C2-6 alkynyl", respectively.
[0017] A heteroaliphatic group (including heteroalkyl, heteroalkenyl and heteroalkynyl) and an aliphatic group as described above, additionally containing one or more heteroatoms. The 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.
[0018] An alicyclic group is a saturated or partially unsaturated monocyclic or polycyclic aliphatic ring system (including fused, bridged and spiro-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, even more preferably 3 to 6 carbon atoms. The term "alicyclic" encompasses cycloalkyl, cycloalkenyl and cycloalkynyl groups. It will be appreciated that the alicyclic group may comprise an alicyclic ring may comprise a ring that carries one or more alkyl bonding or non-bonding substituents, such as -CH2-cyclohexyl. Specifically, examples of the C3-20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and cyclooctyl.
[0019] A heteroalicyclic group is an alicyclic group as defined above having, in addition to carbon atoms, one or more ring hetero atoms, 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. Heteroalicyclic groups preferably contain from 5 to 20 atoms, more preferably from 5 to 14 atoms, even more preferably from 5 to 12 atoms.
[0020] An aryl group is a monocyclic or polycyclic ring system having 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 monocyclic ring group or cyclic ring group and others. Specifically, examples of "C6-10 aryl group" include phenyl group, biphenyl group, indenyl group, naphthyl group or azulenyl group and others. It should be noted that condensed rings, such as indane and tetrahydro naphthalene are also included in the aryl group.
[0021] A heteroaryl group is an aryl group having, 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, methylimidazole and dimethylaminopyridine.
[0022] Examples of alicyclic groups, heteroalicyclic, aryl, and heteroaryl include, but are not limited to cyclo-hexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, ditiane , dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, naptiridine, oxazole, oxadiazine, oxadiazine, oxatiazine, oxatiazine, oxatiazine, oxatiazine , phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazol, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinoline, tetrahydrofin, tetrahydrofin, tetrahydrofin, tetrahydrofin, tetrahydrofin, tetrahydrofin , thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazine, triazole and tritian.
[0023] The term "halide" or "halogen" are used interchangeably and, as used here means a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and others, preferably a fluorine atom, a bromine atom or a chlorine atom and more preferably a fluorine atom.
[0024] A haloalkyl group, 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 is a C1-20 alkyl group, a C1-15 alkyl, a C1-12 alkyl, a C1-10 alkyl, a C1-8 alkyl or a C1-6 alkyl, respectively, as described above replaced by at least one halogen atom, preferably 1, 2 or 3 halogen atoms. Specifically, examples of "C1-20 haloalkyl group" include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluroethyl group, trifluoroethyl group, chloromethyl group, bromomethyl group, iodomethyl group and others.
[0025] 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 "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, group n-pentyloxy, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, isohexyloxy group, n-hexyloxy, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n group -undecyloxy, 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-nonyl group , 1-dimethylpropoxy, 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, group 1,2-dimethylbutoxy, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2-ethylbutoxy group, 2-methylpentyloxy group, 3-methylpentyloxy group and others.
[0026] An aryloxy group is preferably a "C5-20 aryloxy group", more preferably a "C6-12 aryloxy group", even more preferably a "C6-10 aryloxy group" and is an oxide group that is attached to the aryl group C5-20, C6-12 aryl or C6-10 aryl previously defined, respectively.
[0027] An alkylthio group is preferably "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", still more preferably a "C1-8 alkylthio group", even more preferably a "C1-6 alkylthio group" and it is a thio 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.
[0028] An arylthio group is preferably a "C5-20 arylthio group", more preferably an "C6-12 arylthio group", even more preferably an "C6-10 arylthio group" and is an unio (-S-) group that is linked to the previously defined aryl C5-20, C6-12 aryl or C6-10 aryl group, respectively.
[0029] An alkylaryl group is preferably a "C6-12 aryl C1-20 alkyl group", more preferably a "C6-12 aryl C1-16 alkyl group", even more preferably a "C6-12 aryl C1-6 alkyl group" ”And is an aryl group as defined above attached at any position to an alkyl group as defined above. The point of attachment of the alkylaryl group to a molecule and can be through the alkyl moiety and, therefore, preferably, the alkylaryl group is -CH2-Ph or -CH2CH2-Ph. An alkylaryl group can also be referred to as "aralkyl".
[0030] A silyl group is preferably a -Si (Rs) s group, where each Rs can independently be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each Rs is independently an aliphatic, alicyclic or non-aliphatic aryl. Preferably, each Rs is an alkyl group selected from methyl, ethyl or propyl.
[0031] A silyl ether group is preferably an OSi (R6) 3 group wherein each R6 can independently be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group, as defined above. In certain embodiments, each R6 can be independently an aliphatic, alicyclic or unsubstituted aryl. Preferably, each R6 is an optionally substituted phenyl or optionally substituted alkyl group selected from methyl, ethyl, propyl or butyl (such as n-butyl or tert-butyl (tBu)). Exemplary silyl ether groups include OSi (Me) 3, OSi (Et) 3, OSi (Ph) 3, OSi (Me) 2 (tBu), OSi (tBu) 3 and OSi (Ph) 2 (tBu).
[0032] A nitrile group (also referred to as a cyano group) is a CN group.
[0033] 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.
[0034] An acetylide group contains a triple bond -C = C-R9, preferably where R9 can be hydrogen, 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 group, a silyl, aryl or heteroaryl group as defined above. It will be estimated that when the amino group is N (R10) 2, each R10 group can be the same or different. In certain embodiments, each R10 is independently an aliphatic, alicyclic, silyl or unsubstituted aryl. Preferably R10 is methyl, ethyl, propyl, SiMe3 or phenyl.
[0036] A starch group is preferably -NRIIC (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. The starch group can be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.
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. The ester group can be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.
[0038] A sulfoxide is preferably -S (O) R13 and a sulfonyl group is preferably -S (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.
[0039] 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 (e.g., 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.
[0040] 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.
[0041] A phosphinate group is preferably an -OP (O) (R16) 2 or -P (O) (OR16) group in which each R16 is independently selected from hydrogen or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl group or heteroaryl as defined above. In certain embodiments, R16 is aliphatic, alicyclic or aryl, which are optionally replaced 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) .
[0042] The sulfinate group is preferably -OSOR17 where R17 may 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.
[0043] A carbonate group is preferably OC (O) OR18, where R18 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R18 is aliphatic, alicyclic or optionally substituted aryl. Preferably, R18 is hydrogen, methyl, ethyl, propyl, butyl (for example, n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyla, octyl, nonila, decila, undecila, dodecila, tridecila, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl or adamantyl.
[0044] It will be estimated that when any of the above groups are present on a Lewis G basis, one or more additional R groups may be present, as appropriate, to complete the valency. For example, in the context of an amino group, an additional R group may be present to give RNHR10., 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.
[0045] Any of the aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, haloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylaryl, silyl, silyl ether, ester, sulfoxide, sulfonyl, carboxylate, carbonate, imine, acetate amino, phosphinate, sulfonate or starch, when mentioned in the definitions above and, can be optionally substituted by halogen, hydroxy, nitro, carboxylate, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, starch, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, phosphinate, sulfonate or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl optionally substituted groups (for example, optionally substituted by halogen, hydroxy, nitro, carbonate, alkoxy, aryloxy alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinate, sulfonate or acetylide).
[0046] It will be estimated that although in formula (I), groups X and G are illustrated as being associated with a metal center of simple M1 or M2, one or more groups X and G can form a bridge between the metal centers M1 and M2.
[0047] For the purposes of the present invention, the epoxide substrate is not limited. The term epoxide, therefore, refers to any compound that comprises a portion of epoxide. Examples of epoxides that can be used in the present invention include, but are not limited to, cyclohexene oxide, styrene oxide, propylene oxide, butylene 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), unsubstituted and substituted oxiranes (such as oxirane, epichlorohydrin, 2- (2-methoxyethoxy) methyl oxirane (MEMO), 2- (2- (2-methoxyethoxy) ethoxy) methyl oxirane (ME2MO), 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) methyl oxirane (ME3MO ), 1,2-epoxybutane, glycidyl ethers, vinyl cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2, Functionalized 3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide and 3,5-dioxaepoxides Examples of functionalized 3,5-dioxaepoxides include:

[0048] The epoxide portion can be a glycidyl ether, glycidyl ester or glycidyl carbonate. Examples of glycidyl ethers, glycidyl ethers of glycidyl esters include:

[0049] The epoxy substrate can contain more than one deeppoxy portion, that is, it can be a portion containing a bis-epoxide, a tris-epoxide or a multi-epoxide. Examples of compounds including more than one epoxy portion include bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It will be understood that reactions carried out in the presence of one or more compounds having more than one epoxide moiety can lead to crosslinking in the resulting polymer.
[0050] The person skilled in the art will estimate that the epoxide can be obtained from "green" or renewable resources. The epoxide can be obtained from an (poly) unsaturated compound, such as that derived from fatty acid and / or terpene, obtained using standard oxidation chemicals.
[0051] The epoxy portion may contain - OH portions or protected -OH portions. The -OH portions can be protected by any suitable protection group. Suitable protecting groups include methyl or other alkyl, benzyl, allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C (O) alkyl), benzolyl (C (O) Ph), dimethoxytrityl ( DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (such as trimethylsilyl (TMS), t -Butyldimethylsilyl (TBDMS), t - Butyldiphenylsilyl (TBDPS), tri-iso-propylsilyloxymethyl (TOM) and tri - isopropylsilyl (TIPS)), (4-methoxyphenyl) diphenylmethyl (MMT), tetrahydrofuranyl (THF) and tetrahydropyranyl (THP).
[0052] The epoxide preferably has a purity of at least 98%, more preferably> 99%.
[0053] It will be understood that the term "an epoxide" is intended to cover one or more epoxides. In other words, the term "an epoxide" refers to a simple epoxide or a mixture of two or more different epoxides. For example, the epoxide substrate can be the mixture of ethylene oxide and propylene oxide, the mixture of cyclohexene oxide and propylene oxide, the mixture of ethylene oxide and cyclohexene oxide or the mixture of oxide ethylene, propylene oxide and cyclohexene oxide.
[0054] The skilled person will also understand that substituted and unsubstituted oxetanes can be used in place of and in addition to the epoxides of the second aspect of the invention. Suitable oxetanes include substituted or unsubstituted oxetanes (preferably substituted in position 3 by halogen, alkyl (substituted or unsubstituted by -OH or halogen), amino, hydroxyl, aryl (eg, phenyl), alkylaryl (eg, benzyl) ). Exemplary oxetanes include oxethane, 3-ethyl-3-oxetanomethanol, oxethane-3-methanol, 3-methyl-3-oxetanomethanol, 3-methyloxethane, 3-ethyloxetene, etc.
[0055] The term anhydride refers to any compound that comprises an anhydride moiety in a ring system (i.e. a cyclic anhydride). Preferably, the anhydrides that are useful in the present invention have the following formula:

[0056] Where m '' is 1, 2, 3, 4, 5 or 6 (preferably 1 or 2), eachRa1, Ra2, Ra3 and Ra4 is independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkyletheroaryl optionally substituted; or two or more of Ra1, Ra2, Ra3 and Ra4 can be used together to form an optionally substituted 3- to 12-membered saturated, partially saturated or unsaturated ring system, optionally containing one or more heteroatoms or can be used together to form a double bond. Each Q is independently C, O, N or S, preferably C, where Ra3 and Ra4 are present or absent and can be == or, according to the valence of Q. It will be estimated that when Q is C and is ==, Ra3 and Ra4 (or two Ra4 in the adjacent carbon atoms) are absent. The qualified person will appreciate that the anhydrides can be obtained from “green” or renewable sources. Preferred anhydrides are shown below.


[0057] The term lactone refers to any cyclic compound that comprises a -C (O) O- moiety on the ring. Preferably, the lactones that are useful in the present invention have the following formula:
where m is 1 to 20 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 ), preferably 2, 4 or 5; and RL1 and RL2 are independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylar, heteroaryl, alkylar replaced. Two or more of RL1 and RL2 can be used together to form an optionally substituted 3- to 12-membered saturated, partially saturated or unsaturated ring system, optionally containing one or more heteroatoms. When m is 2 or more, the RL1 and RL2 on each carbon atom can be the same or different. Preferably RL1 and RL2 are selected from hydrogen or alkyl. Preferably, the lactone has the following structure:

[0058] The term lactide is a cyclic compound containing two ester groups. Preferably, the lactides that are useful in the present invention have the following formula:
where m 'is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, (preferably 1 or 2, more preferably 1) and RL3 and RL4 are independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl optionally substituted. Two or more of RL3 and RL4 can be used together to form an optionally substituted 3 to 12 saturated, partially saturated or unsaturated ring system, optionally containing one or more heteroatoms. When m 'is 2 or more, the RL3 and RL4 on each carbon atom may be the same or different, or one or more RL3 and RL4 on adjacent carbon atoms may be absent, thereby forming a double or triple bond. It will be estimated that while the compound has two portions represented by (-CRL3RL4) m ', both portions will be identical. Preferably, m 'is 1, RL4 is H, and RL3 is H, hydroxyl or C1-6 alkyl, preferably methyl. The stereochemistry of the portion represented by (- CRL3RL4) m 'can be the same (for example, RR-lactide or SS-lactide) or different (for example, meso-lactide). The lactide can be a racemic mixture or it can be an optically pure isomer. Preferably, the lactide has the following formula:

[0059] The term "lactone and / or lactide" used in this covers a lactone, a lactide and a combination of a lactone and a lactide. Preferably, the term "lactone and / or lactide" means a lactone or a lactide.
[0060] Preferred optional substituents from the groups Ra1, Ra2, Ra3, Ra4, RL1, RL2, RL3 and RL4 include halogen, nitro, hydroxyl, unsubstituted aliphatic, unsubstituted heteroaliphatic, unsubstituted heteroaryl, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide and carboxylate. Detailed Description
[0061] In the first aspect of the invention, a catalyst of formula (I) is provided here:
where: M1 and M2 are independently selected from Zn (II), Cr (II), Co (II), Cu (II), Mn (II), Mg (II), Ni (II), Fe (II), Ti (II), V (II), Cr (III) -X, Co (III) - X, Mn (III) -X, Ni (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; wherein at least one of M1 or M2 is selected from Ni (II) and Ni (III) -X; R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an alicyclic or heteroalicyclic alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio optionally substituted group; R3 is independently selected from alkylene, alkenylene, alkylene, heteroalkenylene, heteroalkenylene, heteroalkenylene, arylene, heteroarylene or cycloalkylene optionally substituted, in which alkylene, alkenylene, alkylene, heteroalkylene, heteroalkenylene and heteroalkenylene, can be optionally interrupted by aryl, heteroalicylic, aryl, heteroalkenyl heteroalicyclic; R5 is independently selected from H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or optionally substituted alkylaryl; E1 is C, E2 is O, S or NH or E1 is N and E2 is O; E3, E4, E5 and E6 are selected from N, NR4, O and S, where when E3, E4, E5 or E6 are N, it is == m and when E3, E4, E5 or E6 are NR4, O or S, is; R4 is independently selected from H or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or optionally substituted alkylaryl; X is independently selected from OC (O) Rx, OSO2Rx, OSORx, OSO (Rx) 2, S (O) Rx, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, starch or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic , optionally substituted aryl or heteroaryl; Rx is independently hydrogen or aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl optionally substituted and G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base.
[0062] Each of the occurrences of groups R1 and R2 can be the same or different. Preferably R1 and R2 are independently selected from optionally substituted hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio. Preferably R2 is the same. Preferably, each occurrence of R2 is the same and is hydrogen.
[0063] Even more preferably, R2 is hydrogen and R1 is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio optionally substituted, such as hydrogen, C1-6 alkyl (eg, haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, eg, tBu, iPr, Me, OMe, H, nitro, SO2Me, SiEt3 , halogen or phenyl.
[0064] Each occurrence of R1 can be the same or different, and R1 and R2 can be the same or different. Preferably each occurrence of R1 is the same. Preferably each occurrence of R2 is the same. Preferably, each occurrence of R1 is the same and each occurrence of R2 is the same, and R1 is different from R2.
[0065] Preferably both occurrences of R1 are the same and are selected from optionally substituted hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio . Most preferably both occurrences of R1 are the same and are selected from optionally substituted halide, sulfoxide, silyl and an alkyl, heteroaryl or alkoxy. Even more preferably both occurrences of R1 are the same and are selected from tbutyl, methoxy, trialkylsilyl such as triethylsilyl, bromide, methanesulfonyl or piperidinyl. Most preferably, both occurrences of R1 are the same and are selected from t-butyl or trialkylsilyl. More preferably, both occurrences of R1 are the same and are tbutyl.
[0066] It will be estimated that the R3 group may be a bisubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl or heteroalkynyl group that can be optionally disrupted by an aryl, heteroaryl, alicyclic or heteroalicyclic group or may be a bisalkyl aryl or cycloalkyl group. acts as a linking group between two nitrogen centers in the catalyst of formula (I). Thus, where R3 is an alkylene group, such as dimethylpropylenyl, the group R3 has the structure - CH2-C (CH3) 2-CH2-. The definitions of the alkyl, aryl, cycloalkyl, etc. groups, presented above, therefore, also refer respectively to the divalent alkylene, arylene, cycloalkylene groups etc. presented by R3 and can be optionally substituted. Exemplary options for R3 include ethylene, 2,2-fluoropropylenyl, 2,2-dimethylpropylenyl, propylenyl, butylenyl, phenylenyl, cyclohexylenyl or biphenylenyl. When R3 is cyclohexylenyl, it can be the forms, RR- or SS- racemic.
[0067] R3 can be independently selected from substituted or unsubstituted alkylene and substituted or unsubstituted arylene, preferably substituted or unsubstituted propylene, such as substituted or unsubstituted propylene and 2,2-dimethylpropylenyl and phenylenyl or biphenylenyl. Preferably both occurrences of R3 are the same. Even more preferably R3 is a substituted propylenyl, such as 2,2-di (alkyl) propylenyl, especially 2,2-di (methyl) propylenyl.
[0068] R3 can be independently selected from substituted or unsubstituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene, arylene or cycloalkylene. Preferably, R3 is selected from substituted or unsubstituted alkylene, cycloalkylene, alkenylene, heteroalkylene and arylene. More preferably, R3 is selected from 2,2-dimethylpropylenyl, -CH2 CH2 CH2-, - CH2CH (CH3) CH2-, -CH2C (CH2C6H5) 2CH2-, phenylene, -CH2 CH2-, -CH2 CH2 CH2-, - CH2 CH2N (CH3) CH2 CH2-, 1,4-cyclohexandiyl or -CH2CH2CH (C2H5) -. Even more preferably R3 is selected from 2,2-dimethylpropylenyl, -CH2 CH2 CH2-, -CH2CH (CH3) CH2-, - CH2C (CH2C6H5) 2CH2-, -CH2CH2CH (C2H5) -, -CH2 CH2 CH2 CH2-. Even more preferably, R3 is selected from 2,2-dimethylpropylenyl, -CH2C (CH2C6H5) 2CH2-, CH2CH (CH3) CH2 and -CH2 C (C2H5) 2 CH2-.
[0069] More preferably R3 is a substituted propylenyl, such as 2,2-di (alkyl) propylenyl, more preferably 2,2-dimethylpropylenyl.
[0070] Preferably each R4 is independently selected from hydrogen and an optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl. Preferably R4 is hydrogen. Preferably each R4 is the same. Preferably, each R4 is the same and is selected from hydrogen and an optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl. Exemplary options for R4 include H, Me, Et, Bn, iPr, tBu or Ph. An additional exemplary option is -CH2- (pyridine). Even more preferably, each R4 is hydrogen.
[0071] Preferably each R5 is independently selected from hydrogen and optionally substituted aliphatic or aryl. More preferably, each R5 is independently selected from optionally substituted hydrogen and alkyl or aryl. Even more preferably, each R5 is the same and is selected from optionally substituted hydrogen and alkyl or aryl. Exemplary R5 groups include hydrogen, methyl, ethyl, phenyl and trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl. Even more preferably, each R5 is hydrogen.
[0072] Preferably both occurrences of E1 are C and both occurrences of E2 are the same and selected from O, S or NH. Even more preferably, both occurrences of E1 are C and both occurrences of E2 are O.
[0073] Preferably, each occurrence of E3, E4, E5 and E6 are NR4. Even more preferably, E3, E4, E5 and E6 are the same and are NH. In other words, the catalyst of the first aspect preferably has the following preferred structure:

[0074] Each X is independently selected from OC (O) Rx, OSO2Rx, OS (O) Rx, OSO (Rx) 2, S (O) Rx, ORx, phosphinate, halide, nitro, hydroxyl, carbonate, amino, nitrate , starch and aryl or aliphatic heteroaryl, heteroaliphatic (e.g., silyl), alicyclic, optionally substituted heteroalicyclic. Preferably each X is independently OC (O) Rx, OSO2Rx, OS (O) Rx, OSO (Rx) 2, S (O) Rx, ORx, halide, nitrate, hydroxyl, carbonate, amino, nitro, starch, alkyl (for branched alkyl), heteroalkyl, (e.g., silyl), aryl or heteroaryl. Even more preferably, each X is independently OC (O) Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx. Preferred optional substituents for when X is aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl include halogen, hydroxyl, nitro, cyano, amino or aryl or aliphatic, heteroaliphatic, alicyclic, substituted or unsubstituted. Each X can be the same or different and preferably each X is the same. It will be estimated that X can form a bridge between the two metal centers.
[0075] Rx is independently hydrogen or aryl, alkylaryl or heteroaryl aliphatic, haloaliphatic, heteroaliphatic, alicyclic, optionally substituted heteroalicyclic. Preferably, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. Preferred optional substituents for Rx include halogen, hydroxyl, cyano, nitro, amino, alkoxy, alkylthio or aryl or aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, substituted or unsubstituted (e.g., alkyl, aryl or optionally substituted heteroaryl).
[0076] Exemplary options for X include OAc, OC (O) CF3, halogen, OSO (CH3) 2, Et, Me, OMe, OiPr, OtBu, Cl, Br, I, F, N (iPr) 2 or N (SiMe3) 2, OPh, OBn, salicylate, dioctyl phosphinate, etc.
[0077] Preferably each X is the same and is selected from OC (O) Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl , heteroaryl or alkylaryl. More preferably each X is the same and is OC (O) Rx, ORx, halide, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx. Even more preferably, each X is the same and is OC (O) Rx. Even more preferably each X is the same and is selected from OAc, O2CCF3 or O2C (CH2) 3Cy. More preferably each X is the same and is OAc.
[0078] Preferably each Rx is the same and is selected from an optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. More preferably each Rx is the same and is an optionally substituted alkyl, alkenyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl. Even more preferably each Rx is the same and is an optionally substituted alkyl, alkenyl, heteroalkyl or cycloalkyl. Even more preferably Rx is an optionally substituted alkyl, heteroalkyl or cycloalkyl. More preferably Rx is an optionally substituted alkyl.
[0079] As detailed above, M1 and M2 are independently selected from any of: Zn (II), Cr (III) -X, Cr (II), Co (III) -X, Co (II), Cu (II ), Mn (III) -X, Mn (II), Mg (II), Ni (II), Ni (III) -X, Fe (II), Fe (III) -X, Ca (II), Ge ( II), Ti (II), Al (III) -X, Ti (III) -X, V (II), V (III) -X, Ge (IV) - (X) 2 or Ti (IV) - ( X) 2, wherein at least one of M1 and M2 is selected from Ni (II) and Ni (III) -X, even more preferably however at least one of M1 and M2 is Ni (II).
[0080] Preferably, M1 and M2 are independently selected from Zn (II), Cr (III) -X, Co (II), Cu (II), Mn (II), Mg (II), Ni (II), Ni (III) -X, Fe (II), Fe (III) and V (II), even more preferably, M1 and M2 are independently selected from Zn (II), Cr (III) -X, Co (II), Mn (II), Mg (II), Ni (II), Ni (III) -X, Fe (II) and Fe (III) -X and even more preferably, M1 and M2 are independently selected from Zn (II), Mg (II), Ni (II) and Ni (III) -X, where at least one of M1 and M2 is selected from Ni (II) and Ni (III) -X, even more preferably at least one of M1 and M2 is Ni (II).
[0081] More preferably, both M1 and M2 are selected from Ni (II) and Ni (III) -X, even more preferably both M1 and M2 are Ni (II).
[0082] It will be estimated that when one of M1 or M2 is Cr (III), Co (III), Mn (III), Ni (III), Fe (III), Al (III), Ti (III) or V ( III) the catalyst of formula (I) will contain an additional group X coordinated to the metal plant, where X is as defined above. It will be estimated that when one of M1 or M2 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 one of M1 or M2 is Ge (IV) - (X) 2 or Ti (IV) - (X) 2, both G may be present.
[0083] When G is not absent, this is a group that is able to donate a pair of electrons alone (this is a Lewis base). In certain embodiments, G is a Lewis base containing nitrogen. 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 (ie N (R12) 4+), iminium ions (ie (R12) 2C = N (R12) 2+, such as bis (triphenylphosphino) iminium ions) 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.
[0084] 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 and water. More preferably, G is independently selected from water, an alcohol (eg, methanol), a substituted or unsubstituted heteroaryl (imidazole, methyl imidazole (eg, 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 (morpholino, piperidine, tetrahydrofuran, tetrahydrothiophene, etc.), one 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 examples 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 preferred embodiments, 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 examples of G are negatively charged (for example, halide). Still in the modalities, one or both examples of G is an optionally substituted heteroaryl. Exemplary G groups include chloride, bromide, pyridine, methylimidazole (for example, N-methyl imidazole) and dimethylaminopyridine (for example, 4-methylaminopyridine).
[0085] It will be estimated that when a group G is present, the group G can be associated with a simple 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 metallic centers, as shown below in formula (Ia):

[0086] Where R1, R2, R3, R4, R5, M1, M2, G, X, E1 and E2, are co-defined for formula (I) and formula (II).
[0087] It will be estimated that X can form a bridge between the two metal centers.
[0088] The qualified person will understand that, in the solid state, the catalysts of the first aspect can be associated with solvent molecules such as alcohol or alcohol (for example, methanol or ethanol). It will be estimated that solvent molecules may be present in a ratio less than 1: 1 relative to the catalyst molecules of the first aspect (ie 0.2: 1, 0.25: 1, 0.5: 1), in a ratio of 1: 1, relative to the catalyst molecules of the first aspect or in a ratio greater than 1: 1, relative to the catalyst molecules of the first aspect.
[0089] The qualified person will understand that, in the solid state, the catalysts of the first aspect can form aggregates. For example, the catalyst for the first aspect may be a dimer, trimer, tetramer, pentamer or higher aggregate.
[0090] It will be estimated that the preferred characteristics described above for the catalyst of the first aspect may be present in combination mutatis mutandis.
[0091] For example, in the preferred embodiments of the first aspect, each occurrence of R2 and R5 is H, E1 is C and E2 is O, S or NH (preferably E2 is O) and, E3-E6 are NR4.
[0092] Preferably, each occurrence of R2 and R5 is H, R3 is an optionally substituted or unsubstituted alkylene and substituted or unsubstituted arylene in which alkylene, can be optionally interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic, E1 is C and E2 is O, S or NH (preferably E2 is O), each occurrence of E3 to E6 is NR4, R4 is hydrogen or alkyl (preferably hydrogen), each X is independently OC (O) Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl, each R1 is independently hydrogen, alkyl, alkenyl, aryl, heteroaryl, alkoxy, alkylthio, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl or silyl ether, each G (where present) 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, at least one of M1 and M2 is Ni (II) or Ni (III ) -X and the remaining M1 or M2 are selected from Mg (II), Zn (II), Cr (III) -X, Co (II), Co (III) -X, Mn (II), Ni (II) , Ni (III) -X, Fe (II) and Fe (III) -X.
[0093] Even more preferably, each occurrence of R2 and R5 is H, R3 is an optionally substituted or unsubstituted alkylene and substituted or unsubstituted arylene, E1 is C and E2 is O, S or NH (preferably E2 is O), each occurrence of E3 to E6 is NR4, R4 is hydrogen or alkyl (preferably hydrogen), each X is the same and is OC (O) Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl, each R1 is the same and is hydrogen, alkyl, alkenyl, aryl, heteroaryl, alkoxy, alkylthio, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate , silyl or silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy or alkylthio, each G (where present) 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, at least one of M1 and M2 is Ni (II) or Ni (III ) -X and the remaining M1 or M2 is selected from Mg (II), Zn (II), Cr (II), Cr (III) -X, Co (II), Co (III) -X, Mn (II) , Ni (II), Ni (III) -X, Fe (II) and Fe (III) -X, preferably both M1 and M2 are selected from Ni (II) and Ni (III) -X.
[0094] In a preferred embodiment, the catalyst of formula (I) has the formula (Ib):
Where: both occurrences of R1 are the same and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio ; R3 is selected from substituted or unsubstituted alkylene, heteroalkylene arylene or heteroarylene in which alkylene and heteroalkylene can be optionally interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic; Each X is the same and is selected from OC (O) Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl ; Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; Each G (where present) is independently selected from halide; Water; a heteroaryl optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile; and at least one of M1 and M2 is Ni (II) or Ni (III) -X and the remaining M1 or M2 is selected from Mg (II), Zn (II), Cr (III) -X, Co (II) , Co (III) -X, Mn (II), Ni (II), Ni (III) -X, Fe (II) and Fe (III) -X.
[0095] Preferably R1 is optionally substituted hydrogen, halide, silyl, silyl ether, sulfonyl and alkyl, aryl or alkoxy.
[0096] Preferably, R3 is selected from substituted or unsubstituted propylenyl, 2,2-dimethylpropylenyl and phenylenyl or biphenylenyl. Even more preferably R3 is a substituted propylenyl, such as 2,2-di (alkyl) propylenyl.
[0097] Preferably, both M1 and M2 are selected from Ni (II) and Ni (III) -X. Even more preferably, both M1 and M2 are Ni (II).
[0098] Preferably, X is OC (O) Rx, ORx, halide, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx. Preferably, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl. Even more preferably, X is OC (O) Rx, and Rx is alkyl, alkenyl, heteroalkyl, aryl, heteroaryl or alkylaryl, preferably Rx is alkyl (e.g., methyl, ethyl, propyl, t-butyl or trifluoromethyl).
[0099] G may be absent or present and preferably G is absent.
[00100] In a more preferred embodiment, the catalyst of formula (I) has the formula (Ic):
where: both occurrences of R1 are the same and are selected from halide, sulfoxide, silyl and an optionally substituted alkyl, heteroalicyclic or alkoxy; R3 is selected from substituted or unsubstituted alkenyl, cycloalkylenyl, alkenylenyl, heteroalkylenyl and arylenyl in which alkenyl, alkenylenyl, heteroalkylenyl may be optionally interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic; Each X is the same and is OC (O) Rx, Rx is alkyl, alkenyl, heteroalkyl; or cycloalkyl; Each G is not present; and Both M1 and M2 are selected from Ni (II) or Ni (III) -X.
[00101] Still in a more preferred embodiment, the catalyst of formula (I) has the formula (Id):
Where: both occurrences of R1 are the same and are selected from t-butyl, methoxy, triethylsilyl, Br, SO2CH3 or piperidine; R3 is selected from 2,2-dimethylpropylenyl, -CH2 CH2 CH2-, - CH2CH (CH3) CH2-, -CH2C (CH2C6H5) 2CH2-, phenylene, -CH2 CH2-, -CH2 CH2 CH2-, -CH2 CH2N ( CH3) CH2 CH2-, 1,4-cyclohexandiyl, -CH2CH2CH (C2H5) or CH2C (C2H5) 2CH2-; Each X is the same and is selected from OAc, O2CCF3 or O2C (CH2) 3Cy; Each G is not present; and Both M1 and M2 are selected from Ni (II) or Ni (III) -X.
[00102] Still in a more preferred embodiment, the catalyst of formula (I) has the formula (Ie):
Where: both occurrences of R1 are the same and are selected from tBu or triethylsilyl; R3 is selected from 2,2-dimethylpropylenyl, -CH2 CH2 CH2-, - CH2CH (CH3) CH2-, -CH2C (CH2C6H5) 2CH2-, -CH2 CH2 CH2 CH2-, CH2C (C2H5) 2CH2 and -CH2CH2CH (C2H5) -; Each X is the same and is selected from OAc, O2CCF3 or O2C (CH2) 3Cy; Each G is not present; and Both M1 and M2 are selected from Ni (II) or Ni (III) -X.
[00103] Still in a more preferred embodiment, the catalyst of formula (1) has the formula (If):
Where: both occurrences of R1 are the same and are tBu; R3 is selected from 2,2-dimethylpropylenyl, - CH2C (CH2C6H5) 2CH2- and -CH2CH2CH (C2H5) -; Each X is the same and is OAc; Each G is not present; and Both M1 and M2 are selected from Ni (II) or Ni (III) -X.
[00104] The qualified person will estimate that each of these preferred characteristics can be adopted in combination, mutatis mutandis. For example, R1 is optionally substituted hydrogen, halide, silyl, silyl ether, sulfonyl and alkyl or alkoxy; R3 is selected from substituted or unsubstituted propylenyl, 2,2-dimethylpropylenyl and phenylenyl or biphenylenyl; at least one of M1 and M2 is Ni (II) or Ni (III) -X and the remaining M1 or M2 is selected from Mg (II), Zn (II), Ni (II) and Ni (III) -X ( preferably both M1 and M2 are selected from Ni (II) and Ni (III) -X); X is OC (O) Rx, ORx, halide, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx; Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; and G can be present or absent (preferably G is absent).
[00105] The exemplary catalysts of the first aspect are as follows:






[00106] The catalysts of the first aspect are capable of polymerizing (i) carbon dioxide and an epoxide, (ii) an epoxide and an anhydride and (iii) a lactide and / or a lactone. Therefore, in a second aspect of the invention, there is provided a process for the reaction of carbon dioxide with an epoxide, an anhydride with an epoxide or a lactide and / or a lactone in the presence of a catalyst according to the first aspect.
[00107] The process of the second aspect can be carried out in the presence of a chain transfer agent. Suitable chain transfer agents include chain transfer agents, for example, as defined by formula (II), in WO 2013/034750, the total contents of which are incorporated herein by reference. For example, the chain transfer agent can be water or can comprise at least one amine (-NHR), alcohol (-OH), carboxylic acid (CO2H) or thiol moiety (- SH).
[00108] Examples of chain transfer agents useful in the second aspect include water, mono-alcohols (i.e. alcohols with an OH group, for example, 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, trimethylolpropane, preferably glycerol or benzenotriol), tetraols (eg calix [4] arene, 2,2-bis (methyl alcohol) - 1 , 3-propanediol, di (trimethylolpropane)), polyols (eg, dipentaerythritol, D - (+) - glucose or D-sorbitol), dihydroxy-terminated polyesters (eg, polylactic acid), polyethers terminated in di- hydroxy (eg poly (ethylene glycol)), acids (such as diphenylphosphine acid), starch, lignin, mono-amines (i.e. methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine), diamines (by example 1,4-butanediamine), triamines, diamine-terminated polyethers, diamine-terminated polyesters, mono-carboxylic acids (for example, 3,5-di-tert-butylbenzoic acid), dicarboxylic acids (for example, maleic acid, malonic, succinic acid, glutaric acid or terephthalic acid, preferably maleic acid, malonic acid, succinic acid, glutaric acid), tricarboxylic acids (for example, citric acid, 1,3,5-benzenotricarboxylic acid or 1,3,5- cyclohexanotricarboxylic, preferably citric acid), mono-thiols, ditholes, trithols and compounds having a mixture of hydroxyl, amine, carboxylic acid and thiol groups, for example, lactic acid, glycolic acid, 3-hydroxypropionic acid, amino acid natural acids, unnatural amino acids, monosaccharides, disaccharides, oligosaccharides and polysaccharides (including forms of pyranose and furanose). Preferably, 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, tri (methyl alcohol) propane, tri (methyl alcohol) butane, pentaerythritol, poly (propylene glycol), glycerol, mono- and di-ethylene glycol, propylene glycol, 2,2-bis (methyl alcohol) -1,3-propanediol, 1,3, 5-benzenotricarboxylic acid, 1,3,5-cyclohexanotricarboxylic acid, 1,4-butanediamine, 1,6-hexanediol, D-sorbitol, 1-butylamine, terephthalic acid, D - (+) - glucose, acid 3, 5-di-tert-butylbenzoic acid and water.
[00109] The process of the second aspect can be carried out in the presence of a solvent. Examples of solvents useful in the third aspect include toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, tetrahydrofuran (THF), etc.
[00110] When the process of the second aspect involves the reaction of an epoxide, the epoxide can be any compound that comprises a portion of epoxide.
[00111] Preferably the epoxide is ethylene oxide, propylene oxide, butylene oxide or cyclohexene oxide. Most preferably the epoxide is propylene oxide.
[00112] In a preferred embodiment of the second aspect of the invention, here is provided a process for the reaction of carbon dioxide with ethylene oxide, butylene oxide, cyclohexane oxide or propylene oxide, more preferably propylene oxide, an anhydride with ethylene oxide, butylene oxide, cyclohexene oxide or propylene oxide, more preferably propylene oxide or a lactide and / or a lactone in the presence of a catalyst according to the first aspect.
[00113] Preferably, in the preferred embodiment of the second aspect, the catalyst for the first aspect is any of the above listed as exemplary.
[00114] The epoxide can be purified (for example, by distillation, such as in calcium hydride) before reaction with carbon dioxide or anhydride. For example, the epoxide can be distilled before being added to the reaction mixture comprising the catalyst or catalyst system.
[00115] The process of the second aspect of the invention can be carried out at a pressure of 1 to 100 atmospheres, preferably at 1 to 40 atmospheres, such as at 1 to 20 atmospheres, more preferably at 1 or 10 atmospheres. The catalysts used in the process of the second aspect allow the reaction to be carried out at low pressures.
[00116] The process of the second aspect of the invention can be carried out at a temperature of about 0 ° C to about 250 ° C, preferably from about 40 ° C to about 160 ° C, even more preferably from about 50 ° C to about 120 ° C. The process duration can be up to 168 hours, such as from about 1 minute to about 24 hours, for example, from about 5 minutes to about 12 hours, for example, from about 1 to about 6 hours.
[00117] The process temperature, for copolymerizations of carbon dioxide and an epoxide, can be used to control the composition of the product. When the process temperature of the second aspect which involves reacting carbon dioxide and an epoxide is increased, the selectivity of the catalyst towards the formation of cyclic carbonate is also increased. Catalysts and processes can operate at temperatures up to 250 ° C.
[00118] The process of the second aspect of the invention can be performed on low catalytic loading. For example, when the reaction involves the copolymerization of carbon dioxide and an epoxide, the catalytic loading for the process is preferably in the catalyst: epoxide 1: 1,000-100,000 range, more preferably in the catalyst: epoxide 1: 1,000-300,000 region , even more preferably in the region of 1: 10,000-100,000 and most preferably in the region of catalyst: epoxide 1: 50,000-100,000. When the process involves copolymerization of an epoxide and an anhydride or the reaction of a lactide and / or lactone, the catalytic loading for the process is preferably in the catalyst range: total monomer content 1: 1,000-300,000, more preferably in the region of catalyst: total monomer content 1: 10,000-100,000, even more preferably in the catalyst region: total monomer content 1: 50,000-100,000. The above reasons are molar reasons.
[00119] The catalysts of the first aspect and in particular catalysts in which both M1 and M2 are selected from Ni (II) and Ni (III) - X, have high activity and selectivity to supply the polycarbonates by the reaction of carbon dioxide and a epoxide, optionally in the presence of a chain transfer agent and preferably at temperatures between about 40 ° C to about 160 ° C. In this way, the reaction times for the second aspect process can be less than 12 hours and preferably from about 2 to about 6 hours. In particular, the catalysts of the invention have improved activity in relation to bisubstituted meso-epoxides (eg, cyclohexene oxide) and substituted mono-epoxides (eg, propylene oxide) and in addition, improved selectivity to mono- epoxide replaced.
[00120] The process of the second aspect can be carried out in a batch reactor or a continuous reactor.
[00121] It will be estimated that the various characteristics described above for the process of the second aspect may be present in combination mutatis mutandis. All the preferred features of the first aspect apply equally to the second aspect and can be present in combination mutatis mutandis.
[00122] The third aspect of the invention provides a product of the process of the second aspect of the invention. All the preferred features of the second aspect of the invention apply to the third aspect of the invention mutatis mutandis.
[00123] When the process of the second aspect is carried out in the presence of a chain transfer agent, it produces the polymer chains which are terminated substantially at all ends with hydroxyl groups (i.e. polycarbonate polyols or polyester polyols). For "substantially", it is meant that at least 90% of the resulting polymer chains, preferably at least 95% of the resulting polymer chains and even more preferably at least 98% and even more preferably at least about 99% of the polymer chains resultant are terminated at all ends in the hydroxyl groups. In order for at least 90% of the resulting polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the second aspect to be carried out in the presence of at least about 4 equivalents of chain transfer agent, relative to catalyst quantity. In order for at least 95% of the resulting polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the second aspect to be carried out in the presence of at least about 10 equivalents of relative chain transfer agent the quantity of the catalyst. In order for at least 98% of the resulting polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the second aspect to be carried out in the presence of at least about 20 equivalents of chain transfer agent, relative to catalyst quantity. Thus, polyols obtained by the process of the second aspect are considered to form part of the third aspect of the invention.
[00124] The chain transfer agent referred to in the second aspect can be used to control the molecular weight (Mn) of the polymer products produced by the second aspect. Preferably, the molecular weight (Mn) of the polymer products of the third aspect is greater than about 200 g / mol. The molecular weight (Mn) of the polymer products of the third aspect can be from about 200 g / mol to about 200,000 g / mol. The molecular weight of the polymers produced by the third 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 on Mixed B columns, manufactured by Polymer Labs. Narrow molecular weight polystyrene standards can be used to calibrate the instrument.
[00125] It is possible to produce polycarbonate polyols and polyester polyols having an Mn of about 200 g / mol to about 20,000 g / mol, preferably less than about 10,000 g / mol by adding a chain transfer agent to the process the second aspect.
[00126] It is also possible to produce polymers having an Mn greater than about 20,000 g / mol of the second aspect process. Preferably, the polymer having an Mn greater than about 20,000 g / mol is a polycarbonate or a polyester, even more preferably a polycarbonate. Preferably, the polymer having an Mn greater than about 20,000 g / mol is a polycarbonate and is produced by carrying out the process of the second aspect without adding a chain transfer agent (CTA).
[00127] Polymers produced by the second aspect can be produced to have a polydispersity index (PDI) of less than about 2, more preferably less than about 1.5 and even more preferably less than about 1, two. In addition, it is possible to control the molecular weight distribution as well as to produce multi-modal or wide molecular weight distribution polymers by the addition of one or more chain transfer agents.
[00128] The polymers produced by the process of the second aspect (for example, polycarbonates such as PCHC or PPC), are connection blocks useful in the preparation of various copolymeric materials. The polymers produced by the process of the second aspect may undergo additional reaction, for example, to produce polymeric products such as polyureas or polyamines. These processes and reactions are well known to a qualified person (for example, it refers to WO2013 / 034750).
[00129] The polycarbonate or polyester polyols produced by the process of the second aspect can be used in various applications and products that conventionally use polyols, including (but not limited to) adhesives (such as hot melt adhesives and structural adhesives), a binder (such as forest product binders, foundry core binders and rubber chip binders), coatings (such as powder coatings, transport, for example, automotive or marine coatings, fast curing coatings, self curing coatings, coatings and top initiators, varnish and coatings for marine applications, for example, oil platforms), elastomers (such as fusion elastomers, fiber / spandex elastomers, shoe elastomers, RIM / RRIM elastomers, synthetic leather elastomers, microcellular elastomers technical and TPU elastomers), flexible foams (such as viscoelastic foams), rigid foams (such as rigid panels and flexible, rigid molded foams, aerosol crack filler foam, spray foams, cooling foams, in-place foams and foam boards) and sealants (such as glazing sealants for commercial, industrial and transportation applications). automotive) and construction sealants). Polyamines and polyureas can be processed using standard techniques known in the art, such as foaming.
[00130] It will be understood that the polycarbonate and polyester polyols produced by the process of the second aspect can be mixed with other polyols before additional use or reaction.
[00131] Polycarbonates and in particular polycarbonates having an Mn greater than about 20,000 g / mol (for example, produced without adding chain transfer agent to the process of the second aspect) can have a number of beneficial properties including high strength , high hardness, high brightness, high transparency, low turbidity, high gas content (eg, oxygen and carbon dioxide) or water barrier properties, flame resistance, UV resistance, high durability, rigidity and hardness, compatibility with plasticizers, temperature of wide dimensional stability, biodegradability and biocopatability and elasticity modulus and yield strength comparable to LDPE. In this way, these polymers can be used in various applications and products, such as electronic components, building materials, data storage products, and aircraft and automotive products, safety components, medical applications, cell phones, packaging (including bottles) , optical applications (such as safety glass, windshields, etc.).
[00132] The modalities of the invention will now be described with reference to the attached examples and figures in which: -
[00133] Figure 1 shows the selectivity of several catalysts.
[00134] Figure 2 shows the activity of several catalysts.
[00135] Figure 3 is an approximation of figure 2. Examples Example 1: Synthesis of nickel-containing catalysts
[00136] H2L1-18 ligands were synthesized by the method previously described by Kember et al, Angew. Chem. Int. Ed., 2009, 48, 931-933.
[00137] The ligands H2L1, H2L3, H2L5, H2L6, H2L7 and H2L8 (2 mmol) were dissolved in MeOH (50 mL), Ni (OAc) 2.4H2O (0.498 g, 4 mmol) was added in portions over 15 minutes and the solution stirred overnight. The solvent was removed in vacuo and excess water / AcOH was removed by the azeotrope with toluene (3 x 40 ml) to give a green or blue solid. [L1Ni2 (OAc) 2]: IR (ÜC = O, cm-1, pure): 1581 and 1413. MALDI-TOF MS: m / z: 727.6 ([M -OAc)] +, 100%); [L3Ni2 (OAc) 2]: IR (ÜC = O, cm-1, pure): 1577 and 1413. [L5Ni2 (OAc) 2]: IR (DC = O, cm-1, pure): 1585 and 1413. APCI-MS: m / z: 829 ([M -2 -OAc + -O2CH] +, 100%); [L6Ni2 (OAc) 2]: IR (DC = O, cm-1, pure): 1577 and 1439. APCI-MS: m / z: 754 ([M -2 -OAc + -O2CH] +, 100%) ; [L7Ni2 (OAc) 2]: IR (ÜC = O, cm-1, pure): 1581 and 1413. APCI-MS: m / z: 757 ([M -2 -OAc + -O2CH] +, 100%) . [L8Ni2 (OAc) 2]: IR (ÜC = O, cm-1, pure): 1581 and 1413. APCI-MS: m / z: 779.2 ([M - -OAc] +, 75%), 765 , 2 ([M - 2 -OAc + -O2CH] +, 95%).

[00138] The H2Lx ligand (2 mmol) was dissolved in MeOH (50 mL), Ni (X) 2.xH2O (4 mmol) was added in portions over 15 minutes and the solution stirred overnight. The solvent was removed in vacuo and excess water / acid was removed by the azeotrope with toluene (3 x 40 ml) to give a green or blue solid. [L1NÍ2 (G2CCF3) 2]: IR (ÜC = O, cm-1, pure): 1674 and 1480. ESI-MS: m / z = 779.3 (100%, [M - O2CCF3] +). [L1NÍ2 (G2C (CH2) 3Cy) 2]]: IR (ÜC = G, cm-1, pure): 1581 and 1406: ESI-MS: m / z = 835.2 (100%, [M - (G2c (cH2) 3cy)] +). L14Ni2 (G2CCF3) 2: IR (DC = G, cm-1, pure): 1678 and 1480. ESI-MS: m / z: 711.2 ([M -2 -GAc + -G2CH] +, 100%) ;

[00139] G ligand H2LX (2 mmol) was dissolved in MeGH (50 mL), Ni (GAc) 2.4H2G (0.498 g, 4 mmol) was added in portions over 15 minutes and the solution stirred overnight. The solvent was removed in vacuo and excess water / acid was removed by the azeotrope with toluene (3 x 40 ml) to give a green or blue solid. L9NÍ2 (GAc) 2: IR (ÜC = O, cm-1, pure): 1573 and 1421. APCI-MS: m / z: 655.1 ([M -2 -OAc + -O2CH] +, 85%) ; L10NÍ2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1577 and 1421. APCI-MS: m / z: 685.1 ([M -2 -OAc + -O2CH] +, 70%) ; L11NÍ2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1581, 1413. APCI-MS: m / z: 1017.2 ([M -2 -OAc + -O2CH] +, 70%) , 969.2 ([M -2 -OAc] +, 100%); L12Ni2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1559 and 1417. APCI-MS: m / z: 725.1 ([M -2 -OAc + -O2CH] +, 50%) ; L13Ni2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1551 and 1436. APCI-MS: m / z: 629.1 ([M -2 -OAc + -O2CH] +, 50%) ; L14Ni2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1573 and 1410. APCI-MS: m / z: 725.2 ([M - -OAc] +, 100%). L15Ni2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1566, 1413. APCI-MS: m / z: 685.1 ([M -2 -OAc + -O2CH] +, 100%) ; L16Ni2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1577 and 1402. ESI-MS: m / z: 741.3 ([M -2 -OAc + -O2CH] +, 55%) ; 755.3 ([M - -OAc] +, 20%). L17Ni2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1566, 1454. APCI-MS: m / z: 735.2 ([M -2 -OAc + -O2CH] +, 100%) ; L18Ni2 (OAc) 2: IR (ÜC = O, cm-1, pure): 1585, 1424. APCI-MS: m / z: 769.2 ([M - 2 -OAc + -O2CH] +, 95%) ; Example 2: Copolymerization in 1 atm of CHO with CO2 using Ni catalysts
[00140] The catalyst (0.0247 or 0.00494 mmol) was added and a Schlenk tube dried and dried under vacuum for 30 minutes. CHO (2.5 mL, 24.7 mmol) was added under CO2 via a syringe, the vessel was heated to 100 ° C and stirred for 2-16 hours, after which the heating was removed and a sample removed for the GPC / NMR analysis.

Table 1: Copolymerization of CHO and CO2 (1 atm) using Ni catalysts
[00141] The catalysts showed more than 90% selectivity for parapolymer towards the cyclohexene oxide reagent,> 99% selectivity for polyether polycarbonate (ie> 99% carbonate incorporation), high activities and activity under low pressures (1 atm). Example 3: Polymerization of CO2 and PO at 90 ° C and 0.21 mmol [L1Ni2 (OAc) 2]
[00142] [L1Ni2 (OAc) 2] (0.21 mmol) was dissolved in depropylene oxide (214 mmol) in a Schlenk tube and the solution transferred to a 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (3.0 MPa) and heated to 90 ° C. The solution was mechanically stirred for 6 hours, giving 7.5 g of poly (propylene carbonate) (Mn 19000/9700, PDI 1.03 / 1.04) as a white solid with a high polymer selectivity and> 99% of carbonate bonds. Example 4: Polymerization of CO2 and PO at 80 ° C and 0.11 mmol [L1Ni2 (OAc) 2]
[00143] [L1Ni2 (OAc) 2] (0.11 mmol) was dissolved in depropylene oxide (214 mmol) in a Schlenk tube and the solution transferred to a 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (4.0 MPa) and heated to 80 ° C. The solution was mechanically stirred for 16 hours, giving 7.4 g of poly (propylene carbonate) (Mn 23000/11400, PDI 1.03 / 1.05) as a white solid with a high polymer selectivity and> 99% carbonate bonds. Example 5: Polymerization of CO2 and PO at 90 ° C and 0.11 mmol of [L1Ni2 (OAc) 2]
[00144] [L1Ni2 (OAc) 2] (0.11 mmol) was dissolved in depropylene oxide (214 mmol) in a Schlenk tube and the solution transferred to a 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (4.0 MPa) and heated to 90 ° C. The solution was mechanically stirred for 17 hours, giving 11.5 g of poly (propylene carbonate) (Mn 39900/17600, PDI 1.03 / 1.09) as a white solid with a high polymer selectivity and> 99% carbonate bonds. Example 6: Polymerization of CO2 and CHO at 100 ° C and 0.05 mmol of [L1Ni2 (OAc) 2]
[00145] [L1Ni2 (OAc) 2] (0.05 mmol) was dissolved in cyclohexene oxide (50 mmol) in a Schlenk. The vessel was degassed, loaded with CO2 (0.1 MPa) and heated to 100 ° C with magnetic stirring for 3 hours, giving 2.9 g of poly (cyclohexene carbonate). The polymer contained> 99% carbonate bonds and was produced with> 99% selectivity (Mn 12000/5000, PDI 1.04 / 1.11). Example 7: Polymerization of CO2 and CHO at 80 ° C and 0.09 mmol of [L1Ni2 (OAc) 2]
[00146] [L1Ni2 (OAc) 2] (0.09 mmol) was dissolved in cyclohexene oxide (0.9 mmol) and propylene oxide (0.9 mmol) and the solution transferred in a Parr pressure vessel of pre-dried stainless steel to 100 mL using a syringe. The vessel was charged with CO2 (1.5 MPa) and heated to 80 ° C. The solution was mechanically stirred for 7 hours, giving 13.1 g of poly (cyclohexene-co-propylene) carbonate containing> 99% carbonate bonds with a very high selectivity for polymer formation. Example 8: Comparison of polymerization of CO2 and PO with [L1Ni2 (OAc) 2], [L5Ni2 (OAc) 2] and [L1Mg2 (OAc) 2] in a temperature range.
[00147] The catalyst ([L5Ni2 (OAc) 2] / [L1Ni2 (OAc) 2] / [L1Mg2 (OAc) 2]) (0.21 mmol) was dissolved in propylene oxide (214 mmol) in a Schlenk tube and the solution transferred in a Parr stainless steel pressure vessel pre-dried to 100 mL using a syringe. The container was loaded with CO2 pressure at 0.4-0.5 MPa and heated to temperature. Once at temperature, the CO2 pressure was raised to 4.0 MPa. The solution was mechanically stirred for the desired period of time and the reaction followed by ATR-FT-IR spectroscopy in situ. The selectivity and reaction activity were determined by ATR-FT-IR spectroscopy and confirmed with 1H NMR spectroscopy of the crude product. The results are shown in Figure 1 and Figure 2.
[00148] Figure 1 shows that the selectivity of the catalyst having a magnesium center [L1Mg2 (OAc) 2] is much less than compared to a catalyst having the same structure as the ligand but with a nickel metal center [L1Ni2 (OAc) two]. In addition, Figure 1 shows that the selectivity of catalysts having nickel metal centers remains high over a wide temperature range, at 100C, the selectivity of catalysts nickel-centered, [L1Ni2 (OAc) 2], [L5Ni2 (OAc) 2], is still at least 55%, considering at 100C the selectivity of the catalyst centered in magnesium, [L1Mg2 (OAc) 2], dropped to 0%.
[00149] Figure 2 shows that the activity of the catalyst having a magnesium center [L1Mg2 (OAc) 2] is much less than compared to a catalyst having the same structure as the ligand but with a nickel metal center [L1Ni2 (OAc) 2] across a temperature range. In addition, Figure 2 shows that the activity of the nickel-centered catalyst significantly increases at higher temperature, while retaining selectivity for PPC, unlike the magnesium-centered catalyst which shows less activity and no selectivity at higher temperatures (see Figure 1 ).
[00150] Figure 3 is an approximation of Figure 2 in the window 65-85 ° C and shows more closely the comparative activities of [L1Ni2 (OAc) 2] and [L1Mg2 (OAc) 2] in this temperature range. It more clearly demonstrates that [L1Ni2 (OAc) 2] is twice as surprising as active as its magnesium analog. Example 9: Comparison of Copolymerization in 1 atm of CHO and CO2 with equivalent Ni and Mg complexes under identical conditions
Table 2: Comparison of catalytic activity of equivalent Ni and Mg complexes under identical conditions for CHO and CO2 copolymerization (1 atm).
[00151] Catalysts having nickel metal centers show 99% selectivity to the cyclohexene oxide reagent. Catalysts having nickel metal centers also have a higher rotation number and a higher rotation frequency when compared to catalysts having the same structure as the ligand but with magnesium metal centers and when tested under identical reaction conditions. In particular, the frequency of rotation of the catalysts having nickel metal centers is in some cases double that showing catalysts having magnesium metal centers.
[00152] All features disclosed in this specification (including any claims, summary and accompanying drawings) and / or all steps of any method or process so disclosed, may be combined in any combination, except for combinations where at least any such characteristics and / or stages are mutually exclusive.
[00153] Each feature disclosed in this specification (including any claims, summary and accompanying drawings) may be replaced by alternative features serving the same, similar or equivalent purpose, unless expressly stated otherwise. In this way, unless expressly stated otherwise, each feature disclosed is an example only of a generic series of equivalent or similar features.
[00154] The invention is not restricted to the details of the preceding modalities. The invention extends to any novelty or any new combination, of the features disclosed in this specification (including any claims, summary and accompanying drawings), or to any novelty or any new combination, of the steps of any method or process so disclosed.

权利要求:
Claims (55)
[0001]
1. Catalyst, characterized by the fact that it is of formula (I):
[0002]
2. Catalyst according to claim 1, characterized by the fact that at least one of M1 or M2 is Ni (II).
[0003]
3. Catalyst according to any of the preceding claims characterized by the fact that one of MI or M2 is selected from Ni (II) and Ni (III) -X and the remaining occurrence of M1 and M2 is selected from Zn (II) , Cr (III) -X, Cr (II), Co (III) -X, Co (II), Cu (II), Mn (III) -X, Mn (II), Mg (II), Ni (II ), Ni (III) -X, Fe (II), Fe (III) -X, Ti (II), Ti (III) -X, V (II), V (III) -X, Ge (IV) - (X) 2 and Ti (IV) - (X) 2.
[0004]
4. Catalyst according to claim 3, characterized by the fact that the remaining occurrence of M1 and M2 is selected from Zn (II), Cr (III) -X, Co (II), Cu (II), Mn (II ), Mg (II), Ni (II), Ni (III) -X, Fe (II), Fe (III) -X and V (II).
[0005]
Catalyst according to either of claims 3 or 4, characterized by the fact that the remaining occurrence of Mi and M2 is selected from Zn (II), Cr (III) -X, Co (II), Mn (II) , Mg (II), Ni (II), Ni (III) -X, Fe (II), and Fe (III) -X.
[0006]
6. Catalyst according to any of claims 3 to 5, characterized by the fact that the remaining occurrence of Mi and M2 is selected from any of: Zn (II), Mg (II), Ni (II), Co (II), Co (III) -X and Ni (III) -X.
[0007]
7. Catalyst according to any of the preceding claims, characterized by the fact that both Mi and M2 are Ni (II).
[0008]
Catalyst according to any one of the preceding claims, characterized in that R3 is selected from substituted alkylene and substituted or unsubstituted arylene, preferably substituted phenylenyl or biphenylenyl and substituted propylenyl, such as 2,2-dimethylpropylenyl.
[0009]
Catalyst according to any one of the preceding claims, characterized in that R3 is selected from alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene and substituted cycloalkylene, preferably R3 is selected from alkylene, cycloalkylene, heteroalkylene and arylene substituted.
[0010]
10. Catalyst according to any one of the preceding claims, characterized in that R3 is selected from 2,2-dimethylpropylenyl, -CH2CH (CH3) CH2-, -CH2C (CH2C6H5) 2CH2-, -CH2 CH2N (CH3) CH2 CH2-, -CH2CH2CH (C2H5) - or -CH2C (C2H5) 2CH2-.
[0011]
Catalyst according to any one of the preceding claims, characterized in that R3 is selected from 2,2-dimethylpropylenyl, -CH2CH (CH3) CH2-, -CH2C (CH2C6H5) 2CH2-, - CH2CH2CH (C2H5) -.
[0012]
12. Catalyst according to any one of the preceding claims, characterized in that R3 is selected from a 2,2-dimethylpropylenyl, -CH2C (CH2C6H5) 2CH2-, -CH2C (C2H5) 2CH2- and - CH2CH2CH (C2H5) - .
[0013]
Catalyst according to any one of claims 1 to 9, characterized in that R3 is a 2,2-dialkylpropylenyl, for example, 2,2-dimethylpropylenyl.
[0014]
14. Catalyst according to any of the preceding claims, characterized by the fact that both occurrences of R3 are the same.
[0015]
Catalyst according to any one of the preceding claims, characterized in that Ei is C and E2 is O, S or NH, preferably E2 is O.
[0016]
16. Catalyst according to any of the preceding claims, characterized by the fact that E3, E4, E5 and E6 are NR4.
[0017]
17. Catalyst according to any one of the preceding claims, characterized by the fact that R4 is selected from hydrogen or an alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl or heteroaryl, such as hydrogen, methyl, ethyl, benzyl, optionally substituted isopropyl, t-butyl, phenyl or -CH2-pyridine, preferably R4 is hydrogen.
[0018]
18. Catalyst according to any of the preceding claims, characterized by the fact that each occurrence of R4 is the same.
[0019]
19. Catalyst according to any of the preceding claims, characterized by the fact that E3, E4, E5 and E6 are the same and are preferably NH.
[0020]
20. Catalyst according to any of the preceding claims, characterized in that Ri is selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl and alkyl ether, alkenyl, aryl, heteroaryl, alkoxy, optionally substituted aryloxy, arylthio or alkylthio, such as hydrogen, C1-6 alkyl (eg, haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, eg, hydrogen, t-butyl, isopropyl, methyl, methoxy, nitro, SO2CH3, triethylsilyl, halogen or phenyl.
[0021]
21. Catalyst according to any one of claims 1 to 19, characterized in that Ri is selected from optionally substituted halide, sulfoxide, silyl and an alkyl, heteroaryl or alkoxy.
[0022]
22. Catalyst according to any one of claims 1 to 19, characterized in that Ri is selected from t-butyl, methoxy, triethylsilyl, bromide, SO2CH3 or piperidinyl.
[0023]
23. Catalyst according to claim 22, characterized by the fact that R1 is selected from t-butyl or triethylsilyl.
[0024]
24. Catalyst according to any of the preceding claims, characterized by the fact that both occurrences of R1 are the same.
[0025]
25. Catalyst according to any of the preceding claims, characterized in that X is selected from OC (O) Rx, OSO2Rx, OS (O) Rx, OSO (Rx) 2, S (O) Rx, ORx, phosphinate , optionally substituted, halide, nitrate, hydroxyl, carbonate, amino, nitro, starch, and alkyl, heteroalkyl, (e.g., silyl), alicyclic, heteroalicyclic, aryl, or heteroaryl, preferably OC (O) Rx, OSO2Rx, OS (O) Rx, OSO (Rx) 2, S (O) Rx, ORx, halide, nitrate, hydroxyl, carbonate, amino, nitro, starch, alkyl (for example, branched alkyl), heteroalkyl, (for example, silyl), aryl or heteroaryl, more preferably OC (O) Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx.
[0026]
26. Catalyst according to any of the preceding claims, characterized in that X is selected from OC (O) Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx.
[0027]
27. Catalyst according to any of the preceding claims, characterized by the fact that X is selected from OC (O) Rx, ORx, halide, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx.
[0028]
28. Catalyst according to any of the preceding claims, characterized by the fact that X is OC (O) Rx.
[0029]
29. Catalyst according to any of the preceding claims, characterized by the fact that X is selected from OAc, O2CCF3 or O2C (CH2) 3Cy.
[0030]
30. Catalyst according to any of the preceding claims, characterized by the fact that both occurrences of X are the same.
[0031]
31. Catalyst according to any of the preceding claims, characterized by the fact that Rx is an optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or alkylaryl.
[0032]
32. Catalyst according to any one of the preceding claims, characterized by the fact that Rx is selected from hydrogen or an optionally substituted aliphatic, haloaliphatic, heteroaliphatic, heteroalicyclic, aryl, alkylaryl or heteroaryl, preferably an alkyl, alkenyl, heteroalkyl, optionally substituted aryl, heteroaryl, cycloalkyl or alkylaryl.
[0033]
33. Catalyst according to any one of the preceding claims, characterized in that Rx is selected from an optionally substituted alkyl, alkenyl, heteroalkyl or cycloalkyl.
[0034]
34. Catalyst according to any of the preceding claims, characterized in that Rx is selected from an optionally substituted alkyl, heteroalkyl or cycloalkyl.
[0035]
35. Catalyst according to any one of the preceding claims, characterized by the fact that Rx is an optionally substituted alkyl.
[0036]
36. Catalyst according to any of the preceding claims, characterized by the fact that both occurrences of Rx are the same.
[0037]
37. Catalyst according to any of the preceding claims, characterized by the fact that each occurrence of R2 and R5 is hydrogen.
[0038]
38. Catalyst according to claim 1, characterized by the fact that both occurrences of R1 are the same and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an alkyl, alkenyl , optionally substituted aryl, heteroaryl, alkoxy, aryloxy or alkylthio; R2 is hydrogen; both occurrences of R3 are the same and are selected from substituted alkylene and substituted arylene; E1 is C and E2 is O; E3, E4, E5 and E6 are NR4; R4 is hydrogen; each X is the same and is selected from OC (O) Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, each Rx is the same and is selected from alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; each G (when present) is the same and is selected from halide; Water; a heteroaryl optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile and one of M1 and M2 is Ni (II) or Ni (III) -X and the remaining M1 or M2 are selected from Mg (II ), Zn (II), Cr (III) -X, Co (II), Co (III) -X Mn (II), Ni (II), Ni (III) -X, Fe (II) and Fe (III ) -X, preferably the remaining M1 or M2 are selected from Mg (II), Zn (II), Ni (II) and Ni (III) -X.
[0039]
39. Catalyst according to claim 38, characterized by the fact that both occurrences of Mi and M2 are selected from Ni (II) and Ni (III) -X.
[0040]
40. Catalyst according to claim 38 or 39, characterized in that Ri is optionally substituted hydrogen, halide, silyl, silyl ether, sulfonyl or alkyl or alkoxy, preferably where G is absent.
[0041]
41. Catalyst according to claim 1, characterized by the fact that it is of the formula (Ib):
[0042]
42. Catalyst according to claim 41, characterized in that Ri is optionally substituted hydrogen, halide, silyl, silyl ether, sulfonyl and alkyl or alkoxy.
[0043]
43. Catalyst according to claim 41 or 42, characterized in that R3 is selected from optionally substituted propylenyl, 2,2-dimethylpropylenyl and phenyl or biphenyl, preferably R3 is a substituted propenyl, such as 2,2-di ( alkyl) propylenyl.
[0044]
44. Catalyst according to any of claims 41 to 43, characterized in that Mi and M2 are selected from Ni (II) and Ni (III) -X, preferably both M1 and M2 are Ni (II).
[0045]
45. Catalyst according to any one of claims 41 to 44, characterized in that X is OC (O) Rx, ORx, halide, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, preferably OC (O) Rx.
[0046]
46. Catalyst according to any one of claims 41 to 45, characterized in that Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl, preferably alkyl.
[0047]
47. Catalyst according to any one of claims 41 to 46, characterized by the fact that G is absent.
[0048]
48. Catalyst according to claim 1, characterized by the fact that it is of the formula:
[0049]
49. Catalyst, characterized by the fact that it is of formula (I)
[0050]
50. Process for the reaction of a. carbon dioxide with an epoxide; B. an epoxide and an anhydride and / or c. a lactide and / or a lactone, characterized by the fact that it is in the presence of a catalyst of formula (I):
[0051]
51. Process as defined in claim 50, characterized in that the epoxide is ethylene oxide, butylene oxide, propylene oxide or cyclohexene oxide, preferably propylene oxide.
[0052]
52. Process according to either of claims 50 or 51, characterized in that the process is carried out in a continuous flow reactor or a batch reactor.
[0053]
53. Process according to any of claims 50 to 52, characterized by the fact that the reaction is carried out in a continuous flow reactor.
[0054]
54. Product, characterized by the fact that it is of the process as defined in any of claims 50 to 53.
[0055]
55. Catalyst, product or process, characterized by the fact that it is substantially as defined here with reference to one or more of the examples.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112017001081B1|2020-12-29|CATALYST, PROCESS AND PRODUCT

---

RU2729046C2|2020-08-04|Method of producing polyols

---

JP6162120B2|2017-07-12|Method for synthesizing polycarbonate in the presence of bimetallic catalyst and chain transfer agent

---

KR20190118648A|2019-10-18|Process for preparing polycarbonate ether polyol

---

JP6557669B2|2019-08-07|catalyst

---

BR112020008010A2|2020-10-27|methods for cooling a polymerization process and for purifying a polymer product

---

KR20190123759A|2019-11-01|How to prepare a polyol

---

WO2020049319A9|2020-07-30|Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates

同族专利:

---

公开号 | 公开日

---

TWI675700B|2019-11-01|

---

CN106536047A|2017-03-22|

---

RU2696272C2|2019-08-01|

---

BR112017001086B1|2020-12-15|

---

TW201609258A|2016-03-16|

---

SG11201700233XA|2017-02-27|

---

MX2017000884A|2017-11-02|

---

WO2016012785A1|2016-01-28|

---

AU2015293702B2|2018-11-01|

---

JP6730273B2|2020-07-29|

---

AU2015293702A1|2017-02-02|

---

RU2017105139A3|2018-12-28|

---

US10030102B2|2018-07-24|

---

RU2706004C2|2019-11-13|

---

RU2017105138A3|2018-12-29|

---

US20190055352A1|2019-02-21|

---

RU2017105138A|2018-08-28|

---

TW201609259A|2016-03-16|

---

TWI660778B|2019-06-01|

---

CN106536048B|2020-05-05|

---

AU2015293703B2|2019-06-13|

---

RU2017105139A|2018-08-28|

---

KR20170035999A|2017-03-31|

---

JP2017524800A|2017-08-31|

---

BR112017001086A2|2017-11-21|

---

MX2017000880A|2017-08-18|

---

CN106536047B|2020-10-30|

---

EP3171975A1|2017-05-31|

---

JP2017524064A|2017-08-24|

---

US10556988B2|2020-02-11|

---

KR20170034417A|2017-03-28|

---

US10774180B2|2020-09-15|

---

SG11201700229VA|2017-02-27|

---

BR112017001081A2|2017-11-21|

---

CN106536048A|2017-03-22|

---

US20170204221A1|2017-07-20|

---

EP3180121A1|2017-06-21|

---

US20200140610A1|2020-05-07|

---

JP6728162B2|2020-07-22|

---

US20170210848A1|2017-07-27|

---

WO2016012786A1|2016-01-28|

---

AU2015293703A1|2017-02-02|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

JPS63280086A|1987-05-12|1988-11-17|Hiroyoshi Shirai|Dinuclear complex of salt thereof and langmuir-blodgett membrane|

---

JP2007238601A|2006-02-08|2007-09-20|Sumitomo Chemical Co Ltd|Polynuclear metal complex modified product and application thereof|

---

US20090062110A1|2006-02-08|2009-03-05|Sumitomo Chemical Company Limited|Metal complex and use thereof|

---

CN102290584A|2007-03-09|2011-12-21|独立行政法人产业技术综合研究所|Electrode catalyst for fuel cell|

---

GB0807607D0|2008-04-25|2008-06-04|Imp Innovations Ltd|Catalyst|

---

US9284406B2|2010-09-14|2016-03-15|Novomer, Inc.|Catalysts and methods for polymer synthesis|

---

EP2721032A4|2011-06-16|2014-11-05|Univ South Florida|Polyhedral cage-containing metalloporphyrin frameworks, methods of making, and methods of using|

---

GB201111928D0|2011-07-12|2011-08-24|Norner As|Process|

---

GB201115565D0|2011-09-08|2011-10-26|Imp Innovations Ltd|Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent|

---

SG11201700233XA|2014-07-22|2017-02-27|Econic Technologies Ltd|Catalysts|GB0807607D0|2008-04-25|2008-06-04|Imp Innovations Ltd|Catalyst|

---

GB201308978D0|2013-05-17|2013-07-03|Imp Innovations Ltd|Method for producing polymers and block copolymers|

---

SG11201700233XA|2014-07-22|2017-02-27|Econic Technologies Ltd|Catalysts|

---

GB201514506D0|2015-08-14|2015-09-30|Imp Innovations Ltd|Multi-block copolymers|

---

GB201515350D0|2015-08-28|2015-10-14|Econic Technologies Ltd|Method for preparing polyols|

---

US20190309126A1|2016-11-11|2019-10-10|Dow Global Technologies Llc|Semi-batch process for making polycarbonate polyols via copolymerization of carbon dioxide and an oxirane|

---

GB201703323D0|2017-03-01|2017-04-12|Econic Tech Ltd|Method for preparing polyols|

---

GB201703384D0|2017-03-02|2017-04-19|Econic Tech Ltd|Process for the production of Tetraaminobiphenol macrocyclic ligands; and novel Tetraaminobiphenol macrocyclic ligands|

---

WO2019204553A1|2018-04-18|2019-10-24|Saudi Aramco Technologies Company|End-group isomerization of poly polymers|

---

WO2020028606A1|2018-08-02|2020-02-06|Saudi Aramco Technologies Company|Sustainable polymer compositions and methods|

---

EP3856820A1|2018-09-24|2021-08-04|Saudi Aramco Technologies Company|Polycarbonate block copolymers and methods thereof|

---

EP3917988A1|2019-01-31|2021-12-08|Dow Global Technologies LLC|Purification process for polyether-carbonate polyols|

---

GB201906214D0|2019-05-02|2019-06-19|Econic Tech Ltd|A polyol block copolymer, compositions and processes therefor|

---

GB201906210D0|2019-05-02|2019-06-19|Econic Tech Limited|A polyol block copolymer, compositions and processes therefor|

---

GB202003003D0|2020-03-02|2020-04-15|Econic Tech Ltd|A polyol block copolymer|

---

GB202003002D0|2020-03-02|2020-04-15|Crane Ltd|Method of preparation of a polyol block copolymer|

---

WO2021262845A1|2020-06-24|2021-12-30|Saudi Aramco Technologies Company|Polyol compositions and methods|

法律状态:
2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/07/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

GB1412986.0|2014-07-22|

---

GB201412990A|GB201412990D0|2014-07-22|2014-07-22|Catalysts|

---

GB1412990.2|2014-07-22|

---

GB201412992A|GB201412992D0|2014-07-22|2014-07-22|Catalysts|

---

GB201412986A|GB201412986D0|2014-07-22|2014-07-22|Catalysts|

---

GB1412992.8|2014-07-22|

---

PCT/GB2015/052115|WO2016012786A1|2014-07-22|2015-07-22|Catalysts|

---